CN1914159A

CN1914159A - Method for producing linear pentenenitrile

Info

Publication number: CN1914159A
Application number: CNA2005800036939A
Authority: CN
Inventors: T·容坎普; R·巴默; M·巴尔奇; G·哈德莱恩; H·鲁肯; J·沙伊德尔; T·埃克特纳; P·朴法布; P·德克特; P·巴斯勒; W·塞格尔
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-01-29
Filing date: 2005-01-27
Publication date: 2007-02-14
Anticipated expiration: 2025-01-27
Also published as: CN100545147C; DE102004004671A1

Abstract

The invention relates to a method for producing 3-pentenenitrile, characterised by the following steps: (a) isomerisation of an educt stream containing 2-methyl-3-butenenitrile on at least one dissolved or dispersed isomerisation catalyst to form a stream (1), which contains the isomerisatio n catalyst(s), 2-methyl-3-butenenitrile, 3-pentenenitrile and (Z)-2-methyl-2-butenenitrile; (b) distillation of the stream (1) to obtain a stream (2) as the overhead product, which contains 2-methyl-3-butenenitrile, 3-pentenenitrile and (Z)-2-methyl-2-butenenitrile and a stream (3) as the bottom product, which contains the isomerisation catalyst(s); (c) distillation of the stream (2) to obtain a stream (4) as the overhead product, which is enriched with (Z)-2-methyl-2-butenenitrile in comparison to stream (2), (in relation to the sum of all pentenenitriles in stream (2)) and a stream (5) as the bottom product, which is enriched with 3-pentenenitrile and 2-methyl-3-butenenitril e in comparison to stream (2), (in relation to the sum of all pentenenitriles in stream (2); (d) distillation of stream (5) to obtain a stream (6) as the bottom product, which contains 3-pentenenitrile and a stream (7) as the head product, which contains 2-methyl-3-butenenitrile.

Description

The method for preparing linear pentenenitrile

The present invention relates to a kind of materials flow that comprises 2-methyl-3-crotononitrile by isomerization and prepare the method for 3 pentene nitrile.

In the preparation of the important intermediate-adiponitrile in nylon is produced, 1,3-butadiene and prussic acid are reacted in the presence of with the stable nickel of phosphorus part (0) obtain pentenenitrile.Except hydrocyanation principal product 3 pentene nitrile and 2-methyl-3-crotononitrile, also obtain level component many times.The example is 2-pentenenitrile, 2-methyl-2-butene nitrile, C ₉Nitrile and methyl cellosolve acetate glutaronitrile.Form 2-methyl-3-crotononitrile with significant quantity.Depend on catalyst system therefor, the 2-methyl-3-crotononitrile of formation and the mol ratio of 3 pentene nitrile can be up to 2: 1.

In second hydrocyanation, under the adding Lewis acid, make 3 pentene nitrile on identical nickel catalyzator, obtain adiponitrile subsequently with the prussic acid reaction.For this second hydrocyanation, necessary is that 3 pentene nitrile does not contain 2-methyl-3-crotononitrile substantially.2-methyl-the hydrocyanation of 3-crotononitrile will cause constituting the methyl cellosolve acetate glutaronitrile of undesirable by product.Therefore, in the economic means of preparation adiponitrile, must separate 3 pentene nitrile and 2-methyl-3-crotononitrile.

In order 2-methyl-3-crotononitrile to be used to prepare adiponitrile equally, proposed 2-methyl-3-crotononitrile is isomerizated into linear pentenenitrile, especially the method for 3 pentene nitrile.

For example, US 3,676, and 481 have described 2-methyl-3-crotononitrile is semicontinuous, isomerization in batches in the presence of Ni (0), phosphite ester ligand and some Lewis acid.After isomerization, the products therefrom mixture is steamed from catalyst system.The shortcoming of this method is the high residence time in isomerization process, the high thermal stress in isomerization and still-process subsequently on the thermo-sensitivity catalyzer.High thermal stress on the catalyzer causes undesirable degraded of catalyzer.

The priority date of being submitted to by BASF AG has been described in the presence of a kind of Ni of comprising (0) catalyzer and the lewis acidic system early but at still unpub German patent application DE 103 11 119.0 before the application's the priority date 2-methyl-3-crotononitrile has been isomerizated into the method for linear pentenenitrile.In this case, in isomerization process, from reaction mixture, distill the mixture that taking-up comprises 2-methyl-3-crotononitrile and linear pentenenitrile.The shortcoming of this method is that the product materials flow of taking out still contains the unconverted 2-methyl-3-crotononitrile of significant quantity.

To the currently known methods of all isomerization 2-methyl-3-crotononitriles commonly 2-methyl-3-crotononitrile because the position of thermodynamic(al)equilibrium and can not change into 3 pentene nitrile fully.For the economic performance of this method, unconverted 2-methyl-3-crotononitrile must infeed in the isomerization steps.Yet, in the isomerization of 2-methyl-3-crotononitrile, (Z)-2-methyl-2-butene nitrile obtains with by product and it will be assembled in recycle stream under the situation of recirculation 2-methyl-3-crotononitrile, because removing from the isomerization product materials flow in the process of 3 pentene nitrile by distillation, it will steam with 2-methyl-3-crotononitrile owing to closely similar vapour pressure.

US3,865,865 described from the mixture of 2-methyl-3-crotononitrile remove 2-methyl-2-butene nitrile.This is removed by using the aqueous solution of being made up of inferior sulfate radical and sulfurous acid hydrogen radical ion to handle mixture of nitriles and is undertaken.This has formed the bisulfite adduct of the 2-methyl-2-butene nitrile of transferring to water.It is 50% of former content that the gained organic phase is removed to 2-methyl-2-butene nitrile.US3,865,865 method is required great effort, because require being separated of organic phase and water.In addition, this separation only can be incorporated in total method of preparation adiponitrile difficultly.The additional drawback of this method is that the gained organic phase at first must be removed fully and anhydrates before the hydrocyanation reaction that is further used for using nickel (0) catalyzer have phosphorus (III) part, because irreversibly hydrolysis and therefore inactivation of phosphorus (III) part otherwise.Another shortcoming of this method is in order to re-use the conjugation nitrile, gained bisulfite adduct such as US3,865,865 described only under violent condition only with moderate productive rate disassociation.

Therefore, the purpose of this invention is to provide and a kind ofly prepare the method for 3 pentene nitrile by isomerization 2-methyl-3-crotononitrile, wherein be used for isomerized catalyzer and can plain mode remove and recirculation, and can from 2-methyl-3-crotononitrile, remove (Z)-2-methyl-2-butene nitrile and recirculation is poor contains the 2-methyl-3-crotononitrile of (Z)-2-methyl-2-butene nitrile from reaction mixture.This method is should be preferably simple and economical and can be incorporated in total method of preparation adiponitrile.

This purpose realizes by a kind of method for preparing 3 pentene nitrile according to the present invention.

Embodiment I

In an embodiment I, the method is characterized in that following process steps:

(a) isomerization comprises the educt flow of 2-methyl-3-crotononitrile at least a dissolving or dispersive isomerization catalyst, obtain comprising the materials flow 1 of this at least a isomerization catalyst, 2-methyl-3-crotononitrile, 3 pentene nitrile and (Z)-2-methyl-2-butene nitrile

(b) distillation materials flow 1 obtains comprising the materials flow 2 of 2-methyl-3-crotononitrile, 3 pentene nitrile and (Z)-2-methyl-2-butene nitrile and obtains comprising the materials flow 3 of this at least a isomerization catalyst with bottoms with top product,

(c) distillation materials flow 2, obtaining comparing with materials flow 2 summation based on all pentenenitriles in the materials flow 2 with top product is rich in the materials flow 4 of (Z)-2-methyl-2-butene nitrile and obtains comparing with materials flow 2 materials flow 5 of being rich in 3 pentene nitrile and 2-methyl-3-crotononitrile based on the summation of all pentenenitriles in the materials flow 2 with bottoms

(d) distillation materials flow 5, the materials flow 7 that obtains comprising the materials flow 6 of 3 pentene nitrile and obtain comprising 2-methyl-3-crotononitrile with top product with bottoms.

Educt flow

In processing step (a), the isomerization that comprises the educt flow of 2-methyl-3-crotononitrile is carried out at least a isomerization catalyst.

In the particular embodiment of the inventive method, educt flow can obtain by following process steps:

(e) use prussic acid hydrocyanation 1,3-butadiene at least a hydrocyanation catalyst, obtain comprising the materials flow 8 of this at least a hydrocyanation catalyst, 3 pentene nitrile, 2-methyl-3-crotononitrile, 1,3-butadiene and residual prussic acid,

(f) with materials flow 8 distillation once or more than once, obtain comprising the materials flow 9 of 1,3-butadiene, comprise the materials flow 10 of this at least a hydrocyanation catalyst and comprise the materials flow 11 of 3 pentene nitrile and 2-methyl-3-crotononitrile,

(g) distillation materials flow 11, the materials flow 13 that obtains comprising the materials flow 12 of 3 pentene nitrile and obtain comprising 2-methyl-3-crotononitrile with top product with bottoms.

In processing step (e), educt flow is by at first using prussic acid hydrocyanation 1 at least a hydrocyanation catalyst, 3-divinyl and obtain comprising the materials flow 8 of this at least a hydrocyanation catalyst, 3 pentene nitrile, 2-methyl-3-crotononitrile and unconverted 1,3-butadiene and prepare.

Used hydrocyanation catalyst is preferably with stable homogeneous phase nickel (0) catalyzer of phosphorus part.

The phosphorus part of nickel (0) title complex and free phosphorus part are preferably selected from monodentate-or bidentate phosphine, phosphorous acid ester, phosphinate (phosphinite) and phosphinate.

These phosphorus parts preferably have formula I:

P(X ¹R ¹)(X ²R ²)(X ³R ³) (I)。

In the context of the invention, Compound I is the mixture of single following formula compound or different following formula compound.

According to the present invention, X ¹, X ², X ³Be oxygen or singly-bound independently of one another.When all radicals X ¹, X ²And X ³During for singly-bound, Compound I is formula P (R ¹R ²R ³) phosphine, R wherein ¹, R ²And R ³Definition such as specification sheets defined.

Work as radicals X ¹, X ²And X ³In two be singly-bound and one during for oxygen, Compound I is formula P (OR ¹) (R ²) (R ³) or P (R ¹) (OR ²) (R ³) or P (R ¹) (R ²) (OR ³) phosphinate, R wherein ¹, R ²And R ³Be defined as follows defined.

Work as radicals X ¹, X ²And X ³In one of be singly-bound and two during for oxygen, Compound I is formula P (OR ¹) (OR ²) (R ³) or P (R ¹) (OR ²) (OR ³) or P (OR ¹) (R ²) (OR ³) phosphinate, R wherein ¹, R ²And R ³Definition such as specification sheets defined.

In preferred embodiments, all radicals X ¹, X ²And X ³Should be oxygen, thereby make Compound I advantageously be formula P (OR ¹) (OR ²) (OR ³) phosphorous acid ester, R wherein ¹, R ²And R ³Be defined as follows defined.

According to the present invention, R ¹, R ², R ³Be identical or different organic group independently of one another.R ¹, R ²And R ³Be the alkyl that preferably has 1-10 carbon atom such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl independently of one another, aryl such as phenyl, o-tolyl, a tolyl, p-methylphenyl, 1-naphthyl, 2-naphthyl, or the alkyl that preferably has a 1-20 carbon atom is as 1,1 '-xenol, 1,1 '-dinaphthol.Radicals R ¹, R ²And R ³Can Direct Bonding together, promptly not merely via central phosphorus atom.Preferred group R ¹, R ²And R ³Direct Bonding is not together.

In preferred embodiments, R ¹, R ²And R ³For being selected from the group of phenyl, o-tolyl, a tolyl and p-methylphenyl.In particularly preferred embodiments, radicals R ¹, R ²And R ³In maximum two should be phenyl.

In another preferred embodiment, radicals R ¹, R ²And R ³In maximum two should be o-tolyl.

Operable particularly preferred Compound I is those of formula Ia:

(o-tolyl-O-) _w(tolyl-O-) _x(p-methylphenyl-O-) _y(phenyl-O-) _zP (Ia)

Respectively do for oneself natural number and satisfy following condition: w+x+y+z=3 and w, z≤2 of w, x, y and z wherein.

Such Compound I a for example is the ((phenyl-O-) of p-methylphenyl-O-) ₂P, (tolyl-and O-) (phenyl-O-) ₂P, (o-tolyl-and O-) (phenyl-O-) ₂P, (p-methylphenyl-O-) ₂(P of phenyl-O-), (tolyl-O-) ₂(P of phenyl-O-), (o-tolyl-O-) ₂(P of phenyl-O-), (tolyl-O-) (p-methylphenyl-O-) (P of phenyl-O-), (o-tolyl-O-) (p-methylphenyl-O-) (P of phenyl-O-), (o-tolyl-O-) (tolyl-O-) (P of phenyl-O-), (p-methylphenyl-O-) ₃P, (tolyl-and O-) (p-methylphenyl-O-) ₂P, (o-tolyl-and O-) (p-methylphenyl-O-) ₂P, (tolyl-O-) ₂(P of p-methylphenyl-O-), (o-tolyl-O-) ₂(P of p-methylphenyl-O-), (o-tolyl-O-) (tolyl-O-) (P of p-methylphenyl-O-), (tolyl-O-) ₃P, (o-tolyl-and O-) (tolyl-O-) ₂P, (o-tolyl-O-) ₂(the mixture of the P of a tolyl-O-) or this compounds.

Comprise (tolyl-O-) ₃P, (tolyl-O-) ₂(P of p-methylphenyl-O-), (tolyl-and O-) (p-methylphenyl-O-) ₂P and (p-methylphenyl-O-) ₃The mixture of P for example can be by making especially comprising the mixture of meta-cresol and p-cresol and phosphorus trihalide such as phosphorus trichloride reaction with 2: 1 mol ratio and obtaining of obtaining in the distillation aftertreatment of crude oil.

In another same embodiment preferred, the phosphorus part is the phosphorous acid ester that is specified in the formula Ib among the DE-A 199 53 058:

P(O-R ¹) _x(O-R ²) _y(O-R ³) _z(O-R ⁴) _p (Ib)

Wherein

R ¹: have C at the ortho position that phosphorus atom is connected in the Sauerstoffatom on the aromatic systems ₁-C ₁₈Alkyl substituent or the aromatic group that has aromatic substituent or have fused aromatic systems at the ortho position that phosphorus atom is connected in the Sauerstoffatom on the aromatic systems at the ortho position that phosphorus atom is connected in the Sauerstoffatom on the aromatic systems,

R ²: phosphorus atom is connected in Sauerstoffatom on the aromatic systems between the position have C ₁-C ₁₈Alkyl substituent or phosphorus atom is connected in Sauerstoffatom on the aromatic systems between the position have aromatic substituent or phosphorus atom is being connected in Sauerstoffatom on the aromatic systems between the aromatic group of position with fused aromatic systems, this aromatic group has hydrogen atom at the ortho position that phosphorus atom is connected in the Sauerstoffatom on the aromatic systems

R ³: have C in the contraposition that phosphorus atom is connected in the Sauerstoffatom on the aromatic systems ₁-C ₁₈Alkyl substituent or have the aromatic group of aromatic substituent in the contraposition that phosphorus atom is connected in the Sauerstoffatom on the aromatic systems, this aromatic group has hydrogen atom at the ortho position that phosphorus atom is connected in the Sauerstoffatom on the aromatic systems,

R ⁴: have R in the ortho position that phosphorus atom is connected in the Sauerstoffatom on the aromatic systems, a position and contraposition ¹, R ²And R ³Defined those substituent aromatic groups in addition, this aromatic group has hydrogen atom at the ortho position that phosphorus atom is connected in the Sauerstoffatom on the aromatic systems,

X:1 or 2,

Y, z, p are 0,1 or 2 independently of one another, and condition is x+y+z+p=3.

The phosphorous acid ester of preferred formula Ib can find in DE-A 199 53 058.Radicals R ¹Can advantageously be o-tolyl, adjacent ethylphenyl, adjacent n-propyl phenyl, o-isopropyl phenyl, adjacent n-butylphenyl, o-sec-butyl phenyl, o-tert-butyl phenyl, (adjacent phenyl) phenyl or 1-naphthyl.

Preferred radicals R ²Be a tolyl, an ethylphenyl, a n-propyl phenyl, an isopropyl phenyl, a n-butylphenyl, a secondary butyl phenenyl, a tert-butyl-phenyl, (phenyl) phenyl or 2-naphthyl.

Favourable radicals R ³For p-methylphenyl, to ethylphenyl, to n-propylbenzene base, p-isopropyl phenyl, to n-butylphenyl, to secondary butyl phenenyl, to tert-butyl-phenyl or (to phenyl) phenyl.

Radicals R ⁴Be preferably phenyl.P is preferably 0.There are following possibility in symbol x, y, z and p in the compounds ib:

x	y	z	p
x	y	z	p		1	0	0	2
1	0	1	1		1	0	0	2
1	0	1	1	1	1	0	1
2	0	0	1	1	1	0	1
2	0	0	1	1	0	2	0
1	1	1	0	1	0	2	0
1	1	1	0	1	2	0	0
2	0	1	0	1	2	0	0
2	0	1	0	2	1	0	0

The phosphorous acid ester of preferred formula Ib is that wherein p is 0, R ¹, R ²And R ³Be selected from o-isopropyl phenyl, a tolyl and p-methylphenyl and R independently of one another ⁴Be those of phenyl.

The phosphorous acid ester of particularly preferred formula Ib is R wherein ¹Be o-isopropyl phenyl, R ²Be a tolyl, R ³For p-methylphenyl and each symbol are as above shown those of defined; And R wherein ¹Be o-tolyl, R ²Be a tolyl, R ³For p-methylphenyl and each symbol as those of defined in the table; Additionally also has wherein R ¹Be 1-naphthyl, R ²Be a tolyl, R ³For p-methylphenyl and each symbol as those of defined in the table; R wherein ¹Be o-tolyl, R ²Be 2-naphthyl, R ³For p-methylphenyl and each symbol as those of defined in the table; And R wherein ¹Be o-isopropyl phenyl, R ²Be 2-naphthyl, R ³For p-methylphenyl and each symbol as those of defined in the table; The mixture that also has these phosphorous acid esters.

The phosphorous acid ester of formula Ib can obtain by the following method:

A) make phosphorus trihalide and be selected from R ¹OH, R ²OH, R ³OH and R ⁴Alcohol or its mixture reaction of OH obtain dihalo phosphorous acid monoesters,

B) make described dihalo phosphorous acid monoesters and be selected from R ¹OH, R ²OH, R ³OH and R ⁴OH alcohol or its mixture reaction, obtain single halo phosphorous acid diester and

C) make described single halo phosphorous acid diester and be selected from R ¹OH, R ²OH, R ³OH and R ⁴Alcohol or its mixture reaction of OH obtain the phosphorous acid ester of formula Ib.

This reaction can be carried out in three steps of separating.Equally, can be with two combinations in these three steps, promptly a) and b) combination or b) and c) combination.Perhaps can be with all step a), b) and c) combine.

Suitable parameters and be selected from R ¹OH, R ²OH, R ³OH and R ⁴The alcohol of OH or the amount of its mixture can easily be determined by several simple tentative experiments.

Useful phosphorus trihalide is all phosphorus trihalides in principle, and preferably wherein used halogen is Cl, Br, I, especially those of Cl and composition thereof.The mixture that can also use the phosphine that various identical or different halogens replace is as phosphorus trihalide.Preferred especially PCl ₃About the reaction conditions of the preparation of phosphorous acid ester Ib and other details of aftertreatment can find in DE-A 199 53 058.

The form of mixtures of all right different phosphorous acid ester Ib of phosphorous acid ester Ib is as part.Such mixture for example can obtain in the preparation of phosphorous acid ester Ib.

Yet preferred phosphorus part is polydentate ligand, especially bitooth ligand.Therefore used part preferably has formula II:

Wherein

X ¹¹, X ¹², X ¹³, X ²¹, X ²², X ²³Be oxygen or singly-bound independently of one another,

R ¹¹, R ¹²Be independently of one another identical or different separately or the organic group of bridge joint,

R ²¹, R ²²Be independently of one another identical or different separately or the organic group of bridge joint,

Y is the bridge joint group.

In the context of the invention, Compound I I is the simplification compound of following formula or the mixture of different following formula compound.

In preferred embodiments, X ¹¹, X ¹², X ¹³, X ²¹, X ²², X ²³The oxygen of can respectively doing for oneself.At this moment, bridge joint group Y is bonded on the phosphorous acid ester group.

In another preferred embodiment, X ¹¹And X ¹²Oxygen and X can respectively do for oneself ¹³Be singly-bound, perhaps X ¹¹And X ¹³Oxygen and X respectively do for oneself ¹²Be singly-bound, thereby make by X ¹¹, X ¹²And X ¹³The phosphorus atom that surrounds is the central atom of phosphinate.At this moment, X ²¹, X ²²And X ²³Oxygen, perhaps X can respectively do for oneself ²¹And X ²²Oxygen and X can respectively do for oneself ²³Be singly-bound, perhaps X ²¹And X ²³Oxygen and X can respectively do for oneself ²²Be singly-bound, perhaps X ²³Can be oxygen and X ²¹And X ²²Singly-bound, perhaps X respectively do for oneself ²¹Can be oxygen and X ²²And X ²³Singly-bound, perhaps X respectively do for oneself ²¹, X ²²And X ²³The singly-bound of can respectively doing for oneself, thus make by X ²¹, X ²²And X ²³The phosphorus atom that surrounds can be phosphorous acid ester, phosphinate, phosphinate or phosphine, the central atom of preferred phosphinate.

In another preferred embodiment, X ¹³Can be oxygen and X ¹¹And X ¹²Singly-bound, perhaps X respectively do for oneself ¹¹Can be oxygen and X ¹²And X ¹³The singly-bound of respectively doing for oneself, thus make by X ¹¹, X ^L2And X ^L3The phosphorus atom that surrounds can be the central atom of phosphinate.At this moment, X ²¹, X ²²And X ²³Oxygen, perhaps X can respectively do for oneself ²³Can be oxygen and X ²¹And X ²²Singly-bound, perhaps X respectively do for oneself ²¹Can be oxygen and X ²²And X ²³Singly-bound, perhaps X respectively do for oneself ²¹, X ²²And X ²³The singly-bound of can respectively doing for oneself, thus make by X ²¹, X ²²And X ²³The phosphorus atom that surrounds can be phosphorous acid ester, phosphinate or phosphine, the central atom of preferred phosphinate.

In another preferred embodiment, X ¹¹, X ¹²And X ¹³The singly-bound of can respectively doing for oneself, thus make by X ¹¹, X ¹²And X ¹³The phosphorus atom that surrounds can be the central atom of phosphine.At this moment, X ²¹, X ²²And X ²³Oxygen, perhaps X can respectively do for oneself ²¹, X ²²And X ²³The singly-bound of can respectively doing for oneself, thus make by X ²¹, X ²²And X ²³The phosphorus atom that surrounds can be phosphorous acid ester or phosphine, the central atom of preferred phosphine.

Bridge joint group Y is preferably for example by C ₁-C ₄Alkyl, halogen such as fluorine, chlorine, bromine, haloalkyl such as trifluoromethyl, the aryl that aryl such as phenyl replace perhaps is unsubstituted aryl, preferably has group, the especially pyrocatechol of 6-20 carbon atom, two (phenol) or two (naphthols) in aromatic systems.

Radicals R ¹¹And R ¹²Can be identical or different organic group independently of one another.Favourable radicals R ¹¹And R ¹²Be aryl, preferably have those of 6-10 carbon atom, they can not be substituted or especially by C ₁-C ₄Alkyl, halogen such as fluorine, chlorine, bromine, haloalkyl such as trifluoromethyl, aryl such as phenyl or unsubstituted aryl list-or polysubstituted.

Radicals R ²¹And R ²²Can be identical or different organic group independently of one another.Favourable radicals R ²¹And R ²²Be aryl, preferably have those of 6-10 carbon atom, they can not be substituted or especially by C ₁-C ₄Alkyl, halogen such as fluorine, chlorine, bromine, haloalkyl such as trifluoromethyl, aryl such as phenyl or unsubstituted aryl list-or polysubstituted.

Radicals R ¹¹And R ¹²Can separate separately or bridge joint.Radicals R ²¹And R ²²Also can separate separately or bridge joint.Radicals R ¹¹, R ¹², R ²¹And R ²²Can separate separately in this way, two can bridge joint and two separately, perhaps all 4 can bridge joint.

In particularly preferred embodiments, useful compound is US 5,723, those of formula I, II, III, IV and the V of defined in 641.In particularly preferred embodiments, useful compound is US 5,512, those of formula I, II, III, IV, V, VI and the VII of defined in 696, the compound that uses among the embodiment 1-31 especially therein.In particularly preferred embodiments, useful compound is US 5, those of the formula I of defined, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV in 821,378, the compound that uses among the embodiment 1-73 especially therein.

In particularly preferred embodiments, useful compound is US 5,512, those of formula I, II, III, IV, V and the VI of defined in 695, the compound that uses among the embodiment 1-6 especially therein.In particularly preferred embodiments, useful compound is US 5, those of the formula I of defined, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII and XIV in 981,772, the compound that uses among the embodiment 1-66 especially therein.

In particularly preferred embodiments, useful compound is US 6,127, the compound that uses among those and the embodiment 1-29 therein of defined in 567.In particularly preferred embodiments, useful compound is US 6,020, those of formula I, II, III, IV, V, VI, VII, VIII, IX and the X of defined in 516, the compound that uses among the embodiment 1-33 especially therein.In particularly preferred embodiments, useful compound is US 5,959, the compound that uses among those and the embodiment 1-13 therein of defined in 135.

In particularly preferred embodiments, useful compound is US 5,847, those of formula I, the II of defined and III in 191.In particularly preferred embodiments, useful compound is US 5, those of defined in 523,453 are especially therein with the compounds of

formula

1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20 and 21 explanations.In particularly preferred embodiments, useful compound is those of defined among the WO 01/14392, and is preferred therein with the compound of formula V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XXI, XXII, XXIII explanation.

In particularly preferred embodiments, useful compound is those of defined among the WO 98/27054.In particularly preferred embodiments, useful compound is those of defined among the WO 99/13983.In particularly preferred embodiments, useful compound is those of defined among the WO 99/64155.

In particularly preferred embodiments, useful compound is those of defined among the German patent application DE 100 38037.In particularly preferred embodiments, useful compound is those of defined among the German patent application DE 100 460 25.In particularly preferred embodiments, useful compound is those of defined among the German patent application DE 101 502 85.

In particularly preferred embodiments, useful compound is those of defined among the German patent application DE 101 50286.In particularly preferred embodiments, useful compound is those of defined among the German patent application DE 102 071 65.In further particularly preferred embodiment of the present invention, useful phosphorus chelating ligand is those of defined among US 2003/0100442 A1.

In further particularly preferred embodiment of the present invention, useful phosphorus chelating ligand is those of defined among the German patent application reference number DE 103 50 999.2 on October 30th, 2003, and this application has priority date early but announces as yet at the application's priority date.

Described Compound I, Ia, Ib and II and preparation thereof itself are known.Used phosphorus part can also be at least two kinds a mixture among inclusion compound I, Ia, Ib and the II.

In the particularly preferred embodiment of the inventive method, the phosphorus part of nickel (0) title complex and/or free phosphorus part are selected from the phosphorous acid ester of tricresyl phosphite, diphenylphosphino chelating ligand and formula Ib:

P(O-R ¹) _x(O-R ²) _y(O-R ³) _z(O-R ⁴) _p (Ib)

Its R ¹, R ²And R ³Be selected from o-isopropyl phenyl, a tolyl and p-methylphenyl independently of one another, R ⁴Be phenyl; X be 1 or 2 and y, z, p be 0,1 or 2 independently of one another, condition is x+y+z+p=3; And composition thereof.

Processing step (e) can carry out in the known suitable equipment of any those skilled in the art.Therefore useful conversion unit is conventional equipment, for example as Kirk-Othmer, and Encyclopedia ofChemical Technology, the 4th edition, the 20th volume, John Wiley ﹠amp; Sons, New York1996, the 1040-1055 page or leaf is described, and as stirred-tank reactor, annular-pipe reactor, gas circulation reactor, bubble-column reactor or tubular reactor, suitable in each case voice band has the device of removing reaction heat.This reaction can be a plurality of, as carrying out in 2 or 3 equipment.

In the preferred embodiment of the inventive method, have been found that favourable reactor be have the back mixing feature those or have the set of reactors of back mixing feature.Have been found that particularly advantageous is the set of reactors with back mixing feature with cross-flow mode operation of being metered into respect to prussic acid.

Hydrocyanation can carry out in the solvent existence or not.When using solvent, this solvent should be inertia for liquid and to unsaturated compound and described at least a catalyzer under given temperature of reaction and given reaction pressure.Usually, solvent for use is hydrocarbon such as benzene or dimethylbenzene, perhaps nitrile such as acetonitrile or benzonitrile.Yet, preferably part is used as solvent.

This reaction can batch mode, carry out continuously or with semi-batch operation.

Hydrocyanation reaction can be by carrying out in all reactant adding equipment.Yet, preferably use catalyzer, unsaturated organic compound and suitable, solvent loads this equipment.The gas phase prussic acid preferably swims on the reaction mixture surface or passes through reaction mixture.To another reinforced program of this equipment is that solvent loads this equipment, and unsaturated compound slowly is metered in the reaction mixture with catalyzer, prussic acid and suitable.In addition, reactant can also be introduced in the reactor and reaction mixture transferred to prussic acid is added temperature of reaction in this mixture with liquid form.In addition, prussic acid can also add before being heated to temperature of reaction.This is reflected under the conventional hydrocyanation condition in temperature, atmosphere, reaction times etc. and carries out.

Preferably in the processing step of one or more stirrings, carry out hydrocyanation continuously.When using a plurality of processing step, preferably these processing steps are connected in series.At this moment, directly product is transferred in next processing step by a processing step.Prussic acid directly can be added in first processing step or between each processing step.

When carrying out the inventive method with semi-batch operation, preferably at first in reactor, add catalyst component and 1,3-butadiene, in the reaction times, prussic acid is metered in the reaction mixture simultaneously.

This reaction is more preferably carried out under the absolute pressure of 0.5-50MPa, especially 1-5MPa preferably at 0.1-500MPa.This reaction is more preferably carried out under the temperature of 313-423K, especially 333-393K preferably at 273-473K.The favourable mean residence time that has been found that the liquid reactor phase each reactor in each case is 0.001-100 hour, preferred 0.05-20 hour, and more preferably 0.1-5 hour.

In one embodiment, this reaction can be in the presence of gas phase be carried out in liquid phase in the presence of mutually at solid suspension with suitable.Raw material prussic acid and 1,3-butadiene in each case can liquid or gas form be metered into.

In another embodiment, this reaction can be carried out in liquid phase, and the pressure in the reactor should make all raw materials such as 1,3-butadiene, prussic acid and at least a catalyzer be metered into liquid form and be present in the reaction mixture with liquid phase at this moment.Solid suspension may reside in the reaction mixture mutually and can also be metered into at least a catalyzer, for example is made up of the degraded product of the catalyst system that especially comprises nickel (II) compound.

In processing step (e), obtain comprising the materials flow 8 of 3 pentene nitrile, 2-methyl-3-crotononitrile, at least a catalyzer and unconverted 1,3-butadiene.

The materials flow 8 that will comprise 3 pentene nitrile, 2-methyl-3-crotononitrile, at least a catalyzer and unconverted 1,3-butadiene is then transferred in the distillation plant in processing step (f).In this distillation plant, with materials flow 8 distillation once or more than once, obtain comprising the materials flow 9 of 1,3-butadiene, comprise the materials flow 10 of at least a hydrocyanation catalyst and comprise the materials flow 11 of 3 pentene nitrile and 2-methyl-3-crotononitrile.

The distillation of processing step (f) can two sections be carried out, and carries out with processing step (b) with (c) as described in DE-A-102 004 004 720.The distillation of processing step (f) can also be carried out with processing step (b) with (c) according to DE-A-102 004 004 729.

The distillation of processing step (f) can be carried out in the known any suitable equipment of those skilled in the art.Suitable distillation plant for example is described in Kirk-Othmer, Encyclopedia of ChemicalTechnology, the 4th edition, the 8th volume, John Wiley ﹠amp; Sons, New York, in 1996, the 334-348 pages or leaves, as sieve-tray tower, bubble-cap tray column, have the tower of structured packing or random packing, the latter also can be used as the operation of partition tower.These distillation unit are equipped with the device that is suitable for evaporating separately, as falling-film evaporator, thin-film evaporator, heterogeneous screw and vertical tube evaporator, natural-circulation evaporator or pump circulation flasher and the device of condensing steam materials flow also is housed.Each distillation is can each leisure a plurality of, as carrying out in 2 or 3 equipment, advantageously carries out in single equipment in each case.

Evaporate under the situation of incoming flow in part, distillation can additionally be carried out in one section separately.

Pressure in the processing step (f) is preferably the 0.001-10 crust, more preferably 0.010-1 crust, especially 0.02-0.5 crust.Distillation more preferably 50-150 ℃, is especially carried out under 60-120 ℃ the distillation plant bottom temp preferably at 30-200 ℃.Distillation, is especially carried out under 5-45 ℃ the distillation plant top condensing temperature more preferably-15 to 60 ℃ preferably at-15 to 150 ℃.In the particularly preferred embodiment of the inventive method, all keep the said temperature scope in the two at the bottom of distillation plant and top.

Subsequently materials flow 11 is further being distilled in the processing step (g).This distillation can be carried out in the known any suitable equipment of those skilled in the art.Suitable distillation plant for example is described in Kirk-Othmer, Encyclopedia of Chemical Technology, the 4th edition, the 8th volume, John Wiley ﹠amp; Sons, New York, in 1996, the 334-348 pages or leaves, as sieve-tray tower, bubble-cap tray column, have the tower of structured packing or random packing, the latter also can be used as the operation of partition tower.These distillation unit are equipped with the device that is suitable for evaporating separately, as falling-film evaporator, thin-film evaporator, heterogeneous screw and vertical tube evaporator, natural-circulation evaporator or pump circulation flasher and the device of condensing steam materials flow also is housed.This distillation can as carrying out in 2 or 3 equipment, advantageously be carried out in single equipment a plurality of.Evaporate under the situation of incoming flow in part, distillation can additionally be carried out in one section separately.

Pressure in the processing step (g) is preferably the 0.001-100 crust, more preferably 0.01-20 crust, especially 0.05-2 crust.Distillation more preferably 50-200 ℃, is especially carried out under 60-180 ℃ the distillation plant bottom temp preferably at 30-250 ℃.Distillation more preferably 0-180 ℃, is especially carried out under 15-160 ℃ the distillation plant top condensing temperature preferably at-50 to 250 ℃.In the particularly preferred embodiment of the inventive method, all keep the said temperature scope in the two at the bottom of distillation plant and top.

In processing step (g), obtain comprising 1 with bottoms, the materials flow 12 of 3 pentene nitrile also obtains comprising the materials flow 13 of 2-methyl-3-crotononitrile with top product.Preferably materials flow 13 is prepared the educt flow in the method for 3 pentene nitrile as the present invention.

In another preferred embodiment of the inventive method, directly the materials flow 8 that will obtain in processing step (e) is transferred in the processing step (g).Substantially comprised the materials flow of 3 pentene nitrile and at least a hydrocyanation catalyst via the bottom at this processing step (g).In addition, comprised the materials flow of 2-methyl-3-crotononitrile and 1,3-butadiene substantially at the top.This materials flow of being rich in 2-methyl-3-crotononitrile and 1,3-butadiene can be used as educt flow equally in the present invention prepares the method for 3 pentene nitrile.If this educt flow is used for the inventive method, then preferred the 2-methyl-content of 3-crotononitrile in this materials flow is 10-90 weight %, and more preferably 20-85 weight %, especially 30-80 weight % are in each case based on this materials flow.

Perhaps, can also in processing step (f), only remove 1,3-butadiene in the materials flow 8 that in processing step (e), obtains.Substantially the materials flow 11a that is comprised 3 pentene nitrile, 2-methyl-3-crotononitrile and at least a hydrocyanation catalyst via the bottom of processing step (f).In this case, this materials flow 11a subsequently further in processing step (g) aftertreatment remove 2-methyl-3-crotononitrile on the other hand on the one hand to remove 3 pentene nitrile and at least a hydrocyanation catalyst.Materials flow 13a at the distillation top from processing step (g) comprises 2-methyl-3-crotononitrile substantially.This materials flow 13a can be used as educt flow equally in the present invention prepares the method for 3 pentene nitrile.

In another embodiment, in processing step (f), only remove from the materials flow 8 of processing step (e) 1, the 3-divinyl is also transferred to this materials flow 8 in the processing step (g), obtains comprising the materials flow 12 of 3 pentene nitrile and hydrocyanation catalyst in this step in the bottom.

In another embodiment of the present invention, used educt flow is from the hydrocyanation of processing step (e) and the aftertreatment in processing step (f) subsequently, and suitable in this case words are only removed 1,3-butadiene in processing step (f).The materials flow 11b that will obtain thus then transfers in the processing step (a) of the inventive method.Preferably will be present in hydrocyanation catalyst among this materials flow 11b then as at least a isomerization catalyst in the inventive method processing step (a).Can additionally add suitable Lewis acid, for example as described in the DE-A-102 004 004 696.

In another embodiment of the present invention, used educt flow can be corresponding to the materials flow 11 of processing step (f) in the processing step of the present invention (a), thereby saves the separation of materials flow 11 in processing step (g).

In another embodiment of the inventive method, used educt flow is the materials flow 8 from processing step (e).Therefore in this case, save processing step (f) and (g) in the preparation of the educt flow that is used for the inventive method.

Processing step (a)

In processing step (a), isomerization comprises the educt flow of 2-methyl-3-crotononitrile at least a isomerization catalyst.Obtain comprising the materials flow 1 of isomerization catalyst, unconverted 2-methyl-3-crotononitrile, 3 pentene nitrile and (Z)-2-methyl-2-butene nitrile thus.

According to the present invention, isomerization is carried out comprising in the presence of the system of following component:

A) nickel (0),

B) contain phosphorous compound and suitable as what part cooperated with nickel (0),

C) Lewis acid.

The catalyst system of nickeliferous (0) can be by known method preparation itself.

The part of isomerization catalyst can be and be used for the identical phosphorus part of hydrocyanation catalyst in processing step (e).Therefore, hydrocyanation catalyst can be identical with isomerization catalyst.Yet, needn't be necessarily identical for the selection of the part of the reaction among processing step (a) and (e).

In addition, the words that this system is suitable comprise Lewis acid.

In the context of the invention, Lewis acid refers to single Lewis acid or multiple, as 2,3 or 4 kind of lewis acidic mixture.

Useful Lewis acid is inorganic or organometallic compound, and wherein positively charged ion is selected from scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminium, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium and tin.Example comprises ZnBr ₂, ZnI ₂, ZnCl ₂, ZnSO ₄, CuCl ₂, CuCl, Cu (O ₃SCF ₃) ₂, CoCl ₂, CoI ₂, FeI ₂, FeCl ₃, FeCl ₂, FeCl ₂(THF) ₂, TiCl ₄(THF) ₂, TiCl ₄, TiCl ₃, ClTi (O-sec.-propyl) ₃, MnCl ₂, ScCl ₃, AlCl ₃, (C ₈H ₁₇) AlCl ₂, (C ₈H ₁₇) ₂AlCl, (i-C ₄H ₉) ₂AlCl, (C ₆H ₅) ₂AlCl, (C ₆H ₅) AlCl ₂, ReCl ₅, ZrCl ₄, NbCl ₅, VCl ₃, CrCl ₂, MoCl ₅, YCl ₃, CdCl ₂, LaCl ₃, Er (O ₃SCF ₃) ₃, Yb (O ₂CCF ₃) ₃, SmCl ₃, B (C ₆H ₅) ₃, TaCl ₅, for example as US 6,127,567, US 6,171,996 and US 6,380,421 is described.Also usefully metal-salt such as ZnCl ₂, CoI ₂And SnCl ₂And organometallic compound such as RAlCl ₂, R ₂AlCl, RSnO ₃SCF ₃And R ₃B, wherein R is an alkyl or aryl, for example as US 3,496,217, US 3,496,218 and US 4,774,353 is described.According to US 3,773,809, used promotor can be the metal that is cationic form, be selected from zinc, cadmium, beryllium, aluminium, gallium, indium, thallium, titanium, zirconium, hafnium, erbium, germanium, tin, vanadium, niobium, scandium, chromium, molybdenum, tungsten, manganese, rhenium, palladium, thorium, iron and cobalt, preferred zinc, cadmium, titanium, tin, chromium, iron and cobalt, and the anionicsite of this compound can be selected from halogenide such as fluorochemical, muriate, bromide and iodide, negatively charged ion with lower fatty acid of 2-7 carbon atom, HPO ₃ ^2-, H ₃PO ^2-, CF ₃COO ^-, C ₇H ₁₅OSO ₂ ^-Or SO ₄ ^2-Other are by US 3,773, and 809 disclosed suitable promotor are hydroborate, organic hydroborate and formula R ₃B and B (OR) ₃Boric acid ester, wherein R is selected from hydrogen, has the aryl of 6-18 carbon atom, is had aryl that the alkyl of 1-7 carbon atom replaces and the aryl of the alkyl replacement with 1-7 carbon atom that replaced by cyano group, advantageously triphenyl-boron.In addition, as US 4,874,884 is described, can use lewis acidic Synergistic active combination, to increase the activity of catalyst system.Suitable promotor for example can be selected from CdCl ₂, FeCl ₂, ZnCl ₂, B (C ₆H ₅) ₃(C ₆H ₅) ₃SnX, wherein X=CF ₃SO ₃, CH ₃C ₆H ₄SO ₃Or (C ₆H ₅) ₃BCN, and the preferred proportion of promotor and nickel is about 1: 16 to about 50: 1.

In the context of the invention, the term Lewis acid also comprises US 3,496,217, US 3,496,218, US 4,774,353, US 4,874,884, US 6,127,567, US 6,171,996 and US 6,380, and the promotor described in 421.

At described particularly preferred Lewis acid metal-salt especially in those, more preferably metal halide such as fluorochemical, muriate, bromide, iodide, especially muriate, wherein preferred especially zinc chloride, iron(ic) chloride (II) and iron(ic) chloride (III).

Isomerization can be carried out in the presence of liquid diluent, and described thinner for example is:

-hydrocarbon such as hexane, heptane, octane, hexanaphthene, methylcyclohexane, benzene, naphthane,

-ether such as ether, tetrahydrofuran (THF), two  alkane, glycol dimethyl ether, phenylmethylether,

-ester such as ethyl acetate, methyl benzoate, or

-nitrile such as acetonitrile, benzonitrile, or

The mixture of-such thinner.

In particularly preferred embodiments, useful isomerization is carried out not existing under such liquid diluent.

In addition, have been found that the advantageously isomerization in processing step (a) in non-oxidizing atmosphere, for example under the protective gas atmosphere of forming by nitrogen or rare gas such as argon gas, carry out.

Processing step (a) can carry out in the known suitable equipment of any those skilled in the art.Useful conversion unit is a conventional equipment, for example as Kirk-Othmer, and Encyclopedia ofChemical Technology, the 4th edition, the 20th volume, John Wiley ﹠amp; Sons, New York, 1996, the 1040-1055 pages or leaves are described, as stirred-tank reactor, annular-pipe reactor, gas circulation reactor, bubble-column reactor or tubular reactor.This reaction can be a plurality of, as carrying out in 2 or 3 equipment.

In the preferred embodiment of the inventive method, isomerization is carried out in tubular reactor at interval.

In the further preferred embodiment of the inventive method, at least two reactors that are connected in series, carry out isomerization, first reactor had stirring tank feature and second reactor design substantially and became to have substantially the tubular type feature this moment.

In the particularly preferred embodiment of the inventive method, isomerization is carried out in reactor, and this reactor has the stirring tank combined feature corresponding to 2-20 stirring tank, an especially 3-10 stirring tank.

In an embodiment of the inventive method, this reaction can be carried out in a distillation plant, and isomerization reaction this moment is carried out at the bottom section of distillation plant at least.The known distillation plant of any those skilled in the art is suitable, for example as Kirk-Othmer, and Encyclopedia ofChemical Technology, the 4th edition, the 8th volume, John Wiley ﹠amp; Sons, New York 1996, the 334-348 pages or leaves are described, and as sieve-tray tower, bubble-plate column, have the tower of structured packing or random packing, the latter also can be used as the operation of partition tower.These distillation unit are equipped with the device that is suitable for evaporating separately, as falling-film evaporator, thin-film evaporator, heterogeneous screw and vertical tube evaporator, natural-circulation evaporator or pump circulation flasher and the device that is used for the condensing steam materials flow also is housed.The distillation of reacting simultaneously can as carrying out in 2 or 3 equipment, advantageously be carried out in individual equipment a plurality of.Evaporate under the situation of incoming flow in part, distillation can also be carried out in one section.

The processing step of the inventive method (a) preferably 0.1 millibar to 100 the crust, more preferably 1 millibar to 16 the crust, especially 10 millibars to 6 the crust absolute pressures under carry out.Temperature in the processing step (a) is preferably 25-250 ℃, and more preferably 30-180 ℃, especially 40-140 ℃.

The composition that depends on incoming flow can pass through the structure of temperature, catalyst concn, the residence time and reactor with regard to the mol ratio of 2-methyl-3-crotononitrile and linear pentenenitrile and the composition of therefore regulating the materials flow of taking out with regard to the transforming degree of used 2-methyl-3-crotononitrile in technical simple mode.In the preferred embodiment of the inventive method, by these measures transforming degree is adjusted to 10-99%, more preferably 30-95%, especially 60-90%.

Processing step (b)

In processing step (b), the materials flow 1 that distillation obtains in processing step (a).Obtain comprising the materials flow 2 of 2-methyl-3-crotononitrile, 3 pentene nitrile and (Z)-2-methyl-2-butene nitrile thus with top product.In addition, in processing step (b), obtain comprising the materials flow 3 of at least a isomerization catalyst with bottoms.

The processing step of the inventive method (b) can be undertaken by the known any suitable distillation plant of those skilled in the art.Suitable distillation plant for example is described in Kirk-Othmer, Encyclopedia of Chemical Technology, the 4th edition, the 8th volume, John Wiley ﹠amp; Sons, New York, in 1996, the 334-348 pages or leaves, as sieve-tray tower, bubble-cap tray column, have the tower of structured packing or random packing, the latter also can be used as the operation of partition tower.These distillation unit are equipped with the device that is suitable for evaporating separately, as falling-film evaporator, thin-film evaporator, heterogeneous screw and vertical tube evaporator, natural-circulation evaporator or pump circulation flasher and the device that is used for the condensing steam materials flow also is housed.Distillation can as carrying out in 2 or 3 equipment, advantageously be carried out in individual equipment a plurality of.Evaporate under the situation of incoming flow in part, distillation can also additionally be carried out in one section.

The processing step of the inventive method (b) preferably 0.1 millibar to 100 the crust, more preferably 1 millibar to 6 the crust, especially carry out under 10 millibars to 500 millibars the absolute pressure.Distillation is being preferably 25-250 ℃, more preferably 40-180 ℃, especially carries out under 60-140 ℃ the distillation plant bottom temp.Distillation is being preferably-15 to 200 ℃, more preferably 5-150 ℃, especially carries out under 10-100 ℃ the distillation plant head temperature.In the particularly preferred embodiment of the inventive method, all keep the said temperature scope in the two in the top of distillation plant and bottom.

In particularly preferred embodiment of the present invention, the distillation of the materials flow of carrying out in processing step (b) 1 existing isomerization catalyst in this mixture is not so good as in processing step (a) active, or carries out under inactive pressure and temperature condition.

In a preferred embodiment of the invention, the materials flow that comprises at least a isomerization catalyst 3 to the small part that will obtain in processing step (b) is recycled in the processing step (a).

In another embodiment of the inventive method, processing step (a) and (b) in identical device, carry out.Can also from processing step (b), not take out and comprise the materials flow 3 of at least a isomerization catalyst and it is present in processing step (a) and the joint equipment (b).

Perhaps, the materials flow that comprises at least a isomerization catalyst 3 to the small part from processing step (b) can also be used for the educt flow that preparation is used at processing step (e) according to the present invention.In processing step (e), this at least a isomerization catalyst is subsequently as hydrocyanation catalyst.

Processing step (c)

Distillation materials flow 2 in processing step (c).Obtain comparing the materials flow 4 of being rich in (Z)-2-methyl-2-butene nitrile with respect to the summation of all pentenenitriles that exist in the materials flow 2 with top product thus with materials flow 2.In addition, obtain comparing the materials flow 5 that contains (Z)-2-methyl-2-butene nitrile with respect to the summation of all pentenenitriles that exist in the materials flow 2 is poor with bottoms with materials flow 2.

Processing step (c) can carry out in the known any suitable equipment of those skilled in the art.Suitable distillation plant for example is described in Kirk-Othmer, Encyclopedia of ChemicalTechnology, the 4th edition, the 8th volume, John Wiley ﹠amp; Sons, New York, in 1996, the 334-348 pages or leaves, as sieve-tray tower, bubble-cap tray column, have the tower of structured packing or random packing, the latter also can be used as the operation of partition tower.These distillation unit are equipped with the device that is suitable for evaporating separately, as falling-film evaporator, thin-film evaporator, heterogeneous screw and vertical tube evaporator, natural-circulation evaporator or pump circulation flasher and the device that is used for the condensing steam materials flow also is housed.Distillation can as carrying out in 2 or 3 equipment, advantageously be carried out in individual equipment a plurality of.Evaporate under the situation of incoming flow in part, distillation can also additionally be carried out in one section.

The processing step of the inventive method (c) preferably 0.1 millibar to 100 the crust, more preferably 1 millibar to 6 the crust, especially carry out under 10 millibars to 500 millibars the absolute pressure.Distillation is being preferably 25-250 ℃, more preferably 40-180 ℃, especially carries out under 60-140 ℃ the distillation plant bottom temp.Distillation is being preferably-15 to 200 ℃, more preferably 5-150 ℃, especially carries out under 10-100 ℃ the distillation plant head temperature.In the particularly preferred embodiment of the inventive method, all keep the said temperature scope in the two in the top of distillation plant and bottom.

In the particularly preferred embodiment of the inventive method, processing step (b) and (c) in a distillation plant, carry out together, obtain comprise the materials flow 3 of at least a isomerization catalyst with bottoms this moment, comprised the materials flow 4 of (Z)-2-methyl-2-butene nitrile and obtain comprising the materials flow 5 of 3 pentene nitrile and 2-methyl-3-crotononitrile with sideing stream of this tower with top product.

In another preferred embodiment of the inventive method, processing step (a) and (b) and (c) in a distillation plant, carrying out together.Comprised the materials flow 4 of (Z)-2-methyl-2-butene nitrile this moment with top product.Obtain comprising the materials flow 5 of 3 pentene nitrile and 2-methyl-3-crotononitrile with sideing stream of distillation tower.In this embodiment, isomerization catalyst is preferably stayed the bottom of distillation tower.

Processing step (d)

The materials flow 5 that comprises 3 pentene nitrile and 2-methyl-3-crotononitrile that will obtain in processing step (c) is then transferred in another distillation plant.In this distillation plant, materials flow 5 is separated into 3 pentene nitrile materials flow of discharging with bottoms and the 2-methyl-3-crotononitrile materials flow of discharging at the top.

Processing step (d) can carry out at the known any suitable equipment of those skilled in the art.Suitable distillation plant for example is described in Kirk-Othmer, Encyclopedia of ChemicalTechnology, the 4th edition, the 8th volume, John Wiley ﹠amp; Sons, in New York 1996, the 334-348 pages or leaves, as sieve-tray tower, bubble-cap tray column, have the tower of structured packing or random packing, the latter also can be used as the operation of partition tower.These distillation unit are equipped with the device that is suitable for evaporating separately, as falling-film evaporator, thin-film evaporator, heterogeneous screw and vertical tube evaporator, natural-circulation evaporator or pump circulation flasher and the device that is used for the condensing steam materials flow also is housed.Distillation can as carrying out in 2 or 3 equipment, advantageously be carried out in individual equipment a plurality of.Evaporate under the situation of incoming flow in part, distillation can also additionally be carried out in one section.

Absolute pressure in the processing step (d) is preferably the 0.001-100 crust, more preferably 0.01-20 crust, especially 0.05-2 crust.Distillation is being preferably 30-250 ℃, more preferably 50-200 ℃, especially carries out under 60-180 ℃ the distillation plant bottom temp.Distillation is being preferably-50 to 250 ℃, more preferably 0-180 ℃, especially carries out under 15-160 ℃ the distillation plant top condensing temperature.

In the particularly preferred embodiment of the inventive method, all keep the said temperature scope in the two in the top of distillation plant and bottom.

In the particularly preferred embodiment of the inventive method, processing step (d) carries out in identical distillation plant with processing step (g).This moment materials flow 6 with 12 and materials flow 7 identical with 13.In addition, in this preferred embodiment, directly materials flow 5 is sent in processing step (d) and the joint equipment (g).At this moment, materials flow 5 and 11 feed points can be identical or different under as the situation of distillation plant at distillation tower.

In another embodiment of the inventive method, processing step (c) and (g) in the common distillation tower, carry out, save processing step (d) this moment, to send into processing step (g) from the materials flow 2 of processing step (b) with from the materials flow 11 of processing step (f), and in processing step (g), comprised the materials flow 4 of (Z)-2-methyl-2-butene nitrile, the materials flow 13 that obtains comprising the materials flow 12 of 3 pentene nitrile and obtain comprising 2-methyl-3-crotononitrile to side stream with bottoms with top product.

In the inventive method of embodiment I, materials flow 2 directly can be recycled in the processing step (g) and with educt flow and directly send in the processing step (c), will be recycled in the isomerization of processing step (a) this moment from the materials flow 5a of processing step (c).

Perhaps, can also directly materials flow 2 be recycled in the processing step (g) and with educt flow and send in the processing step (c), will be recycled in the processing step (f) this moment from the materials flow 5 of processing step (c).

Perhaps, can also directly materials flow 2 be recycled in the processing step (g) and with educt flow and send in the processing step (c), and will be recycled in the processing step (e) from the materials flow 5 of processing step (c).

Embodiment II

The present invention further provides a kind of method for preparing 3 pentene nitrile according to embodiment II, it is characterized in that following process steps:

(a ') isomerization at least a dissolving or dispersive isomerization catalyst comprises the educt flow of 2-methyl-3-crotononitrile, obtain comprising the materials flow 1 ' of 3 pentene nitrile, 2-methyl-3-crotononitrile, this at least a isomerization catalyst and (Z)-2-methyl-2-butene nitrile

(b ') distillation materials flow 1 ', comprised the materials flow 2 ' of (Z)-2-methyl-2-butene nitrile, 2-methyl-3-crotononitrile, and it is recycled in the isomerization steps (a '), obtain comprising the materials flow 3 ' of this at least a isomerization catalyst and it is recycled to isomerization steps (a ') with bottoms, and the materials flow 4 ' that obtains comprising 3 pentene nitrile from the side material taking mouth of distillation tower.

The educt flow that is used for the processing step (a ') according to the inventive method of embodiment II can obtain by the aforesaid method that is used to prepare according to the educt flow of the inventive method of embodiment I.

For according to the processing step of embodiment II (a '), use and the identical condition of processing step (a), especially with regard to used catalyst complexes and free ligand according to embodiment I.

Absolute pressure in the processing step (b ') is preferably the 0.001-100 crust, more preferably 0.01-20 crust, especially 0.1-2 crust.Distillation is being preferably 25-250 ℃, more preferably 40-180 ℃, especially carries out under 60-140 ℃ the distillation plant bottom temp.Distillation is being preferably-50 to 250 ℃, more preferably 0-150 ℃, especially carries out under 10-100 ℃ the distillation plant top condensing temperature.

In order to prevent the gathering of (Z)-2-methyl-2-butene nitrile, it is suitable that part is discharged materials flow 2 ' in some cases.With residual materials flow recirculation in step (a ').

In a modification, educt flow is sent into processing step (b ') rather than processing step (a ') according to the inventive method of embodiment II.

Leaving the suitable words of the materials flow 2 ' of processing step (b ') in the inventive method according to embodiment II can distill in another optional processing step (c ').This is preferably formed the materials flow 5 ' of being rich in (Z)-2-methyl-2-butene nitrile and the materials flow 6 ' of poor containing (Z)-2-methyl-2-butene nitrile, and preferably materials flow 5 ' is recycled in the processing step (a ').

Suitable words, pending processing step (c ') can also carry out in the equipment of processing step (a '), the distillation plant that this moment isomerization reaction is carried out in the bottom is used for processing step (a '), discharges materials flow 1 ' and discharges the materials flow 6 ' of being rich in (Z)-2-methyl-2-butene nitrile via the top of this distillation plant via the bottom of this distillation plant.

According to the present invention, in method, obtain 3 pentene nitrile according to embodiment I and II.In the context of the invention, the term 3 pentene nitrile refers to the individual isomer or 2,3,4 or 5 kind of such different mixture of isomers of 3 pentene nitrile.Isomer comprises cis-2-pentenenitrile, trans-the 2-pentenenitrile, cis-3 pentene nitrile, trans-3 pentene nitrile, allyl acetonitrile or its mixture, preferred cis-3 pentene nitrile, trans-3 pentene nitrile, allyl acetonitrile or or its mixture, in the context of the invention, all be called 3 pentene nitrile separately and with mixture in each case.

The inventive method is favourable.For example, in the integrated processes of preparation adiponitrile, for example will because being converted into the degree of 3 pentene nitrile, 2-methyl-3-crotononitrile be subjected to thermodynamics equilibrium limit from isomerized unconverted 2-methyl-recirculation of 3-crotononitrile is necessary economically.(the Z)-2-methyl-2-butene nitrile that accumulates in 2-methyl-3-crotononitrile loop has been removed in this recirculation.In the methods of the invention, this is only removed preferably carrying out step (a) and carries out to separate 2-methyl-3-crotononitrile and (Z)-2-methyl-2-butene nitrile by distillation in step (c) afterwards, so that in a controlled manner the loss of valuable product is reduced to minimum.

Describe the inventive method in detail with reference to Fig. 1 according to the optimal way of embodiment I:

In reactor R1, in the presence of nickel (0) catalyzer, infeed prussic acid and 1,3-butadiene.In this reactor, carry out hydrocyanation and form materials flow 8.This materials flow 8 comprises 3 pentene nitrile, 2-methyl-3-crotononitrile, hydrocyanation catalyst and unconverted 1,3-butadiene.Then materials flow 8 is transferred among the distillation tower K1, by the top 1,3-butadiene (materials flow 9) is removed from materials flow 8 therein.Obtain comprising the materials flow 10 of hydrocyanation catalyst in the bottom of distillation tower K1.Obtain comprising the materials flow 11 of 3 pentene nitrile and 2-methyl-3-crotononitrile at the side material taking mouth of distillation tower K1.Then this materials flow 11 is transferred among the distillation tower K2.

In distillation tower K2, materials flow 11 is separated into materials flow 12 that comprises 3 pentene nitrile and the materials flow 13 that comprises 2-methyl-3-crotononitrile.

Then materials flow 13 is transferred among the isomerization unit R2.In this isomerization unit R2, be present in the 2-methyl-3-crotononitrile isomerization on isomerization catalyst in the materials flow 13.Comprise 3 pentene nitrile, 2-methyl-3-crotononitrile, (Z)-2-methyl-2-butene nitrile and isomerization catalyst from this isomerized materials flow 1.

Then this materials flow 1 is separated in distillation plant K3.Obtain comprising the materials flow 3 (bottom stream) of isomerization catalyst thus.Materials flow 2 is discharged at top at this distillation plant K3.This materials flow 2 comprises 3 pentene nitrile, (Z)-2-methyl-2-butene nitrile and 2-methyl-3-crotononitrile.Then this materials flow 2 is transferred among the distillation tower K4.

In this distillation tower K4, materials flow 2 is separated into (the Z)-2-methyl-2-butene nitrile (materials flow 4) that in isomerization process, has formed.In addition, obtain comprising the materials flow 5 of 3 pentene nitrile and 2-methyl-3-crotononitrile in the bottom of distillation tower K4.This materials flow 5 is transferred to distillation tower K2 and obtain 3 pentene nitrile by materials flow 5 in this distillation tower.

Materials flow 9 and 10 can partially or completely be recycled among the reactor R1, perhaps not recirculation.Same situation is applicable to the materials flow 3 on reactor R2 direction.These modification are not presented among Fig. 1.

Describe the inventive method in detail with reference to Fig. 2 according to the optimal way of embodiment II:

In reactor R1, in the presence of nickel (0) catalyzer, infeed prussic acid and 1,3-butadiene.In this reactor, carry out hydrocyanation and form materials flow 8.This materials flow 8 comprises 3 pentene nitrile, 2-methyl-3-crotononitrile, hydrocyanation catalyst and unconverted 1,3-butadiene.Then materials flow 8 is transferred among the distillation tower K1, by the top 1,3-butadiene (materials flow 9) is removed from materials flow 8 therein.Obtain comprising the materials flow 10 of hydrocyanation catalyst in the bottom of distillation tower K1.Obtain comprising the materials flow 11 of 3 pentene nitrile and 2-methyl-3-crotononitrile at the side material taking mouth of distillation tower K1.Then this materials flow 11 is transferred among the isomerization unit R2.

In isomerization unit R2, extra isomerization catalyst (materials flow 3 ') and the 2-methyl-3-crotononitrile of introducing separately from distillation tower K2 (materials flow 2 ').Isomerization takes place in this isomerization unit R2.To transfer among the distillation plant K2 from materials flow 1 ' wherein then, therein materials flow 1 ' is separated into the materials flow 2 ' (2-methyl-3-crotononitrile) that is recycled among the R2, is recycled to the materials flow 3 ' (isomerization catalyst) among the R2 and comprises the materials flow 4 ' of 3 pentene nitrile.

The materials flow that will comprise isomerization catalyst infeeds R2 always can compensate any essential discharge from materials flow 3 ', makes Ni (0) content among the R2 keep constant thus.

Materials flow 9 and 10 can partially or completely be recycled among the reactor R1, perhaps not recirculation.

These recirculation and discharge modification are not presented among Fig. 2.

Embodiment III

In embodiment III, use Catalytic processes step a ^*) and e ^*) the hydrocyanation and isomerization Ni (0) catalyzer of those parts.

Nickel (0) title complex that contains phosphorus part and/or free phosphorus part that is preferably used as catalyzer is preferably homogeneous phase dissolved nickel (0) title complex.

The phosphorus part of nickel (0) title complex and free phosphorus part are preferably selected from monodentate-or bidentate phosphine, phosphorous acid ester, phosphinate and phosphinate, more preferably monodentate-or bidentate phosphite ester, phosphinate and phosphinate, more preferably monodentate-or bidentate phosphite ester and phosphinate, especially monodentate phosphite, phosphinate and phosphinate, most preferably monodentate phosphite and phosphinate.

These phosphorus parts preferably have formula I:

P(X ¹R ¹)(X ²R ²)(X ³R ³) (I)。

Work as radicals X ¹, X ²And X ³In one of be singly-bound and wherein two when the oxygen, Compound I is formula P (OR ¹) (OR ²) (R ³) or P (R ¹) (OR ²) (OR ³) or P (OR ¹) (R ²) (OR ³) phosphinate, R wherein ¹, R ²And R ³Definition such as specification sheets defined.

In one embodiment, all radicals X ¹, X ²And X ³Should be oxygen, is formula P (OR thereby make Compound I ¹) (OR ²) (OR ³) phosphorous acid ester, R wherein ¹, R ²And R ³Be defined as follows defined.

In one embodiment, R ¹, R ²And R ³For being selected from the group of phenyl, o-tolyl, a tolyl and p-methylphenyl.In one embodiment, radicals R ¹, R ²And R ³In maximum two should be phenyl.

In another embodiment, radicals R ¹, R ²And R ³In maximum two should be o-tolyl.

Operable Compound I is those of formula Ia:

(o-tolyl-O-) _w(tolyl-O-) _x(p-methylphenyl-O-) _y(phenyl-O-) _zP (Ia)

In one embodiment, the phosphorus part is the phosphorous acid ester that is specified in the formula Ib among the DE-A 199 53 058:

P(O-R ¹) _x(O-R ²) _y(O-R ³) _z(O-R ⁴) _p (Ib)

Wherein

X:1 or 2,

Y, z, p are 0,1 or 2 independently of one another, and condition is x+y+z+p=3.

x	y	z	p
x	y	z	p		1	0	0	2
1	0	1	1		1	0	0	2
1	0	1	1	1	1	0	1
2	0	0	1	1	1	0	1
2	0	0	1	1	0	2	0
1	1	1	0	1	0	2	0
1	1	1	0	1	2	0	0

2	0	1	0
2	0	1	0	2	1	0	0

The phosphorous acid ester of formula Ib can obtain by the following method:

The phosphorus part can be polydentate ligand, especially bitooth ligand equally.Used part for example has formula II:

Wherein

Y is the bridge joint group.

In one embodiment, X ¹¹, X ¹², X ¹³, X ²¹, X ²², X ²³The oxygen of can respectively doing for oneself.At this moment, bridge joint group Y is bonded on the phosphorous acid ester group.

In another embodiment, X ¹¹And X ¹²Oxygen and X can respectively do for oneself ¹³Be singly-bound, perhaps X ¹¹And X ¹³Oxygen and X respectively do for oneself ¹²Be singly-bound, thereby make by X ¹¹, X ¹²And X ¹³The phosphorus atom that surrounds is the central atom of phosphinate.At this moment, X ²¹, X ²²And X ²³Oxygen, perhaps X can respectively do for oneself ²¹And X ²²Oxygen and X can respectively do for oneself ²³Be singly-bound, perhaps X ²¹And X ²³Oxygen and X can respectively do for oneself ²²Be singly-bound, perhaps X ²³Can be oxygen and X ²¹And X ²²Singly-bound, perhaps X respectively do for oneself ²¹Can be oxygen and X ²²And X ²³Singly-bound, perhaps X respectively do for oneself ²¹, X ²²And X ²³The singly-bound of can respectively doing for oneself, thus make by X ²¹, X ²²And X ²³The phosphorus atom that surrounds can be phosphorous acid ester, phosphinate, phosphinate or phosphine, the central atom of preferred phosphinate.

In another embodiment, X ¹³Can be oxygen and X ¹¹And X ¹²Singly-bound, perhaps X respectively do for oneself ¹¹Can be oxygen and X ¹²And X ¹³The singly-bound of respectively doing for oneself, thus make by X ¹¹, X ¹²And X ¹³The phosphorus atom that surrounds can be the central atom of phosphinate.At this moment, X ²¹, X ²²And X ²³Oxygen, perhaps X can respectively do for oneself ²³Can be oxygen and X ²¹And X ²²Singly-bound, perhaps X respectively do for oneself ²¹Can be oxygen and X ²²And X ²³Singly-bound, perhaps X respectively do for oneself ²¹, X ²²And X ²³The singly-bound of can respectively doing for oneself, thus make by X ²¹, X ²²And X ²³The phosphorus atom that surrounds can be phosphorous acid ester, phosphinate or phosphine, the central atom of preferred phosphinate.

In another embodiment, X ¹¹, X ¹²And X ¹³The singly-bound of can respectively doing for oneself, thus make by X ¹¹, X ¹²And X ¹³The phosphorus atom that surrounds can be the central atom of phosphine.At this moment, X ²¹, X ²²And X ²³Oxygen, perhaps X can respectively do for oneself ²¹, X ²²And X ²³The singly-bound of can respectively doing for oneself, thus make by X ²¹, X ²²And X ²³The phosphorus atom that surrounds can be phosphorous acid ester or phosphine, the central atom of preferred phosphine.

In one embodiment, useful compound is US 5,723, those of formula I, II, III, IV and the V of defined in 641.In one embodiment, useful compound is US 5,512, those of formula I, II, III, IV, V, VI and the VII of defined in 696, the compound that uses among the embodiment 1-31 especially therein.In one embodiment, useful compound is US5, those of the formula I of defined, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV in 821,378, the compound that uses among the embodiment 1-73 especially therein.

In one embodiment, useful compound is US 5,512, those of formula I, II, III, IV, V and the VI of defined in 695, the compound that uses among the embodiment 1-6 especially therein.In one embodiment, useful compound is US 5, those of the formula I of defined, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII and XIV in 981,772, the compound that uses among the embodiment 1-66 especially therein.

In one embodiment, useful compound is US 6,127, the compound that uses among those and the embodiment 1-29 therein of defined in 567.In one embodiment, useful compound is US 6,020, those of formula I, II, III, IV, V, VI, VII, VIII, IX and the X of defined in 516, the compound that uses among the embodiment 1-33 especially therein.In one embodiment, useful compound is US 5,959, the compound that uses among those and the embodiment 1-13 therein of defined in 135.

In one embodiment, useful compound is US 5,847, those of formula I, the II of defined and III in 191.In one embodiment, useful compound is US 5, those of defined in 523,453 are especially therein with the compounds of

formula

1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20 and 21 explanations.In one embodiment, useful compound is those of defined among the WO 01/14392, and is preferred therein with the compound of formula V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XXI, XXII, XXIII explanation.

In one embodiment, useful compound is those of defined among the WO 98/27054.In one embodiment, useful compound is those of defined among the WO 99/13983.In one embodiment, useful compound is those of defined among the WO 99/64155.

In one embodiment, useful compound is those of defined among the German patent application DE 100 380 37.In one embodiment, useful compound is those of defined among the German patent application DE 100,460 25.In one embodiment, useful compound is those of defined among the German patent application DE 101 502 85.

In one embodiment, useful compound is those of defined among the German patent application DE 101 502 86.In one embodiment, useful compound is those of defined among the German patent application DE 102,071 65.In another embodiment of the present invention, useful phosphorus chelating ligand is those of defined among US 2003/0100442 A1.

In another embodiment of the present invention, useful phosphorus chelating ligand is those of defined among the German patent application reference number DE 103 50 999.2 on October 30th, 2003, and this application has priority date early but announces as yet at the application's priority date.

In the particularly preferred embodiment of the inventive method, the phosphorus part and/or the free phosphorus part of nickel (0) title complex are the phosphorous acid esters that is selected from formula Ib:

P(O-R ¹) _x(O-R ²) _y(O-R ³) _z(O-R ⁴) _p (Ib)

R wherein ¹, R ²And R ³Be selected from o-isopropyl phenyl, a tolyl and p-methylphenyl independently of one another, R ⁴Be phenyl; X be 1 or 2 and y, z, p be 0,1 or 2 independently of one another, condition is x+y+z+p=3; And composition thereof, promptly two or more, preferred 2-10 kind, the more preferably mixture of 2-6 kind formula Ib compound.

In an embodiment III, the method is characterized in that following process steps:

(a ^*) at least a dissolving or dispersive isomerization catalyst isomerization comprise the educt flow of 2-methyl-3-crotononitrile, obtain comprising the materials flow 1 of this at least a isomerization catalyst, 2-methyl-3-crotononitrile, 3 pentene nitrile and (Z)-2-methyl-2-butene nitrile

(b ^*) distillation materials flow 1, obtain comprising the materials flow 2 of 2-methyl-3-crotononitrile, 3 pentene nitrile and (Z)-2-methyl-2-butene nitrile with top product, and obtain comprising the materials flow 3 of this at least a isomerization catalyst with bottoms,

(c ^*) distillation materials flow 2, obtain comparing the materials flow 4 of being rich in (Z)-2-methyl-2-butene nitrile based on the summation of all pentenenitriles in the materials flow 2 with top product with materials flow 2, and obtain comparing the materials flow 5 of being rich in 3 pentene nitrile and 2-methyl-3-crotononitrile based on the summation of all pentenenitriles in the materials flow 2 with materials flow 2 with bottoms

(d ^*) distillation materials flow 5, obtain comprising the materials flow 6 of 3 pentene nitrile and obtain comprising the materials flow 7 of 2-methyl-3-crotononitrile with bottoms with top product,

(h ^*) regenerated catalyst to be to replenish from the son stream 14 of materials flow 3 with from nickel (0) content of the son stream 16 of materials flow 10, produces materials flow 18 thus,

(i ^*) suitable words add thinner F in the materials flow 18, produce materials flow 19,

(j ^*) by adding dintrile materials flow 20 and hydrocarbon flow 21 extraction materials flows 18, the catalyst component in the suitable words materials flow 19 and/or the component of breaking, produce two kinds of immiscible phases 22 and 23, wherein materials flow 22 comprises the catalyst component of main ratio and the component of breaking that materials flow 23 comprises main ratio

(k ^*) always distillation removes dealkylation in the catalyst component of materials flow 22, produces the materials flow 25 of the catalyst component that comprises main ratio and suitable, and materials flow 25 partially or completely is recycled to processing step (a ^*) or (e ^*) in.

Educt flow

At processing step (a ^*) in, isomerization comprises the educt flow of 2-methyl-3-crotononitrile at least a isomerization catalyst.

(e ^*) use prussic acid hydrocyanation 1,3-butadiene at least a hydrocyanation catalyst, obtain comprising the materials flow 8 of this at least a hydrocyanation catalyst, 3 pentene nitrile, 2-methyl-3-crotononitrile, 1,3-butadiene and residual prussic acid,

(f ^*) with materials flow 8 distillation once or more than once, obtain comprising the materials flow 9 of 1,3-butadiene, comprise the materials flow 10 of this at least a hydrocyanation catalyst and comprise the materials flow 11 of 3 pentene nitrile and 2-methyl-3-crotononitrile,

(g ^*) distillation materials flow 11, obtain comprising the materials flow 12 of 3 pentene nitrile with bottoms, and obtain comprising the materials flow 13 of 2-methyl-3-crotononitrile with top product.

Processing step e ^*)

Processing step (e in the preparation feedback streams ^*) in, at first use prussic acid hydrocyanation 1,3-butadiene at least a hydrocyanation catalyst, obtain comprising the materials flow 8 of this at least a hydrocyanation catalyst, 3 pentene nitrile, 2-methyl-3-crotononitrile and unconverted 1,3-butadiene.

Processing step (e ^*) can in the known suitable equipment of any those skilled in the art, carry out.Therefore useful conversion unit is conventional equipment, for example as Kirk-Othmer, and Encyclopediaof Chemical Technology, the 4th edition, the 20th volume, John Wiley ﹠amp; Sons, New York, 1996, the 1040-1055 pages or leaves are described, and as stirred-tank reactor, annular-pipe reactor, gas circulation reactor, bubble-column reactor or tubular reactor, suitable in each case voice band has the device of removing reaction heat.This reaction can be a plurality of, as carrying out in 2 or 3 equipment.

In another embodiment, this reaction can be carried out in liquid phase, and the pressure in the reactor should make all raw materials such as 1,3-butadiene, prussic acid and at least a catalyzer be metered into liquid form and be present in the reaction mixture with liquid phase at this moment.Solid suspension may reside in the reaction mixture mutually and can also be metered into at least a catalyzer, and this catalyzer for example is made up of the degraded product of the catalyst system that especially comprises nickel (II) compound.

At processing step (e ^*) in, obtain comprising the materials flow 8 of 3 pentene nitrile, 2-methyl-3-crotononitrile, at least a hydrocyanation catalyst and unconverted 1,3-butadiene.

Processing step (f ^*)

The materials flow 8 that will comprise 3 pentene nitrile, 2-methyl-3-crotononitrile, at least a hydrocyanation catalyst and unconverted 1,3-butadiene then is at processing step (f ^*) in transfer in the distillation plant.In this distillation plant, materials flow 8 is distilled once or more than once, is obtained comprising the materials flow 9 of 1,3-butadiene, comprises the materials flow 10 and the materials flow 11 that comprises 3 pentene nitrile and 2-methyl-3-crotononitrile of at least a hydrocyanation catalyst.

Processing step (f ^*) distillation can two sections carry out, as described in the DE-A-102 004 004 720 with processing step (b ^*) and (c ^*) carry out.Processing step (f ^*) distillation can also be according to DE-A-102 004 004729 with processing step (b ^*) and (c ^*) carry out.

Processing step (f ^*) distillation can in the known any suitable equipment of those skilled in the art, carry out.Suitable distillation plant for example is described in Kirk-Othmer, Encyclopedia ofChemical Technology, the 4th edition, the 8th volume, John Wiley ﹠amp; Sons, New York, in 1996, the 334-348 pages or leaves, as sieve-tray tower, bubble-cap tray column, have the tower of structured packing or random packing, the latter also can be used as the operation of partition tower.These distillation unit are equipped with the device that is suitable for evaporating separately, as falling-film evaporator, thin-film evaporator, heterogeneous screw and vertical tube evaporator, natural-circulation evaporator or pump circulation flasher and the device that is used for the condensing steam materials flow also is housed.Each distillation is can each leisure a plurality of, as carrying out in 2 or 3 equipment, advantageously carries out in single equipment in each case.

Processing step (f ^*) in pressure be preferably 0.001-10 crust, more preferably 0.010-1 crust, especially 0.02-0.5 crust.Distillation more preferably 50-150 ℃, is especially carried out under 60-120 ℃ the distillation plant bottom temp preferably at 30-200 ℃.Distillation, is especially carried out under 5-45 ℃ the distillation plant top condensing temperature more preferably-15 to 60 ℃ preferably at-15 to 150 ℃.In the particularly preferred embodiment of the inventive method, all keep the said temperature scope in the two at the bottom of distillation plant and top.

Subsequently with materials flow 11 at further processing step (g ^*) in distill.This distillation can be carried out in the known any suitable equipment of those skilled in the art.Suitable distillation plant for example is described in Kirk-Othmer, Encyclopedia of Chemical Technology, the 4th edition, the 8th volume, John Wiley ﹠amp; Sons, New York, in 1996, the 334-348 pages or leaves, as sieve-tray tower, bubble-cap tray column, have the tower of structured packing or random packing, the latter also can be used as the operation of partition tower.These distillation unit are equipped with the device that is suitable for evaporating separately, as falling-film evaporator, thin-film evaporator, heterogeneous screw and vertical tube evaporator, natural-circulation evaporator or pump circulation flasher and the device that is used for the condensing steam materials flow also is housed.Each distillation is can each leisure a plurality of, as carrying out in 2 or 3 equipment, advantageously carries out in single equipment.Evaporate under the situation of incoming flow in part, distillation can additionally be carried out in one section.

Processing step (g ^*) in pressure be preferably 0.001-100 crust, more preferably 0.01-20 crust, especially 0.05-2 crust.Distillation more preferably 50-200 ℃, is especially carried out under 60-180 ℃ the distillation plant bottom temp preferably at 30-250 ℃.Distillation more preferably 0-180 ℃, is especially carried out under 15-160 ℃ the distillation plant top condensing temperature preferably at-50 to 250 ℃.In the particularly preferred embodiment of the inventive method, all keep the said temperature scope in the two at the bottom of distillation plant and top.

At processing step (g ^*) in, obtaining comprising 1 with bottoms, the materials flow 12 of 3 pentene nitrile also obtains comprising the materials flow 13 of 2-methyl-3-crotononitrile with top product.Preferably materials flow 13 is prepared the educt flow in the method for 3 pentene nitrile as the present invention.

In another embodiment of the present invention, be used for processing step (a of the present invention ^*) in educt flow can be corresponding to processing step (f ^*) materials flow 11, thereby save materials flow 11 at processing step (g ^*) in separation.

Processing step (a ^*)

At processing step (a ^*) in, isomerization comprises the educt flow of 2-methyl-3-crotononitrile at least a isomerization catalyst.Obtain comprising the materials flow 1 of isomerization catalyst, unconverted 2-methyl-3-crotononitrile, 3 pentene nitrile and (Z)-2-methyl-2-butene nitrile thus.

Nickel (0) and

Contain phosphorous compound as what part cooperated with nickel (0).

The part of isomerization catalyst can be with at processing step (e ^*) in be used for the identical phosphorus part of hydrocyanation catalyst.Therefore, hydrocyanation catalyst can be identical with isomerization catalyst.

At processing step (a ^*) and (e ^*) in catalyzer do not contain Lewis acid substantially, promptly all in catalyzer, do not add Lewis acid at any time, and this catalyzer does not preferably contain any Lewis acid.

Lewis acid refers to inorganic or organometallic compound in context, wherein positively charged ion is selected from scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminium, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium and tin.Example comprises ZnBr ₂, ZnI ₂, ZnCl ₂, ZnSO ₄, CuCl ₂, CuCl, Cu (O ₃SCF ₃) ₂, CoCl ₂, CoI ₂, FeI ₂, FeCl ₃, FeCl ₂, FeCl ₂(THF) ₂, TiCl ₄(THF) ₂, TiCl ₄, TiCl ₃, ClTi (O-sec.-propyl) ₃, MnCl ₂, ScCl ₃, AlCl ₃, (C ₈H ₁₇) AlCl ₂, (C ₈H ₁₇) ₂AlCl, (different-C ₄H ₉) ₂AlCl, (C ₆H ₅) ₂AlCl, (C ₆H ₅) AlCl ₂, ReCl ₅, ZrCl ₄, NbCl ₅, VCl ₃, CrCl ₂, MoCl ₅, YCl ₃, CdCl ₂, LaCl ₃, Er (O ₃SCF ₃) ₃, Yb (O ₂CCF ₃) ₃, SmCl ₃, B (C ₆H ₅) ₃, TaCl ₅, RAlCl ₂, R ₂AlCl, RSnO ₃SCF ₃And R ₃B, wherein R is an alkyl or aryl, B (C ₆H ₅) ₃(C ₆H ₅) ₃SnX, wherein X=CF ₃SO ₃, CH ₃C ₆H ₄SO ₃Or (C ₆H ₅) ₃BCN, for example as US 6,127,567, US 6,171,996, US 6,380,421, US 3,496,217, US 3,496,218, US 4,774,353, US 4,773,809, US 3,496,217 and US 4,874,884 is described.

-ester such as ethyl acetate, methyl benzoate, or

-nitrile such as acetonitrile, benzonitrile, or

The mixture of-such thinner.

In addition, have been found that advantageously at processing step (a ^*) in isomerization in non-oxidizing atmosphere, for example under the protective gas atmosphere of forming by nitrogen or rare gas such as argon gas, carry out.

Processing step (a ^*) can in the known suitable equipment of any those skilled in the art, carry out.Useful conversion unit is the equipment that is usually used in this purpose, for example as Kirk-Othmer, and Encyclopedia of Chemical Technology, the 4th edition, the 20th volume, John Wiley ﹠amp; Sons, New York 1996, the 1040-1055 pages or leaves are described, as stirred-tank reactor, annular-pipe reactor, gas circulation reactor, bubble-column reactor or tubular reactor.This reaction can be a plurality of, as carrying out in 2 or 3 equipment.

In the preferred embodiment of the inventive method, isomerization tubular type at interval anti--answer in the device and carry out.

In an embodiment of the inventive method, this reaction can be carried out in a distillation plant, and isomerization reaction this moment is carried out at the bottom section of distillation plant at least.The known distillation plant of any those skilled in the art is suitable, for example as Kirk-Othmer, and Encyclopedia ofChemical Technology, the 4th edition, the 8th volume, John Wiley ﹠amp; Sons, New York, 1996, the 334-348 pages or leaves are described, and as sieve-tray tower, bubble-cap tray column, have the tower of structured packing or random packing, the latter also can be used as the operation of partition tower.These distillation unit are equipped with the device that is suitable for evaporating separately, as falling-film evaporator, thin-film evaporator, heterogeneous screw and vertical tube evaporator, natural-circulation evaporator or pump circulation flasher and the device that is used for the condensing steam materials flow also is housed.The distillation of reacting simultaneously can as carrying out in 2 or 3 equipment, advantageously be carried out in individual equipment a plurality of.Evaporate under the situation of incoming flow in part, distillation can also additionally be carried out in one section.

Processing step (a of the inventive method ^*) preferably 0.1 millibar to 100 the crust, more preferably 1 millibar to 16 the crust, especially 10 millibars to 6 the crust absolute pressures under carry out.Processing step (a ^*) in temperature be preferably 25-250 ℃, more preferably 30-180 ℃, especially 40-140 ℃.

Processing step (b ^*)

At processing step (b ^*) in, distillation is at processing step (a ^*) in the materials flow 1 that obtains.Obtain comprising the materials flow 2 of 2-methyl-3-crotononitrile, 3 pentene nitrile and (Z)-2-methyl-2-butene nitrile thus with top product.In addition, at processing step (b ^*) in comprise the materials flow 3 of at least a isomerization catalyst with bottoms.

Processing step (the b of the inventive method ^*) can in the known any suitable distillation plant of those skilled in the art, carry out.Suitable distillation plant for example is described in Kirk-Othmer, Encyclopedia of Chemical Technology, the 4th edition, the 8th volume, John Wiley ﹠amp; Sons, New York, in 1996, the 334-348 pages or leaves, as sieve-tray tower, bubble-cap tray column, have the tower of structured packing or random packing, the latter also can be used as the operation of partition tower.These distillation unit are equipped with the device that is suitable for evaporating separately, as falling-film evaporator, thin-film evaporator, heterogeneous screw and vertical tube evaporator, natural-circulation evaporator or pump circulation flasher and the device that is used for the condensing steam materials flow also is housed.Distillation can as carrying out in 2 or 3 equipment, advantageously be carried out in individual equipment a plurality of.Evaporate under the situation of incoming flow in part, distillation can also additionally be carried out in one section.

Processing step (the b of the inventive method ^*) preferably 0.1 millibar to 100 the crust, more preferably 1 millibar to 6 the crust, especially carry out under 10 millibars to 500 millibars the absolute pressure.Distillation is being preferably 25-250 ℃, more preferably 40-180 ℃, especially carries out under 60-140 ℃ the distillation plant bottom temp.Distillation is being preferably-15 to 200 ℃, more preferably 5-150 ℃, especially carries out under 10-100 ℃ the distillation plant head temperature.In the particularly preferred embodiment of the inventive method, all keep the said temperature scope in the two in the top of distillation plant and bottom.

In particularly preferred embodiment of the present invention, at processing step (b ^*) in the distillation of the materials flow 1 carried out in this mixture existing isomerization catalyst not as at processing step (a ^*) in active, or carry out under inactive pressure and temperature condition.

In a preferred embodiment of the invention, will be at processing step (b ^*) in the materials flow that comprises at least a isomerization catalyst 3 to the small part that obtains be recycled to processing step (a ^*) in.

In another embodiment of the inventive method, processing step (a ^*) and (b ^*) in identical device, carry out.Can also be not from processing step (b ^*) in take out and to comprise the materials flow 3 of at least a isomerization catalyst and to make it be present in processing step (a ^*) and (b ^*) joint equipment in.

Processing step (c ^*)

At processing step (c ^*) middle distillation materials flow 2.Obtain comparing the materials flow 4 of being rich in (Z)-2-methyl-2-butene nitrile with respect to the summation of all pentenenitriles that exist in the materials flow 2 with top product thus with materials flow 2.In addition, obtain comparing the materials flow 5 that contains (Z)-2-methyl-2-butene nitrile with respect to the summation of all pentenenitriles that exist in the materials flow 2 is poor with bottoms with materials flow 2.

Processing step (c ^*) can in the known any suitable equipment of those skilled in the art, carry out.Suitable distillation plant for example is described in Kirk-Othmer, Encyclopedia of ChemicalTechnology, the 4th edition, the 8th volume, John Wiley ﹠amp; Sons, in New York 1996, the 334-348 pages or leaves, as sieve-tray tower, bubble-cap tray column, have the tower of structured packing or random packing, the latter also can be used as the operation of partition tower.These distillation unit are equipped with the device that is suitable for evaporating separately, as falling-film evaporator, thin-film evaporator, heterogeneous screw and vertical tube evaporator, natural-circulation evaporator or pump circulation flasher and the device that is used for the condensing steam materials flow also is housed.Distillation can as carrying out in 2 or 3 equipment, advantageously be carried out in individual equipment a plurality of.Evaporate under the situation of incoming flow in part, distillation can also additionally be carried out in one section.

Processing step (the c of the inventive method ^*) preferably 0.1 millibar to 100 the crust, more preferably 1 millibar to 6 the crust, especially carry out under 10 millibars to 500 millibars the absolute pressure.Distillation is being preferably 25-250 ℃, more preferably 40-180 ℃, especially carries out under 60-140 ℃ the distillation plant bottom temp.Distillation is being preferably-15 to 200 ℃, more preferably 5-150 ℃, especially carries out under 10-100 ℃ the distillation plant head temperature.In the particularly preferred embodiment of the inventive method, all keep the said temperature scope in the two in the top of distillation plant and bottom.

In the particularly preferred embodiment of the inventive method, processing step (b ^*) and (c ^*) in a distillation plant, carry out together, obtain comprise the materials flow 3 of at least a isomerization catalyst with bottoms this moment, comprised the materials flow 4 of (Z)-2-methyl-2-butene nitrile and obtain comprising the materials flow 5 of 3 pentene nitrile and 2-methyl-3-crotononitrile with sideing stream of this tower with top product.

In another preferred embodiment of the inventive method, processing step (a ^*), (b ^*) and (c ^*) in a distillation plant, carry out together.Comprised the materials flow 4 of (Z)-2-methyl-2-butene nitrile this moment with top product.Obtain comprising the materials flow 5 of 3 pentene nitrile and 2-methyl-3-crotononitrile with sideing stream of distillation tower.In this embodiment, isomerization catalyst is preferably stayed the bottom of distillation tower.

Processing step (d ^*)

Then will be at processing step (c ^*) in the materials flow 5 that comprises 3 pentene nitrile and 2-methyl-3-crotononitrile that obtains transfer in another distillation plant.In this distillation plant, materials flow 5 is separated into 3 pentene nitrile materials flow of discharging with bottoms and the 2-methyl-3-crotononitrile materials flow of discharging at the top.

Processing step (d ^*) can in the known any suitable equipment of those skilled in the art, carry out.Suitable distillation plant for example is described in Kirk-Othmer, Encyclopedia of ChemicalTechnology, the 4th edition, the 8th volume, John Wiley ﹠amp; Sons, New York, in 1996, the 334-348 pages or leaves, as sieve-tray tower, bubble-cap tray column, have the tower of structured packing or random packing, the latter also can be used as the operation of partition tower.These distillation unit are equipped with the device that is suitable for evaporating separately, as falling-film evaporator, thin-film evaporator, heterogeneous screw and vertical tube evaporator, natural-circulation evaporator or pump circulation flasher and the device that is used for the condensing steam materials flow also is housed.Distillation can as carrying out in 2 or 3 equipment, advantageously be carried out in individual equipment a plurality of.Evaporate under the situation of incoming flow in part, distillation can also be carried out in one section.

Processing step (d ^*) in absolute pressure be preferably 0.001-100 crust, more preferably 0.01-20 crust, especially 0.05-2 crust.Distillation is being preferably 30-250 ℃, more preferably 50-200 ℃, especially carries out under 60-180 ℃ the distillation plant bottom temp.Distillation is being preferably-50 to 250 ℃, more preferably 0-180 ℃, especially carries out under 15-160 ℃ the distillation plant top condensing temperature.

In the particularly preferred embodiment of the inventive method, processing step (d ^*) and processing step (g ^*) in identical distillation plant, carry out.This moment materials flow 6 with 12 and materials flow 7 identical with 13.In addition, in this preferred embodiment, directly processing step (d is sent in materials flow 5 ^*) and (g ^*) joint equipment in.At this moment, materials flow 5 and 11 feed points can be identical or different under as the situation of distillation plant at distillation tower.

In another embodiment of the inventive method, processing step (c ^*) and (g ^*) in the common distillation tower, carry out, save processing step (d this moment ^*), will be from processing step (b ^*) materials flow 2 and from processing step (f ^*) materials flow 11 send into processing step (g ^*), and at processing step (g ^*) in comprised the materials flow 4 of (Z)-2-methyl-2-butene nitrile with top product, the materials flow 13 that obtains comprising the materials flow 12 of 3 pentene nitrile and obtain comprising 2-methyl-3-crotononitrile to side stream with bottoms.

In the inventive method of embodiment III, materials flow 2 directly can be recycled to processing step (g ^*) in and educt flow directly sent into processing step (c ^*) in, this moment will be from processing step (c ^*) materials flow 5a be recycled to processing step (a ^*) isomerization in.

Perhaps, can also directly materials flow 2 be recycled to processing step (g ^*) in and educt flow sent into processing step (c ^*) in, this moment will be from processing step (c ^*) materials flow 5 be recycled to processing step (f ^*) in.

Perhaps, can also directly materials flow 2 be recycled to processing step (g ^*) in and educt flow sent into processing step (c ^*) in, and will be from processing step (c ^*) materials flow 5 be recycled to processing step (e ^*) in.

Processing step h ^*):

Processing step h ^*) comprise that a kind of preparation contains the method for nickel (the 0)-phosphorous ligand complexes of at least one nickel (0) central atom and at least a phosphorus part.

Hereinafter, term reductibility catalyzer synthetic/regeneration and redox catalyst be synthetic/to regenerate be synonym.

Processing step h ₁ ^*):

At processing step h ^*) preferred embodiment (be called processing step h here ₁ ^*)) in, the moisture nickel halogenide (II) of reduction by azeotropic distillation drying in the presence of at least a phosphorus part (moisture before but yes after component distillation exsiccant).

Component distillation

In component distillation, use moisture nickel halogenide (II).Moisture nickel halogenide (II) is the nickel halogenide that is selected from nickelous chloride, nickelous bromide and nickelous iodide and contains at least 2 weight % water.The example is two hydration nickelous chlorides, Nickel dichloride hexahydrate, nickel chloride aqueous solution, three hydration nickelous bromides, the nickelous bromide aqueous solution, hydration nickelous iodide or the nickelous iodide aqueous solution.Under the situation of nickelous chloride, preferably use Nickel dichloride hexahydrate or nickel chloride aqueous solution.Under the situation of nickelous bromide and nickelous iodide, preferably use the aqueous solution.Preferred especially nickel chloride aqueous solution.

Under aqueous solution situation, nickel halogenide (II) concentration in water itself is not crucial.Have been found that the advantageous ratio that has of nickel halogenide (II) is at least 0.01 weight % in the gross weight of nickel halogenide (II) and water, preferably at least 0.1 weight %, more preferably at least 0.25 weight %, especially preferably at least 0.5 weight %.The advantageous ratio that has that has been found that in the gross weight of nickel halogenide (II) and water nickel halogenide (II) is 80 weight % at the most, preferred 60 weight % at the most, more preferably 40 weight % at the most.For actual cause, advantageously be no more than the ratio of nickel halogenide in the mixture of nickel halogenide and water when under given temperature and pressure condition, obtaining solution.Therefore, under the situation of nickel chloride aqueous solution, advantageously select at room temperature the ratio of nickel halogenide in the gross weight of nickelous chloride and water to be 31 weight % at the most for actual cause.Under higher temperature, can correspondingly select higher concentration by the solubleness of nickelous chloride in water.

Moisture nickel halogenide (II) carried out drying by component distillation before reduction.In a preferred embodiment of the invention, component distillation is a kind of method of anhydrating of removing from the moisture nickel halogenide (II) of correspondence, wherein make this moisture nickel halogenide (II) and mixing diluents, described thinner is higher than under the boiling point of water and this boiling point at water and forms azeotrope or heteroazeotrope for liquid or under following distillatory pressure and temperature condition with water not forming boiling point under the situation of azeotrope with water under the following distillatory pressure condition at this thinner, and the distillation mixture that comprises moisture nickel halogenide (II) and thinner with from this mixture except that anhydrating or described azeotrope or described heteroazeotrope and obtain comprising the anhydrous mixture of nickel halogenide (II) and described thinner.

Starting mixt can also comprise other composition such as ionic or nonionic organic or inorganic compound except moisture nickel halogenide (II), especially with all even single-phase molten mixed those of starting mixt or dissolve in the starting mixt those.

According to the present invention, moisture nickel halogenide (II) and boiling point are the mixing diluents of liquid under the boiling point that is higher than water under the distillatory pressure condition and this boiling point at water.

Distillatory pressure condition itself is not crucial subsequently.Have been found that favourable pressure is at least 10 ^-4MPa, preferably at least 10 ^-3MPa, especially at least 5 * 10 ^-3MPa.Have been found that favourable pressure is 1MPa at the most, preferably at the most 5 * 10 ^-1MPa, especially at the most 1.5 * 10 ^-1MPa.

The composition that depends on pressure condition and mixture to be distilled is determined distillation temperature.Under this temperature, thinner preferably is liquid form.In the context of the invention, the term thinner refers to single thinner or diluent mixture, and the physicals that the present invention mentioned under the mixture situation relates to this mixture.

In addition, thinner does not preferably form under the situation of azeotrope than water height with water at thinner at the boiling point under these pressure and temperature conditions, is preferably up to few 5 ℃, and especially at least 20 ℃ and preferably at the most 200 ℃, 100 ℃ especially at the most.

In preferred embodiments, can use the thinner that forms azeotrope or heteroazeotrope with water.Compare with the water yield in the mixture, the amount of thinner itself is not crucial.Advantageously, than treating to use more liquid diluent, so that excess amount of diluent keeps as bottoms accordingly by azeotrope distilled amount.

When use does not form the thinner of azeotrope with water, to compare with the water yield in the mixture, the amount of thinner itself is not crucial.

Used thinner especially is selected from the mixture of organic nitrile, aromatic hydrocarbons, aliphatic hydrocarbon and above-mentioned solvent.For organic nitrile, preferably use acetonitrile, propionitrile, n-Butyronitrile, positive valeronitrile, cyano group cyclopropane, vinyl cyanide, crotononitrile, allyl cyanide, cis-2-pentenenitrile, trans-the 2-pentenenitrile, cis-3 pentene nitrile, trans-3 pentene nitrile, allyl acetonitrile, 2-methyl-3-crotononitrile, Z-2-methyl-2-butene nitrile, E-2-methyl-2-butene nitrile, ethyl succinonitrile, adiponitrile, methyl cellosolve acetate glutaronitrile or its mixture.For aromatic hydrocarbons, can preferably use benzene, toluene, o-Xylol, m-xylene, p-Xylol or its mixture.Aliphatic hydrocrbon can be preferably selected from linearity or branched aliphatic hydrocarbon, more preferably is selected from cycloaliphatic hydrocarbon such as hexanaphthene or methylcyclohexane, or its mixture.Especially preferably use cis-3 pentene nitrile, trans-3 pentene nitrile, adiponitrile, methyl cellosolve acetate glutaronitrile or its mixture as solvent.

When used thinner is an organic nitrile or when comprising the mixture of at least a organic nitrile, have been found that the amount of advantageously selecting thinner is so that the ratio of nickel halogenide (II) in the gross weight of nickel halogenide (II) and thinner is at least 0.05 weight % in the final mixture, preferably at least 0.5 weight %, more preferably at least 1 weight %.

When used thinner is an organic nitrile or when comprising the mixture of at least a organic nitrile, have been found that the amount of advantageously selecting thinner so that the ratio of nickel halogenide (II) in the gross weight of nickel halogenide (II) and thinner is 50 weight % at the most in the final mixture, preferred 30 weight % at the most, more preferably 20 weight % at the most.

According to the present invention, distillation comprises the mixture of moisture nickel halogenide (II) and thinner to remove the anhydrous mixture that anhydrates and obtain comprising nickel halogenide (II) and described thinner from this mixture.In preferred embodiments, at first prepare this mixture, then distillation.In another preferred embodiment, with moisture nickel halogenide, more preferably the nickel halogenide aqueous solution adds in the ebullient thinner gradually in still-process.This has prevented to form substantially sees reluctant grease-like solid from the Technology angle.

Under the situation of pentenenitrile as thinner, distillation can be advantageously at 1MPa at the most, carry out under the pressure of preferred 0.5MPa.

Under the situation of pentenenitrile as thinner, distillation can be preferably at 1kPa at least, preferably 5kPa at least more preferably carries out under the pressure of 10kPa at least.

Distillation can advantageously be undertaken by single-stage evaporation, preferably by one or more, carries out as the fractionation in 2 or 3 distillation plants.Useful distillation plant is the equipment that is usually used in this purpose, for example as Kirk-Othmer, and Encyclopedia of Chemical Technology, the 3rd edition, the 7th volume, John Wiley ﹠amp; Sons, New York is described in 1979, the 870-881 pages or leaves, as sieve-tray tower, bubble-cap tray column, the tower with structured packing or random packing, the tower with side material taking mouth or partition tower.

Distillation can be carried out in batches or continuously.

Reduction

The method that contains nickel (0) phosphorous ligand complexes of at least one nickel (0) central atom and at least a phosphorus part by the reduction preparation is preferably carried out in the presence of solvent.Solvent especially is selected from the mixture of organic nitrile, aromatic hydrocarbons, aliphatic hydrocarbon and above-mentioned solvent.For organic nitrile, preferably use acetonitrile, propionitrile, n-Butyronitrile, positive valeronitrile, cyano group cyclopropane, vinyl cyanide, crotononitrile, allyl cyanide, cis-2-pentenenitrile, trans-the 2-pentenenitrile, cis-3 pentene nitrile, trans-3 pentene nitrile, allyl acetonitrile, 2-methyl-3-crotononitrile, Z-2-methyl-2-butene nitrile, E-2-methyl-2-butene nitrile, ethyl succinonitrile, adiponitrile, methyl cellosolve acetate glutaronitrile or its mixture.For aromatic hydrocarbons, can preferably use benzene, toluene, o-Xylol, m-xylene, p-Xylol or its mixture.Aliphatic hydrocrbon can be preferably selected from linearity or branched aliphatic hydrocarbon, more preferably is selected from cycloaliphatic compounds such as hexanaphthene or methylcyclohexane or its mixture.Especially preferably use cis-3 pentene nitrile, trans-3 pentene nitrile, adiponitrile, methyl cellosolve acetate glutaronitrile or its mixture as solvent.

The preferred inert solvent that uses.

The concentration of solvent is preferably 10-90 quality %, and more preferably 20-70 quality %, especially 30-60 quality % are in each case based on final reacting mixture.

In particular embodiment of the present invention, it is identical that solvent and above-mentioned preparation comprise in the inventive method of anhydrous mixture of nickel halogenide (II) and thinner used thinner.

In the methods of the invention, the concentration of part in solvent is preferably 1-90 weight %, more preferably 5-80 weight %, especially 50-80 weight %.

Used reductive agent is preferably selected from than nickel and has more electropositive metal in the inventive method, metal alkyls, electric current, complex hydride and hydrogen.

When reductive agent used in the inventive method is that this metal is preferably selected from sodium, lithium, potassium, magnesium, calcium, barium, strontium, titanium, vanadium, iron, cobalt, copper, zinc, cadmium, aluminium, gallium, indium, tin, lead and thorium when having more electropositive metal than nickel.At this preferred especially iron and zinc.When with aluminium when the reductive agent, advantageously by with mercury (II) salt of catalytic amount or metal alkyls reaction and with its pre-activation.Preferably with 0.05-50mol%, more preferably the amount of 0.5-10mol% uses triethyl aluminum to activate in advance.The reducing metal is preferably in small, broken bits, and phrase " in small, broken bits " is meant that metal with less than 10 orders, is more preferably less than 20 purpose granularities and uses.

When used reductive agent in the inventive method is that the amount of metal is preferably 0.1-50 weight % based on reaction mixture when having more electropositive metal than nickel.

When with metal alkyls during as the reductive agent in the inventive method, they are preferably lithium alkylide, sodium alkyl, alkyl magnesium, especially Grignard reagent, zinc alkyl(s) or aluminum alkyls.Special preferred alkyl aluminium such as trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand or its mixture, especially triethyl aluminum.Metal alkyls can be used under solvent-free or be dissolved in inert organic solvents such as hexane, heptane or the toluene.

When complex hydride during as the reductive agent in the inventive method, is preferably used metal alanates such as lithium aluminum hydride, or metal borohydride such as sodium borohydride.

The mol ratio of the oxid-reduction equivalent between nickel (II) source and reductive agent is preferably 1: 1-1: 100, more preferably 1: 1-1: 50, especially 1: 1-1: 5.

In the methods of the invention, used part can also be with at hydrocyanation reaction such as step e ^*) or isomerization reaction such as step a ^*) in use and the ligand solution of poor nickeliferous (0) exists as catalyst solution.These materials flows are respectively materials flow 3 and 10, they or part or be respectively independently at step h in each case ^*) and the step of back, suitable words step I ^*), j ^*) and K ^*) middle selected son stream of carrying 14 (from son stream 3) and sub-stream 16 (from son stream 10).Any residual son stream 15 (from materials flows 3) and 17 (from materials flows 10) are not all carried and are passed through h ^*), i ^*), j ^*) and K ^*), but directly be recycled to step a ^*) or e ^*).Should " return catalizer solution " have following composition usually:

-2-60 weight %, especially 10-40 weight % pentenenitrile,

-0-60 weight %, especially 0-40 weight % adiponitrile,

-0-10 weight %, especially other nitrile of 0-5 weight %,

-10-90 weight %, especially 50-90 weight % phosphorus part and

-0-2 weight %, especially 0-1 weight % nickel (0).

In the method for the invention, therefore the free ligand that exists in this return catalizer solution can be changed into again nickel (0) title complex.

In particular embodiment of the present invention, nickel (II) source is 1 with the ratio of phosphorus part: 1-1: 100.Further preferred nickel (II) source is 1 with the ratio of phosphorus part: 1-1: 3, especially 1: 1-1: 2.

The inventive method can be carried out under any pressure.Because actual, preferred pressure is the 0.1-5 bars absolute, preferred 0.5-1.5 bars absolute.

The inventive method can batch mode or is carried out continuously.

In the methods of the invention, can not use excessive nickel halogenide (II) or reductive agent such as zinc to operate, thereby need not after nickel (0) title complex forms, to remove them.

In particular embodiment of the present invention, the inventive method comprises following process steps:

(1) by the moisture nickel halogenide of azeotropic distillation drying (II),

(2) in the presence of the phosphorus part in solvent the nickel halogenide of its pre-mated azeotropic drying (II),

(3) under 20-120 ℃ charge temperature, at least a reductive agent added in the solution or suspension from processing step (2),

(4) under 20-120 ℃ temperature of reaction, stir suspension or solution from processing step (3).

Its pre-mated temperature, charge temperature and temperature of reaction can be 20-120 ℃ independently of one another.In its pre-mated, reinforced and reaction, preferred 30-80 ℃ temperature especially.

Its pre-mated time, reinforced time and reaction times can be 1 minute to 24 hours independently of one another.Its pre-mated time especially is 1 minute to 3 hours.The reinforced time is preferably 1-30 minute.Reaction times is preferably 20 minutes to 5 hours.

Processing step h ₂ ^*):

Processing step h ^*) another preferred embodiment (be described as the h of processing step here ₂ ^*)) comprise for example by in nickel powder, stirring and nickel (0) content of make-up stream 14 or 16.When doing like this, the free phosphorus part in the materials flow 14 or 16 forms material or adds fresh part as title complex.

Catalyst complexes can be by nickel powder and suitable halide source preparation as initiator, and the latter for example be the halogenide or the alkyl replacement halogenide of phosphorus, arsenic or antimony, as CH ₃PCl ₂, CH ₃AsCl ₂Or CH ₃SbCl ₂, or suitable metal halide, elemental halogen such as chlorine, bromine or iodine, or corresponding hydrogen halide or thionyl halide.Metal halide is the halogenide of Cr, Ni, Ti, Cu, Co, Fe, Hg, Sn, Li, K, Ca, Ba, Sc, Ce, V, Mn, Be, Ru, Rh, Pd, Zn, Cd, Al, Th, Zr and Hf used according to the present invention.Halogenide can be muriate, bromide or iodide.Specially suitable halide source is PX ₃, TiX ₄, ZrX ₄, HfX ₄Or HX, wherein X is muriate, bromide or iodide.When carrying out the present invention and react, can also use two or more initiators or mixture of catalysts.

Catalyst regeneration can carry out in batches, and for example similar US 3,903,120 carries out with batch mode, or similar and US 4,416,825 carries out continuously, and temperature is 0-200 ℃, and preferred 25-145 ℃, more preferably 50-100 ℃.The residence time of catalyzer can change in wide region and be generally 15 minutes to 10 hours, and preferred 20 minutes to 5 hours, more preferably 30 minutes to 2 hours.

When carrying out processing step h ₂ ^*) rather than processing step h ₁ ^*) time, suitable words can be omitted processing step i wholly or in part ^*), j ^*) and k ^*).

Processing step i ^*):

Necessary words can be in step I) before by for example at the 0.1-5000 millibar, preferred 0.5-1000 millibar, especially the absolute pressure of 1-200 millibar and 10-150 ℃, distill or adopt other suitable measures that materials flow 18 is concentrated under preferred 40-100 ℃ the temperature and for example be the 50-95% of its initial volume, preferred 60-90%.In particularly preferred embodiments, this materials flow contains 10 weight % at the most after concentrating, i.e. 0-10 weight %, preferably 0.01-8 weight % pentenenitrile.

Step I ^*): add nonpolar aprotic liquids L

In step I ^*) in, will obtain materials flow 19 in the nonpolar aprotic liquids L adding materials flow 18.Thus, liquid is meant that compound L is in step I ^*) the pressure and temperature condition under exist with liquid form; Under other pressure and temperature conditions, L also can be solid or gas.

Suitable nonpolar aprotic liquids L is in step I ^*) condition under for liquid and only non-(if having words) significantly change catalyzer with chemistry or physics mode, for example have all compounds of Ni (0) title complex of phosphorus part and/or free phosphorus part.The compound that is suitable as liquid L does not contain any ionizable proton and has low relative permittivity (ε usually in molecule _r＜15) and low electric dipole moment (μ＜2.5 debye).

Especially suitable is for example can be not halo or halogenated hydro carbons, also has amine, especially tertiary amine, and dithiocarbonic anhydride.

In preferred embodiments, liquid L is hydrocarbon H ^*Suitable hydrocarbon H ^*Be aliphatic series, cyclic aliphatic or aromatic hydrocarbon.Suitable aliphatic hydrocrbon is for example for having 5-30, linearity or branched paraffin or alkene, especially pentane, hexane, heptane, octane, nonane, decane, undecane and the dodecane (being all isomer in each case) of preferred 5-16 carbon atom.

Suitable cycloaliphatic hydrocarbon for example has 5-10 carbon atom, as pentamethylene, hexanaphthene, suberane, cyclooctane, cyclononane and cyclodecane.Replace, especially C _1-10The cycloaliphatic hydrocarbon that alkyl replaces also is suitable as methylcyclohexane.Suitable aromatic hydrocarbons is preferably those with 6-20 carbon atom, especially benzene, toluene, o-Xylol, m-xylene, p-Xylol, naphthalene and anthracene.Can also use replacement, preferred C _1-10Aromatic hydrocarbons such as ethylbenzene that alkyl replaces.

Hydrocarbon H ^*The compound of below more preferably being selected from hydrocarbon H being mentioned.Hydrocarbon H very particularly preferably ^*H is identical with hydrocarbon, is about to identical hydrocarbon and is used for step j ^*) in extraction and as liquid L.

The mode that adds liquid

Can in conventional mixing equipment, nonpolar aprotic liquids L be added in the materials flow 18.Because see from technical standpoint simple especially, preferably in stirred vessel or pumping circulation system with nonpolar aprotic liquids L and materials flow 18 in step I ^*) the middle mixing.

Preferably with nonpolar aprotic liquids and materials flow 18 uniform mixing.Suitable stirred vessel is the conventional liq mixing tank that powerful mixing element and/or static or mobile internals can be housed.

The same preferred pumping circulation system that uses.It is 0.1 that its operation should make pumping circulation amount and ratio from the work output of pumping circulation system usually: 1-1000: 1, preferred 1: 1-100: 1, more preferably 2: 1-25: 1 suitable recycle pump for example is toothed gear pump or other conventional pumps.Recycle pump is preferably facing to for example operating for the surplus valve of opening under the qualification pressure of 3-10 bars absolute.

When in step I ^*) and j ^*) in when using identical hydrocarbon, in these two steps, can also use fresh hydrocarbon in each case.Equally can be at step j ^*) in utilize step I again ^*) used hydrocarbon, perhaps in step I ^*) recirculation step j afterwards ^*) in used hydrocarbon and wherein utilizing again again.

In embodiment very particularly preferably, liquid L is the son stream (be rich in the hydrocarbon H of catalyzer, see below) of materials flow 22, and this son stream is at step j ^*) in obtain.This means at step j ^*) in a part of materials flow 22 told and this told part in step I ^*) the middle adding in the materials flow 18.In this embodiment, a part of materials flow 22 that therefore circulates.

In another same embodiment preferred, directly nonpolar aprotic liquids L is metered into delay zone (seeing below), for example begin the place and add at it.

Liquid L is usually at 0-150 ℃, and preferred 10-100 ℃, especially 20-80 ℃ temperature and 0.01-100 crust adds under the absolute pressure that preferred 0.1-10 crust, especially 0.5-5 cling to.

The required amount of liquid L can change in wide region.This amount is usually less than at step j ^*) in the amount of used hydrocarbon H when extracting, but also can be greater than described amount.Based on being used for step j ^*) in the hydrocarbon H amount of extraction, the amount of liquid L is preferably 0.1-200 volume %, especially 1-50 volume %, more preferably 5-30 volume %.

Optional with ammonia or amine processing

As step h ^*) when comprising oxidation-reduction and regeneration, suitable words can be in materials flow 18 or materials flow 19 or in step I ^*) or step j ^*) add ammonia or aromatics or aliphatic series primary, the second month in a season or tertiary amine in the process itself.Aromatic amine comprises that alkyl aromatic amine and aliphatic amine comprise cycloaliphatic amine.

Have been found that the processing of this ammonia or amine can be at extraction (step j ^*)) in reduce catalyzer, especially nickel (0) title complex in second phase (materials flow 23) be rich in dintrile or the content of part, promptly in extraction, Ni (0) title complex or part being distributed with between two-phase are beneficial to first phase (materials flow 22) and are offset.It is long-pending that this ammonia or amine are handled the catalyst-rich of having improved in the materials flow 22; This means that in catalyst return catalyst loss is littler and improved the economic feasibility of hydrocyanation.

Therefore, in this embodiment, before extraction, handle materials flow 18 or materials flow 19, perhaps in extraction process, carry out described processing with ammonia or amine.It is not too preferred handling in extraction process.

Especially preferably ammonia or amine are added with nonpolar aprotic liquids L.Especially in same mixture equipment, add liquid L and ammonia or amine.

Used amine is monoamine, diamines, triamine or higher functional amine (polyamines).Monoamine has alkyl, the aryl or aralkyl that contains 1-30 carbon atom usually; Suitable monoamine for example is a primary amine, monoalkylamine for example, secondary amine or tertiary amine, for example dialkylamine.Suitable uncle's monoamine for example is butylamine, hexahydroaniline, 2-methylcyclohexyl amine, 3-methylcyclohexyl amine, 4-methylcyclohexyl amine, benzylamine, tetrahydrofurfuryl amine and chaff amine.Useful secondary monoamine for example is diethylamine, dibutylamine, di-n-propylamine and N-methylbenzylamine.Suitable tertiary amine is for example for having C _1-10The trialkylamine of alkyl is as Trimethylamine 99, triethylamine or Tributylamine.

Suitable diamines for example is formula R ¹-NH-R ²-NH-R ³Those, R wherein ¹, R ²And R ³Be hydrogen or alkyl, aryl or aralkyl independently of one another with 1-20 carbon atom.Alkyl can be linearity, or especially for R ²Can also be ring-type.Suitable diamines for example is a quadrol, propylene diamine (1 and 1, the 3-diaminopropanes), N-methyl ethylenediamine, piperazine, tetramethylene-diamine (1, the 4-diaminobutane), N, N '-dimethyl-ethylenediamine, N-ethylethylenediamine, 1,5-diamino pentane, 1,3-diamino-2, the 2-diethyl propane, 1,3-two (methylamino) propane, hexamethylene-diamine (1), 1,5-diamino-2-methylpentane, 3-(propyl group amino) propylamine, N, N '-two (3-aminopropyl) piperazine, N, N '-two (3-aminopropyl) piperazine and isophorone diamine (IPDA).

Suitable triamine, tetramine or higher functional amine for example are three (2-amino-ethyl) amine, three (2-aminopropyl) amine, diethylenetriamine (DETA), Triethylenetetramine (TETA) (TETA), tetren (TEPA), isopropylidene triamine, dipropylenetriamine and N, N '-two (3-aminopropyl quadrol).Amino-benzylamine and amino hydrazides with 2 or more a plurality of amino are suitable equally.

Certainly can also use the mixture of ammonia and one or more amine, or the mixture of various kinds of amine.

Preferably use ammonia or aliphatic amine, especially have the trialkylamine of 1-10 carbon atom in alkyl, for example Trimethylamine 99, triethylamine or Tributylamine also have diamines such as quadrol, hexamethylene-diamine or 1,5-diamino-2-methylpentane.

Especially preferably only use ammonia, promptly especially preferably except ammonia, do not use amine.Anhydrous ammonia very particularly preferably; Thus, the anhydrous water-content that is meant is lower than 1 weight %, preferably is lower than 1000 ppm by weight, especially is lower than 100 ppm by weight.

The mol ratio of amine and ammonia can change in wide region and be generally 10000: 1-1: 10000.

The factor of the consumption of decision ammonia or amine comprises type and the consumption and the use of catalyzer such as nickel (0) catalyzer and/or part, is used as the lewis acidic type and the consumption of promotor in hydrocyanation.Usually, it is crucial usually and for example be 100: 1 that ammonia or amine and lewis acidic mol ratio are at least the upper limit of 1: 1 this mol ratio, but the excessive of ammonia or amine should be greatly to making the decomposition of Ni (0) title complex or its part.Ammonia or amine and lewis acidic mol ratio are preferably 1: 1-10: 1, more preferably 1.5: 1-5: 1, and especially about 2: 1.When using the mixture of ammonia and amine, these mol ratios are applicable to the summation of ammonia and amine.

Temperature in handling with ammonia or amine is not crucial usually and for example be 10-140 ℃, and preferably 20-100 ℃, especially 20-90 ℃.Pressure is not crucial usually yet.

Ammonia or amine can gases, liquid (depressing adding) or the solubilized form in solvent add in the materials flow 18.Suitable solvent for example is nitrile, especially those that exist in hydrocyanation, also has the aliphatic series, cyclic aliphatic or the aromatic hydrocarbons that are used as extraction agent in the methods of the invention, for example hexanaphthene, methylcyclohexane, normal heptane or octane.

Ammonia or amine conventional equipment as be used for that gas introduces those or in liquid mixer, add.Precipitated solid can be stayed in the materials flow 18 in many cases, is about to suspension and infeeds in the extraction, perhaps can as described belowly remove.

Optional solid is removed

In preferred embodiments, at extraction (step j ^*)) before will be in the step I of this method ^*) in the solid that is precipitated out from materials flow 19, remove.

In many cases, this makes the extracting operation of the inventive method be able to further improvement, because the solid that occurs reduces the separation performance of extraction equipment usually.Having found also that solid before extraction is removed in many cases obviously to reduce again or to have suppressed undesirable broken foam (rag) fully forms.

Preferably carry out solid and remove and make and to remove hydraulic diameter, especially greater than 1 μ m, more preferably greater than the solid particulate of 100nm greater than 5 μ m.

Remove for solid, can use ordinary method, for example filtration, cross flow filter, centrifugal, sedimentation, classification or preferred decantation can use conventional equipment such as strainer, whizzer or decantor for this reason.

The temperature and pressure that solid is removed is not crucial usually.For example, can in above-mentioned or following temperature and pressure scope, operate.

Solid remove can materials flow 18 or materials flow 19 are optional handle with ammonia or amine before, among or carry out afterwards.Preferably among ammonia or amine are handled or remove afterwards, especially preferably after handling, remove.

When among ammonia or amine are handled or when removing solid afterwards, the compound that solid is generally ammonia or amine and used Lewis acid or is slightly soluble in the promotor in the materials flow 18.For example when using ZnCl ₂The time, sl. sol. substantially ZnCl ₂2NH ₃In ammonia treatment, be precipitated out.

When before ammonia or amine are handled, removing solid, or if ammonia of no use or amine are handled at all, solid is generally+nickel compound of II oxidation state, for example nickel cyanide (II) or similar nickel (II) compound that contains the cyanogen root, or Lewis acid or its compound.Described compound for example can be precipitated out, because their solubleness for example reduces by temperature variation.

Optional delay zone

As from step I ^*) the materials flow 19 of effluent can for example directly transfer to step j by pipeline ^*) in.Be meant that directly the mean residence time of materials flow 19 in pipeline was less than 1 minute.

Yet, in the preferred embodiment of the inventive method, in step I ^*) afterwards and at step j ^*) materials flow 19 is carried pass through delay zone before.Therefore delay zone is positioned at the reinforced downstream of liquid L and the upstream of extraction.

Suitable delay zone for example is container or groups of containers and these combination of elements of pipeline, static mixer, stirring or not stirring.Preferably delay zone is configured to the mean residence time of materials flow 19 in this delay zone and is at least 1 minute, preferably at least 5 minutes.

Above-mentioned optional solid is removed also and can be carried out in delay zone.At this moment, delay zone can settled zone of silence as solid.In this way, delay zone works as decantor or cross-flow filter.Can be provided for carrying and/or discharging solid equipment.

As mentioned above, in preferred embodiments, directly nonpolar aprotic liquids L is metered into delay zone, for example begins the place at it.In this embodiment, materials flow 18 and the mixed uniformly delay zone of liquid L are guaranteed in preferred especially selection.Similarly, as described above, delay zone may cause being separated of materials flow 19.

Delay zone is usually at 0-200 ℃, and preferred 10-150 ℃, especially 20-100 ℃ temperature and 0.01-100 crust is operated under the absolute pressure that preferred 0.1-10 crust, especially 0.5-5 cling to.

In preferred embodiments, the flow velocity in used in the methods of the invention all pipelines of materials flow 19 is at least 0.5m/s, 1m/s especially at least, more preferably 2m/s at least.

The suitable words of the materials flow that in step a), obtains 19 after handling and/or after removing solid and/or after passing through delay zone with ammonia or amine at step j ^*) middle extraction.

Processing step j ^*):

Technological principle

The inventive method be suitable for by adding C6 dintrile such as adiponitrile (ADN), 2-methyl cellosolve acetate glutaronitrile (MGN) or 2-ethyl succinonitrile (ESN) with regard to the component of breaking purification by liquid extraction in materials flow 19 or suitable words ought not carry out step I ^*) time in materials flow 18, contain Ni (0) title complex of phosphorus part and/or free phosphorus part, the described component of breaking increases the C5 mononitrile that is unsuitable for hydrocyanation such as the formation of E-2-methyl-2-butene nitrile and/or Z-2-methyl-2-butene nitrile.

In addition, reduced the catalyst loss in the extraction by in materials flow 21, introduce hydrocarbon H in the entrance of the exit point of comparing more close extraction liquid with the entrance of incoming flow 18 or 19.Compare the exit point of the more close raffinate in entrance of dintrile (materials flow 20) with the entrance of incoming flow 18 or 19.Thus, more closely should understand from the theoretical plate number between 2 o'clock.Between the entrance of materials flow 18 or 19 and 21, have 0-10 usually, the preferred theoretical extraction of 1-7 (separation) section (extraction section again of catalyzer); Between the entrance of materials flow 18 or 19 and 20, have 1-10 usually, preferred 1-5 theoretical extraction (separation) section (purification section with regard to the component of breaking).

Usually, the first phase [raffinate; Materials flow 22] temperature T (℃) form down and compare and be rich in described Ni (0) title complex or part with materials flow 18, and the second [extraction liquid mutually that is rich in dintrile is compared in formation with materials flow 18; Materials flow 23; Be rich in the component of breaking].Usually, first be light phase mutually, i.e. upper strata phase, and second be than heavy phase mutually, i.e. lower floor's phase.

After being separated, 50-99 weight % is preferably contained on the upper strata mutually, more preferably 60-97 weight %, the especially 80-95 weight % hydrocarbon that is used to extract.

(particularly be to work as in some cases at processing step h ₁ ^*) in carry out redox catalyst when regeneration) Lewis acid that is present in the inlet materials flow of extraction is preferably most of, more preferably be retained in fully lower floor mutually in.Residual concentration in mutually is more preferably less than 0.5 weight %, especially less than 500 ppm by weight preferably less than 1 weight % to the Lewis acid that is meant fully here on the upper strata.

The discharge of the component of breaking has improved process choice, because form the less C5 mononitrile that is unsuitable for hydrocyanation (reducing incorrect isomerization).

The special advantage of embodiment III is at processing step e ^*) in a small amount of form and therefore accumulate in dintrile in the materials flow 10 such as ADN, MGN, ESN and discharge mutually to the lower floor of small part with extraction.

Use processing step j ^*) another special advantage be to be used for processing step e ^*) in reactant can be the divinyl that contains stablizer.This stablizer for example can be tert-butyl catechol.This stablizer is discharged mutually via the lower floor of extraction.Therefore, the concentration of stablizer can not gather the infringement catalyzer in catalyst return.

Another special advantage is to be used for according to h ₁ ^*) replenish the catalyzer of Ni (0) value oxidation-reduction and regeneration can be at processing step h ^*) in carry out because in this way the Lewis acid of Xing Chenging via the extraction lower floor discharge mutually.This Lewis acid otherwise can cause first hydrocyanation (processing step e ^*)) in the formation of dintrile increase.

The lower floor of extraction can suitably carry out aftertreatment mutually, thereby the dintrile that wherein exists can be used as once more the charging of extraction.This aftertreatment for example can be undertaken that (DE-A-10 2004004683 by distillation; Materials flow 7 from step c)).

The structure of extraction

The counter-current extraction tower that the extraction task can be preferably has an extraction section by use is again finished.Yet, the combination of the combination of the known suitable equipment of any those skilled in the art such as counter-current extraction tower, mixing tank-settling vessel unit or mixing tank-settling vessel unit and tower, for example two counter-current extraction towers be connected in series (for example purification that is used for about the component of breaking, another is used for the extraction again of catalyzer) also have identical function.The counter-current extraction tower of sheet metal filler as dispersive element especially is equipped with in preferred especially use.In further particularly preferred embodiment, extraction adverse current in stirring extraction tower is at interval carried out.

For the dispersive direction, in the preferred embodiment of the inventive method with hydrocarbon as external phase and with the materials flow 18 of hydrocyanation as disperse phase.The formation that this has shortened the time that is separated usually and has reduced broken foam.Yet, also can disperse in the other direction, be about to materials flow 18 and be used as disperse phase as external phase and with hydrocarbon.When remove (seeing below) by preferential solid, higher temperature or use suitable hydrocarbon to reduce or suppress especially to adopt when broken foam forms the latter fully in extraction or in being separated.Usually select the dispersion direction more favourable to the separation performance of extraction equipment.

In extraction, set following charge ratio: materials flow 20 and materials flow 18 or 19 and the ratio of the summation of materials flow 21 be 0.01-10kg/kg, preferred 0.05-5kg/kg.Materials flow 21 is 0.05-20kg/kg with the ratio of materials flow 20, preferred 1-10kg/kg.Materials flow 21 is 0.05-20kg/kg with the ratio of materials flow 18 or 19, preferred 0.5-8kg/kg.

Absolute pressure in extraction process is preferably 10kPa to 1MPa, more preferably 50kPa to 0.5MPa, especially 75kPa to 0.25MPa.

Extraction especially 20-100 ℃, is more preferably carried out under 30-80 ℃ the temperature preferably at-15 to 120 ℃.Have been found that broken foam forms lower under higher extraction temperature.

The structure that is separated

Depend on the equipment structure, be separated and on room and time, regard the final section of extraction as.For being separated, can selecting wide pressure, concentration and temperature range usually, and can easily determine parameter by several simple tentative experiments to specific composition the best of reaction mixture.

Temperature T in being separated is generally at least 0 ℃, and preferably at least 10 ℃, more preferably at least 20 ℃.This temperature is generally 120 ℃ at the most, and preferably at the most 100 ℃, more preferably at the most 95 ℃.For example, be separated, carry out under preferred 60-95 ℃ at 0-100 ℃.Have been found that broken foam forms lower under higher phase separation temperature.

Pressure in being separated is generally 1kPa at least, preferably 10kPa, more preferably 20kPa at least.Pressure is generally 2MPa at the most, preferred 1MPa at the most, more preferably 0.5MPa at the most.

Be separated the time, i.e. materials flow 18 begins to the uniform upper strata of formation mutually with hydrocarbon (extraction agent) mixing and the time of uniform lower floor phase can change in wide region.The time of being separated is generally 0.1-60 minute, and preferred 1-30 minute, especially 2-10 minute.When the inventive method was carried out with technical scale, the time of being separated was no more than 15 minutes, especially be no more than 10 minutes technology and economically feasible normally.

Have been found that especially when with long chain aliphatic paraffinic hydrocarbons such as normal heptane or octane during as hydrocarbon H, the time that is separated reduces with advantageous manner.

Be separated and in one or more known equipment of field those of skill in the art that are separated, carry out.In advantageous embodiment, be separated and can in extraction equipment, carry out, for example in one or more mixing tanks-settling vessel combination, carry out, or undertaken by zone of silence is loaded on the extraction tower.

In being separated, obtain two kinds of liquid phases, wherein a gross weight based on this phase has and compares more a high proportion of nickel (0) title complex that has phosphorus part and/or free phosphorus part with other.Other are rich in the component of breaking mutually.

Dintrile

The materials flow of sending in the extraction as incoming flow 20 mainly comprises dintrile, preferred C6 dintrile, especially preferred adiponitrile (ADN), 2-methyl cellosolve acetate glutaronitrile (MGN), 2-ethyl succinonitrile (ESN) or its mixture.Dintrile content in this materials flow is preferably greater than 50 weight %, more preferably greater than 70 weight %, especially is preferably greater than 90 weight %.Preparation dintrile, the especially method of C6 dintrile itself are known.A kind of this possible method is described among the DE-A-10 2,004 004683.The materials flow for preparing the C6 dintrile in this way is especially from DE-A-10 2,004 004683 processing step h) materials flow 15,16 and 17 be suitable as materials flow 20 usually and be used for this paper.

Preferably with at extraction section k ^*) in the degree that is separated add dintrile.

Hydrocarbon

Hydrocarbon is an extraction agent.Its boiling point is preferably at least 30 ℃, and more preferably at least 60 ℃, especially at least 90 ℃, and preferably at the most 140 ℃, more preferably at the most 135 ℃, 130 ℃ especially at the most, in each case 10 ⁵Under the absolute pressure of Pa.

More preferably the hydrocarbon of single hydrocarbon of the context of the invention middle finger or hydrocarbon mixture can be used for especially removing adiponitrile by extraction from comprising adiponitrile and containing Ni (0) mixture of catalysts, the boiling point of described hydrocarbon is 90-140 ℃.Can be advantageously remove dealkylation and obtain adiponitrile, use the hydrocarbon of boiling point in described scope feasible especially economically and technically to remove simply because of can allowing with the hydrocarbon that the river condensation steams by the mixture that after removing, obtains by this method by distillation.

Suitable hydrocarbon for example is described in US 3,773, during 809 the 3rd hurdle 50-62 are capable.Useful hydrocarbon is preferably selected from the octane of heptane, octane, octane-iso, isomery of hexanaphthene, methylcyclohexane, suberane, normal hexane, normal heptane, isomery as 2,2,4-trimethylpentane, cis-and trans-naphthane or its mixture, especially the octane of the heptane of hexanaphthene, methylcyclohexane, normal heptane, isomery, octane, isomery is as 2,2,4-trimethylpentane, or its mixture.Especially preferably use hexanaphthene, methylcyclohexane, normal heptane or octane.

Very particularly preferably normal heptane or octane.Under the situation of these hydrocarbon, undesirable broken foam forms low especially.Broken foam refers to that the upper strata mutually and the zone that not exclusively is separated between mutually of lower floor, is generally liquid/liquid mixture, wherein can also be dispersed with solid.It is undesirable that excessive broken foam forms, because it hinders extraction and extraction equipment to be flooded by broken foam in some cases, the possibility of result can not be finished the separation task.

Used hydrocarbon is preferably anhydrous, and the anhydrous water-content that is meant is lower than 100 ppm by weight, preferably is lower than 50 ppm by weight, especially is lower than 10 ppm by weight.This hydrocarbon can pass through known appropriate method of those skilled in the art such as absorption or component distillation and drying.Dry can carrying out in the step before the inventive method.

Processing step k ^*):

At processing step (k ^*) middle distillation materials flow 22, the materials flow 24 that obtains comprising the materials flow 25 of at least a catalyzer and comprise extraction agent.

This processing step is used to reclaim catalyzer and extraction agent substantially.

Processing step (k ^*) can in the known suitable equipment of any those skilled in the art, carry out.Processing step k ^*) distillation preferably in one or more evaporator sections, carry out, perhaps in rectifying tower/distillation tower, carry out.

Be used for two or more the combination of separation internals of the preferably structurized sheet metal filler of internals of rectifying tower/distillation tower, structurized fabric filler, bubble deck, double-pass tray or random packing bed or these classifications.Processing step k ^*) rectifying tower/distillation tower can be constructed with one or more liquid or gas side material taking mouth.Processing step k ^*) rectifying tower/distillation tower can be constructed with the partition tower of one or more gases or hydraulic fluid side material taking mouth.

Processing step k ^*) one or more evaporator sections or rectifying tower/distillation tower falling-film evaporator, thin-film evaporator, natural-circulation evaporator, pump circulation flasher and heterogeneous screw and vertical tube evaporator especially can be housed.

In another embodiment of the inventive method, processing step k ^*) evaporation element at least one to separate operation at the bottom of the tower, be transported to vaporizer at the bottom of taking out very big usually first tower of recycle stream by described evaporator section of materials flow with respect to the bottom this moment, but come the liquid output materials flow of flash-pot directly not return at the bottom of this tower, but with at the bottom of second tower that separates at the bottom of this first tower in collect, taking-up materials flow and the excessive part overflow of residue of flash-pot recycle stream in the future enter at the bottom of first tower bottom obtaining at the bottom of this second tower, to obtain from the taking-up materials flow of the bottom at the bottom of second tower and to compare the poor mixture that contains low-boiling point material from the taking-up materials flow at the bottom of first tower.

Processing step k ^*) in absolute pressure be preferably 0.001-2 crust, more preferably 0.01-0.5 crust, especially 0.09-0.12 crust.Distillation more preferably 70-120 ℃, is especially carried out under 80-100 ℃ the distillation plant bottom temp preferably at 40-150 ℃.Distillation more preferably 0-60 ℃, is especially carried out under 20-50 ℃ the distillation plant head temperature preferably at-15 to 100 ℃.In the particularly preferred embodiment of the inventive method, all keep the said temperature scope in the two at bottom and top.

When at processing step k ^*) in remove extraction agent when reclaiming catalyzer, suitable words can add 3 pentene nitrile in the distillation as middle boiling point material.This solvent change has following advantage in some cases: at enough low and used nickel catalyzators of not pyrolytic damage and when using unidentate ligand, can from the high boiling point catalyst materials flow, effectively remove extraction agent under the evaporator temperature of the used nickel catalyzator of not hot preservation (conserve) when using chelating ligand especially in each case, wherein pressure still enough height with still can be in vaporizer section or distillation tower top under the conventional temperature of cooling water at 25-50 ℃ condensation compare with catalyst component and have more lower boiling extraction agent.This solvent change additionally has following advantage in some cases: the flowability and the single phase property of catalyst solution guaranteed, because depend on the residual content of temperature and extraction agent-do not add 3 pentene nitrile-catalyst component to crystallize out in some cases.At this moment, based on processing step j ^*) in the extraction agent inlet materials flow total amount of extraction tower be 10 weight % at the most, more preferably 5 weight % at the most, especially at the most under the concentration of 1 weight %, for example depend on that pressure condition only can not have damaging influence from the 3 pentene nitrile of removing or can not remove fully because the minimum vapor pressure azeotrope forms to the inventive method in difficulty ground from hexanaphthene or methylcyclohexane or heptane or normal heptane extraction agent.

In the preferred embodiment of the inventive method, will be at processing step k ^*) in the materials flow that comprises extraction agent 24 to the small part that obtains be recycled to extraction step j ^*) in.Suitable words are at extraction step j ^*) materials flow 24 of dry recirculation before, thereby make the water-content in this materials flow preferably be lower than 100 ppm by weight, more preferably less than 50 ppm by weight, especially be lower than 10 ppm by weight.

In another preferred embodiment of the inventive method, will be at processing step k ^*) in the materials flow that comprises catalyzer 25 to the small part that obtains be recycled to processing step e ^*) hydrocyanation or processing step a ^*) isomerization in.In the preferred embodiment of the inventive method, the ratio of extraction agent in materials flow 25 preferably is lower than 10 weight % based on the total amount of materials flow 25, more preferably less than 5 weight %, especially is lower than 1 weight %.

Describe by processing step a below with reference to schema 1-5 ^*)-k ^*) the preferred embodiment of catalyst flow control.Processing step i ^*) be not presented among the schema 1-5, but in each case can be at h ^*) and j ^*) between carry out.In schema 1-5, processing step h ^*) be described as processing step h in this embodiment as an example ₁ ^*).In addition, this embodiment also can be used as processing step h ₂ ^*) carry out.In these cases, nickelous chloride (II) is replaced by nickel powder and is not had reductive agent, also without any Lewis acid (LA).ADN represents the dintrile materials flow with the free burial ground for the destitute; Heptane is the hydrocarbon of extraction agent with the free burial ground for the destitute masterpiece.Catalyzer in each case refers to that catalyst complexes adds free ligand.Dotted line among the schema 1-5 is represented the optional bypass stream of catalyst stream.

This method is shown in the schema 1 about the particular embodiment of catalyst flow control.In this schema, catalyst transport workshop section is incorporated in the single catalyst loop.Order by the workshop section that the first time, hydrocyanation began is e ^*), f ^*), a ^*), b ^*), c ^*), h ^*), suitable words i ^*), j ^*), k ^*), send e then back to ^*).Suitable words can be walked around the h of workshop section with the recirculation of catalysis jizi for making dumplings stream ^*), i ^*), j ^*) and k ^*) and directly enter e ^*).Here to a of workshop section ^*) infeed the not separating mixture of 2-methyl-3-crotononitrile and 3 pentene nitrile, can be at a ^*) carry out d afterwards ^*) or g ^*).

This method is shown in the schema 2 about another particular embodiment of catalyst flow control.In this schema, catalyst transport workshop section is incorporated in the single catalyst loop.By the workshop section that the first time, hydrocyanation began is e in proper order ^*), f ^*), a ^*), b ^*), c ^*), h ^*), suitable words i ^*), j ^*), k ^*), send e then back to ^*).Suitable words can be walked around the h of workshop section with the recirculation of catalysis jizi for making dumplings stream ^*), i ^*), j ^*) and k ^*) and directly enter e ^*).Here to a of workshop section ^*) infeed the poor 2-methyl-3-crotononitrile that contains 3 pentene nitrile, promptly at a ^*) carry out d before ^*) or g ^*).

This method is shown in the schema 3 about another particular embodiment of catalyst flow control.In this schema, catalyst stream is cycled through the e of workshop section ^*) and f ^*).Flow and should flow as a of workshop section by son by this materials flow discharging ^*) catalyst charge.Then that this materials flow is complete, suitable words part is carried by the b of workshop section ^*), c ^*), h ^*), suitable words i ^*), j ^*) and k ^*), and get back to e ^*).To a of isomerization workshop section ^*) infeed the poor 2-methyl-3-crotononitrile that contains 3 pentene nitrile, promptly at a ^*) carry out d before ^*) or g ^*).Equally also can be at a ^*Carry out d afterwards ^*Or g ^*

This method is shown in the schema 4 about another particular embodiment of catalyst flow control.In this schema, form two catalyst returns.Catalyst return 1 comprises the e of workshop section ^*) and f ^*), catalyst return 2 comprises a of workshop section ^*), b ^*), c ^*).By these two materials flows via the h of workshop section ^*), suitable words i ^*), j ^*) and k ^*) carry son stream, suitable words also have specific total catalyst materials flow, with the break component and/or additional Ni (0) content of purifying catalyst.The ratio by extraction of carrying in the catalyst return 2 is preferably greater than catalyst return 1.Suitable, the whole materials flow of catalyst return 2 is carried by extraction.Only via the h of workshop section ^*), suitable words i ^*), j ^*) and k ^*), these two catalyst returns are interconnected.From k ^*) and infeed a ^*) or e ^*) materials flow cut apart usually corresponding to incoming flow with from a ^*) and e ^*) h ^*) ratio.To a of isomerization workshop section ^*) infeed the poor 2-methyl-3-crotononitrile that contains 3 pentene nitrile, promptly at a ^*) carry out d before ^*) or g ^*).Equally can be at a ^*Carry out d afterwards ^*Or g ^*

This method is shown in the schema 5 about another particular embodiment of catalyst flow control.According to this schema, catalyst return is via a of workshop section ^*), b ^*), c ^*), h ^*), suitable words i ^*), j ^*) and k ^*) operation.By this catalyst return at h ^*) take out son stream before and operate hydrocyanation e for the first time with its ^*).Via f ^*) this materials flow is recycled to h ^*) in.Suitable, this recirculation also can directly enter a ^*).The son stream in isomerization catalyst loop also can be by c ^*) directly be recycled to a ^*) in.To a of isomerization workshop section ^*) infeed the poor 2-methyl-3-crotononitrile that contains 3 pentene nitrile, promptly at a ^*) carry out d before ^*) or g ^*).Equally also can be at a ^*Carry out d afterwards ^*Or g ^*

Describe the present invention in detail with reference to the following example.

Embodiment

Use following abbreviation in an embodiment:

HCN: prussic acid

T3PN: trans-3 pentene nitrile

C3PN: cis-3 pentene nitrile

The 4PN:4-pentenenitrile

E2M2BN:(E)-2-methyl-2-butene nitrile

T2PN: trans-the 2-pentenenitrile

C2PN: cis-2-pentenenitrile

ADN: adiponitrile

MGN: methyl cellosolve acetate glutaronitrile

VAN: valeronitrile

The VCH:4-vinyl cyclohexene

BD:1, the 3-divinyl

TBP: tert-butyl catechol

C2BU: cis-2-butene

LA: Lewis acid

In an embodiment, processing step is with sequence of event and so inconsistent with the expression in specification sheets and claims.% or the ppm data that characterize in detail are not respectively weight % and ppm by weight.

Embodiment 1:

With reference to Fig. 3 embodiment 1 is described.

In embodiment 1, will be used for the hydrocyanation of divinyl based on the catalyst system of the nickel with ligand mixture (0) title complex.The ligand mixture that is used for hydrocyanation contains the 60mol% tricresyl phosphite of having an appointment (/ right-tolyl) ester and 40mol% chelating phosphinate 1:

In step (1), following materials flow is sent among the loop reactor R1 that capacity is 25L, this reactor is equipped with nozzle, pulse exchange pipe, the external pump recycle system and is arranged in the pump recycle system removing the interchanger of reaction energy, and reactor is heated to 357K:

(1) 10kg/h passes through the not stabilization liquid hydrogen cyanide of dephlegmate,

(2) 22kg/h contains the commercially available BD of 0.25%C2BU, and it is handled by contacting with aluminum oxide, anhydrate and the TBP stablizer to remove,

(3) 8kg/h is from the recirculation BD (materials flow 9) of the K2a in the step (2), and making the whole BD charging that enters reactor R1 that obtains thus is the materials flow that contains 90%BD, 5%C2BU and 5%1-butylene of 30kg/h,

(4) 21kg/h nickel (0) catalyst solution as described belowly obtains with the materials flow 10a from tower K2b in this embodiment.

The materials flow 8 (63kg/h) of being taken out by reactor R1 contains 11%BD and C2BU altogether, this is corresponding to 79% BD transformation efficiency, also has 63% pentenenitrile altogether, 31%T3PN, 29%2M3BN and a small amount of Z2M2BN and E2M2BN, and other pentenenitrile isomers (T2PN, C2PN, C3PN 4PN), also has catalyst component and catalyst degradation products and MGN.

In step (2), infeed materials flow 8 with the operation of rectifying section and stripping stage and falling-film evaporator is housed and separates the end and have among the distillation tower K2a of column internals of structured packing of 10 blocks of theoretical trays of generation.Tower K2a operates with direct condenser at the top, and this condenser is made up of the tower section that structured packing is housed and has total collection cups, pumping circulation system and an external heat exchanger.Tower K2a gets under the material temperature in the bottom of the head temperature of top absolute pressures, the 288K of 2.0 crust and 363K and operates.

Top via tower K2a obtains materials flow 9, as described in starting it is metered among the reactor R1 as recycle stream.The reflux ratio of regulating tower K2a top is so that materials flow 9 contains the 2M3BN of the 100ppm that has an appointment.

Bottom via tower K2a obtains 59kg/h materials flow 1b, and this materials flow contains 2.9%BD, 4.6%C2BU, and 67% pentenenitrile additionally also has catalyst component.With respect to BD, C2BU compares obvious richness with charging long-pending.

In step (2) materials flow 1b is sent among the distillation tower K2b, this tower is with the operation of stripping pattern and the evaporator overhead condenser of falling-film evaporator, band aftercondenser and the column internals with the structured packing that produces 10 blocks of theoretical trays are housed.This tower is got under the material temperature in the head temperature of 150 millibars top absolute pressure, 329K and 373K bottom and is operated.The vapor stream of this tower is also handled under 263K with aftercondenser in the condensation of 308K lower section.The BD materials flow 2c that removes 2M3BN and other pentenenitriles thus is compressed to the absolute pressure of 1.2 crust in compressor V2.With air-flow most of condensation under 279K of this compression, obtain materials flow 2e (5kg/h) and flow 2d (47L (STP)/h contains 44%C2BU) with the discarded son of gas form.Materials flow 2e is recycled in the phlegma collection container of tower K2a with liquid form.

Gaseous state side material taking mouth at tower K2b obtains materials flow 11 (40kg/h), and it contains the 100ppm BD that has an appointment, 46%2M3BN and 48%T3PN, and except other pentenenitrile isomers, also have a small amount of E2M2BN and Z2M2BN.The position of selecting this side material taking mouth is so that with respect to the T3PN in this stripping stage below side material taking mouth, the poor component 2M3BN that contains in the materials flow 10 that obtains via the bottom.

13kg/h is sent among the tower K2b as the sideing stream of tower K4 from step (4) as the catalyst stream that obtains as described at German patent application (B03/0525) embodiment 1 that is entitled as " preparation of dintrile " of BASF AG, this materials flow contains 73% pentenenitrile altogether, 0.5%Ni (0), 18% ligand mixture and about 5%ADN.

Obtain containing the catalyst stream 10 of 0.5%Ni (0), about 100ppm 2M3BN and 73% residual pentenenitrile via the bottom of tower K2b.Materials flow 10 is divided into the son stream 10a (21kg/h) that is recycled among the reactor R1.Another part (10b) (5.4kg/h) is infeeded in the regeneration according to DE-A-103 51 002, after regeneration, for example to be used for hydrocyanation as DE-A-102 004 004 683 embodiment 1 described 3 pentene nitrile.

In step (3), materials flow 11 sent into and circulating evaporator and evaporator overhead condenser are housed and also are equipped with among the distillation tower K3 of the structured packing that produces 30 blocks of theoretical trays.This tower K3 gets under the material temperature in the bottom of the head temperature of 180 millibars top absolute pressure, 345K and 363K and operates.

39kg/h is sent among the tower K3 from the recycle stream 5 of tower K5 in the step (5), and this materials flow contains 54%T3PN, 23%2M3BN and 16%Z2M2BN and other pentenenitrile isomers on a small quantity.

Top via tower K3 obtains 40kg/h materials flow 13, and this materials flow contains 10%T3PN, 68%2M3BN, 16%Z2M2BN and altogether 0.1%BD and C2BU and a small amount of other pentenenitrile isomers (T2PN, C2PN, C3PN, 4PN).

Bottom via tower K3 obtains 39kg/h materials flow 12, and this materials flow contains 97%T3PN altogether, C3PN and 4PN, and on a small quantity other pentenenitrile isomers (T2PN, C2PN), 100ppm2M3BN and about 1%E2M2BN also have an appointment.

In embodiment 1, will be used for 2M3BN is isomerizated into T3PN based on the catalyst system of the nickel with ligand mixture (0) title complex.Be used for the mixing phosphite ester ligand that isomerized this ligand mixture (isomerization part hereinafter referred to as) comprises P (OR) (OR ') (OR ") class, wherein random distribution has R, R ', the R that is selected from a tolyl, p-methylphenyl, o-isopropyl phenyl " and radicals R, R ', R " summation in about 40mol% be o-isopropyl phenyl.Such ligand mixture obtains in meta-cresol and p-cresol ratio are the reaction of the mixture of o-isopropyl phenol of 2: 1 meta-cresol and p-cresol and stoichiometry coupling amount and phosphorus trihalide.

In step (4), materials flow 13 is transported among the reactor R2 that is designed to tubular reactor and is heated to 393K with catalyst recycle materials flow 3a and catalyst make-up materials flow.Summation as catalyst recycle and live catalyst has 20%T3PN with 56kg/h, 5%2M3BN and other pentenenitrile isomers, and the mixture of 55% isomerization part and 0.5% nickel (0) and little amount of catalyst degraded product is sent among the reactor R2.

Product as reactor R2 obtains 96kg/h materials flow 1, and it contains 34%T3PN, and (C3PN 4PN), is 60% corresponding to the 2M3BN transformation efficiency for T2PN, C2PN for 12.3%2M3BN and a small amount of other pentenenitrile isomers.

In step (5), materials flow 1 is sent among the distillation tower K5, this tower is with rectifying tower operation and falling-film evaporator, evaporator overhead condenser, reflux splitter are housed, at the gaseous state side material taking mouth in this tower bottom zone and column internals with the structured packing that produces 30 blocks of theoretical trays.This tower is got under the material temperature in the bottom of the head temperature of 250 millibars top absolute pressure, 353K and 373K and is operated.

The catalyst stream 3 (56kg/h) that obtains reclaiming via the bottom in tower K5, it also contains 20%T3PN except other pentenenitriles, about 5%MGN and 0.5%Ni (0) and 54% isomerization part.With small part materials flow 3 as materials flow 3b discharging gathering with limiting catalyst deactivation component and MGN.In order to replenish the catalytic amount of discharging, be metered into enough live catalysts, so that Ni (0) content remains on 0.5% in the catalyst charge of reactor R2, this live catalyst also contains 15%T3PN except other pentenenitrile isomers, 1%Ni (0) and 80% isomerization part.

In tower K5, obtain materials flow 4 (0.8kg/h) via the top, it contains 0.5%BD and C2BU altogether, 50%2M3BN, 41%Z2M2BN, also has small amount of ethylene basic ring hexene (VCH), the latter at first is present in the BD raw material with trace and forms and finally accumulate in the isomerized 2M3BN circulation and must discharge with 2M3BN secondly on a small quantity in the hydrocyanation of divinyl, because the vapour pressure of 2M3BN and VCH is so approaching each other, so that can not be by conventional fractionation by distillation.The reflux ratio of regulating tower K5 is so that exist 10ppm T3PN in the materials flow 4.Adjusting materials flow 4 exists 20%Z2M2BN and VCH altogether from the speed of tower K5 top discharge so that discharge the materials flow 13 at the top of distillation tower K3.

Obtain materials flow 5 (39kg/h) via the gaseous state side material taking mouth in tower K5, this materials flow also significantly is included in the isomerization unconverted 2M3BN and is recycled among the tower K3 with liquid form after condensation as mentioned above except 3 pentene nitrile.

Embodiment 2:

With reference to Fig. 4 embodiment 2 is described.

In embodiment 2, will be used for the hydrocyanation of BD based on catalyst system with chelating phosphorous acid ester 2 nickel (0) title complex as part:

In step (1), following materials flow sent into by two capacity and respectively do for oneself among the reactor R1a and system that R1b forms of 12L, each reactor is equipped with nozzle, pulse exchange pipe, the external pump recycle system and is arranged in this pump recycle system removing the interchanger of reaction energy, and reactor is heated to 363K:

(1) 6kg/h infeeds the not stabilization liquid hydrogen cyanide of passing through dephlegmate of R1a,

(2) 6kg/h infeeds the not stabilization liquid hydrogen cyanide of passing through dephlegmate of R1b,

(3) 25kg/h infeeds the BD of R1a, and it contains 0.25%C2BU and has handled by contacting with aluminum oxide, anhydrate and the TBP stablizer to remove,

(4) 2kg/h infeeds the recirculation BD (materials flow 9) from tower K2a in the step (2) of R1a, is that 27kg/h contains 98%BD and the materials flow of 2%C2BU and 1-butylene altogether thereby make the whole BD charging of resulting reactor R1,

(5) 14kg/h infeeds nickel (0) catalyst solution of R1a, and conduct in this embodiment as described below obtains from the materials flow 10a of tower K2b.

The materials flow 8 (54kg/h) of taking out from reactor R1b contains 4%BD and C2BU altogether, corresponding to the BD transformation efficiency is 94%, also contain 74% pentenenitrile altogether, wherein 33% is T3PN, 37% is 2M3BN and on a small quantity for Z2M2BN and E2M2BN, also have other pentenenitrile isomers, and catalyst component and catalyst degradation products and MGN.

In step (2) materials flow 8 is infeeded among the distillation tower K2a, this tower is with the rectifying tower operation and falling-film evaporator and the column internals with the structured packing that produces 4 blocks of theoretical trays are housed.Tower K2a is operated by direct condenser at the top, and this condenser is made up of the tower section that random packing is housed and has total collection cups, pumping circulation system and an external heat exchanger.Tower K2a gets under the material temperature in the bottom of the head temperature of top absolute pressure, the 263K of 0.8 crust and 393K and operates.

Top via tower K2a obtains materials flow 9, and this materials flow is metered among the reactor R1a as recycle stream as described in starting.The reflux ratio of regulating tower K2a top is so that materials flow 9 contains 0.1%2M3BN.

Bottom via tower K2a obtains 52kg/h materials flow 1b, and this materials flow contains 0.3%BD, 0.1%C2BU, 76% pentenenitrile and additionally also have catalyst component.

In step (2) materials flow 1b is sent among the distillation tower K2b, this tower is with the operation of stripping pattern and the evaporator overhead condenser of falling-film evaporator, band aftercondenser and the column internals with the structured packing that produces 4 blocks of theoretical trays are housed.This tower is got under the material temperature in the bottom of the head temperature of 70 millibars top absolute pressure, 333K and 373K and is operated.

Gaseous state side material taking mouth at tower K2b obtains materials flow 11 (40kg/h), and it contains 0.4%BD, 54%2M3BN and 42%T3PN, and except other pentenenitrile isomers, also have a small amount of E2M2BN and Z2M2BN.

The 3kg/h catalyst stream is sent among the tower K2b, and this materials flow contains 45% pentenenitrile altogether, 1.5%Ni (0) and chelating ligand and for example by making nickel (0) (cyclooctadiene base) ₂Title complex and chelating phosphorous acid ester 2 react and obtain.

Bottom via tower K2b obtains catalyst stream 10, and it contains 1.2%Ni (0), 0.3%2M3BN and 17% residual pentenenitrile.Materials flow 10 parts are recycled to (14kg/h) among the reactor R1 (materials flow 10a).Another part (materials flow 10b) (3.8kg/h) is infeeded in the regeneration according to DE-A-103 51 002, and being used for the hydrocyanation of 3 pentene nitrile according to DE-A-102 004 004 683, or suitable words are recycled in the BD hydrocyanation according to the inventive method.

In step (3), materials flow 11 is sent among the distillation tower K3 structured packing that this tower is equipped with circulating evaporator and evaporator overhead condenser and produces 45 blocks of theoretical trays.Tower K3 gets under the material temperature in the bottom of the head temperature of top absolute pressures, the 395K of 1.0 crust and 416K and operates.

In step (5) 24kg/h is sent among the tower K3 from the recycle stream 5 of tower K5, this materials flow contains 70%T3PN, 14%2M3BN and 7%Z2M2BN and other pentenenitrile isomers on a small quantity.

Top via tower K3 obtains 30kg/h materials flow 13, and it contains 1%T3PN, 85%2M3BN, 8%Z2M2BN, and the BD and the C2BU that are total up to 3% except other pentenenitrile isomers and VCH.The reflux ratio of regulating tower K3 is to obtain 1%T3PN at the top.

Bottom via tower K3 obtains 38kg/h materials flow 12, and it contains 97%T3PN altogether, C3PN and 4PN, also have an appointment 10ppm 2M3BN and about 2%E2M2BN, and a small amount of MGN and other pentenenitrile isomers.

In embodiment 2, being used for isomerized catalyzer is to the described nickel based on the chelating phosphorous acid ester of BD hydrocyanation (0) title complex as this embodiment.

In step (4), materials flow 13 is sent among the reactor R2 with catalyst recycle materials flow 3a and catalyst make-up materials flow, this reactor design becomes to have the interval reactor of tubulose feature and preheater is housed, and by this preheater reaction mixture is heated to 383K.As the summation of catalyst recycle and live catalyst, the mixture that 12kg/h is had 20%T3PN, 3%2M3BN and other pentenenitrile isomers, 71% ligand mixture and 0.6% nickel (0) and little amount of catalyst degraded product is sent among the reactor R2.

Obtain 43kg/h materials flow 1 as the product that comes autoreactor R2, it contains 53%T3PN, and 12%2M3BN is 80% corresponding to the 2M3BN transformation efficiency.

In step (5), materials flow 1 is sent among the distillation tower K5 column internals that this tower is equipped with falling-film evaporator, evaporator overhead condenser, reflux splitter, the gaseous state side material taking mouth in this tower bottom zone and produces 30 blocks of theoretical trays.This tower is got under the material temperature in the bottom of the head temperature of 377 millibars top absolute pressure, 355K and 368K and is operated.

The catalyst stream 3 (11kg/h) that obtains reclaiming via the bottom in tower K5, it contains 20%T3PN except other pentenenitriles, about 1%MGN, and 0.6%Ni (0) and 54% part.Discharge the gathering of small part (materials flow 3b) with limiting catalyst deactivation component and MGN.In order to compensate the catalytic amount of this discharge, be metered into enough live catalysts (containing 40% pentenenitrile isomers, 1.2%Ni (0) and 55% ligand mixture) so that in the catalyst charge of reactor R2 Ni (0) content remain 0.6%.

Obtain materials flow 4 (1.4kg/h) by the top in tower K5, it contains 18%BD and C2BU altogether, 45%2M3BN, 28%Z2M2BN, and small amount of ethylene basic ring hexene (VCH).The reflux ratio of regulating tower K5 is so that exist 10ppm T3PN in the materials flow 4.Materials flow 4 is taken out in adjusting from tower K8 top speed exists 10%Z2M2BN and VCH so that take out the materials flow 13 at the top of distillation tower K3.

Obtain materials flow 5 (24kg/h) via the gaseous state side material taking mouth in tower K5, it also mainly is included in the isomerization unconverted 2M3BN and is recycled among the tower K3 with liquid form after condensation as mentioned above except 3 pentene nitrile.

Embodiment 3:

With reference to Fig. 5 embodiment 3 is described.

In embodiment 3, will be used for the hydrocyanation of divinyl based on the catalyst system of the nickel with ligand mixture (0) title complex.This ligand mixture that is used for hydrocyanation contains the 60mol% tricresyl phosphite of having an appointment (/ right-tolyl) ester and 40mol% chelating phosphorous acid ester 2.

(3) 25kg/h infeeds the commercially available BD of R1a, and it contains 0.25%C2BU and has handled by contacting with aluminum oxide, anhydrate and the TBP stablizer to remove,

(5) 14kg/h infeeds nickel (0) catalyzer of R1a, and conduct in this embodiment as described below obtains from the materials flow 10a of tower K2b.

Material taking mouth obtains materials flow 11 (40kg/h) at the gaseous state top of tower K2b, and it contains 0.4%BD, 54%2M3BN and 42%T3PN, and except other pentenenitrile isomers, also have a small amount of E2M2BN and Z2M2BN.

The 5kg/h catalyst stream is sent among the tower K2b, this materials flow obtains as taking out materials flow with the bottom of the tower K4 of embodiment 2 steps (4) as described in the embodiment 1 of DE-A-102004004683, it contains 45% pentenenitrile altogether, 1.1%Ni (0), 38% ligand mixture and about 12%ADN.

Bottom via tower K2b obtains catalyst stream 10, and it contains 1.2%Ni (0), 0.3%2M3BN and 17% residual pentenenitrile.Materials flow 10 parts are recycled to (14kg/h) among the reactor R1 (materials flow 10a).Another part (materials flow 10b) (3.8kg/h) is infeeded in the regeneration according to DE-A-103 51002, to be used for the hydrocyanation of 3 pentene nitrile according to DE-A-102 004 004 683.

In step (6) 28kg/h is sent among the tower K3 from the recycle stream 5 of tower K6, this materials flow contains 72%T3PN, 15%2M3BN and 8%Z2M2BN and other pentenenitrile isomers on a small quantity.

Top via tower K3 obtains 30kg/h materials flow 13, and it contains 1%T3PN, 85%2M3BN, 8%Z2M2BN and be total up to 3% BD and C2BU and other pentenenitrile isomers.The reflux ratio of regulating tower K3 is to obtain 1%3PN at the top.

In embodiment 3, will be used for the isomerization of 2M3BN based on the catalyst system of the nickel with ligand mixture (0) title complex to T3PN.Be used for the mixing phosphite ester ligand that isomerized ligand mixture (isomerization part hereinafter referred to as) comprises P (OR) (OR ') (OR ") class, wherein random distribution have be selected from phenyl, a tolyl, p-methylphenyl, R, the R ' of o-tolyl, R " and radicals R, R ', R " summation at least 80mol% be between tolyl and p-methylphenyl.Such ligand mixture obtains in meta-cresol and p-cresol ratio of mixture are the reaction of the mixture of 2: 1 meta-cresol and p-cresol and phosphorus trihalide.The promotor that is used for isomerization reaction is zinc chloride, as US 3,676, and 481, US 3,852,329 and US 4,298,546 is described.

The product that obtains from reactor R2 is 43kg/h materials flow 1, and it contains 53%T3PN, and 12%2M3BN is 80% corresponding to the 2M3BN transformation efficiency.

In step (5) materials flow 1 is sent among the vaporizer section B5, this section is equipped with pump feed evaporator and evaporator overhead condenser.Vaporizer section B5 gets in the bottom of 510 millibars absolute pressure, 403K under the condensing temperature of material temperature and 366K and operates.

The catalyst stream 3 (11kg/h) that obtains reclaiming via the bottom in vaporizer section B5, it contains 20%T3PN except other pentenenitriles, about 10%MGN, and 0.5%Ni (0) and 61% ligand mixture.Discharge the gathering of small part (materials flow 3b) with limiting catalyst deactivation component and MGN.In order to compensate the catalytic amount of this discharge, be metered into enough live catalysts, this catalyzer contains 15% pentenenitrile isomers of having an appointment, about 2.0%Ni (0), and about 70% isomerization part and concentration are corresponding to ZnCl ₂With the mol ratio of nickel (0) be about 5 zinc chloride promotor so that Ni (0) content remains 0.6% in the catalyst charge of reactor R2.

Obtain materials flow 2 (25kg/h) at the evaporator overhead condenser place in vaporizer section B5, it contains 1%BD, 68%T3PN, 16%2M3BN and other pentenenitriles, and a small amount of VCH.

In step (6), materials flow 2 is sent among the distillation tower K6 column internals that this tower is operated and circulating evaporator, evaporator overhead condenser is housed and produces 30 blocks of theoretical trays with rectifying tower.This tower is got under the material temperature in the bottom of the condenser temperature of the head temperature of 340 millibars top absolute pressure, 357K, 313K and 373K and is operated.

The gas phase that obtains at the condenser place of tower K6 is the materials flow of being made up of BD substantially of about 100L (STP)/h.

The liquid phase that obtains at the evaporator overhead condenser place in tower K6 is materials flow 4 (1.1kg/h), and it contains 5%BD and C2BU altogether, 50%2M3BN, 30%Z2M2BN, and small amount of ethylene basic ring hexene (VCH).The reflux ratio of regulating tower K6 is so that exist 1ppm T3PN in the materials flow 4.Adjusting is taken out the speed of materials flow 4 so that have 10% Z2M2BN and VCH altogether the charging of reactor R2 from tower K6 top.

Obtain materials flow 5 (24kg/h) via the bottom in tower K6, it also mainly is included in the isomerization unconverted 2M3BN and is recycled to as mentioned above among the tower K3 except 3 pentene nitrile.

Embodiment 4:

With reference to Fig. 6 embodiment 4 is described.

In embodiment 3, will be used for the hydrocyanation of divinyl based on the catalyst system of the nickel with ligand mixture (0) title complex.This ligand mixture that is used for hydrocyanation contains the 80mol% phosphorous acid of having an appointment (/ right-tolyl) ester and 20mol% chelating phosphorous acid ester 2 (seeing embodiment 2).

In step (1), following materials flow sent into by three capacity that are connected in series and respectively does for oneself among continuous stirred tank R1a, the R1b and system that R1c forms of 10L, each stirring tank is heated to 373K:

(1) 5.2kg/h infeeds the not stabilization liquid hydrogen cyanide of passing through dephlegmate of R1a,

(2) 4.0kg/h infeeds the not stabilization liquid hydrogen cyanide of passing through dephlegmate of R1b,

(3) 20kg/h infeeds the BD of the conduct of R1a from the materials flow 9 of the condenser of vaporizer B1 in the step (2), and this materials flow contains 92%BD, 2%T3PN, 4%2M3BN and about 2%C2BU,

(4) 4.1kg/h infeeds nickel (0) catalyst solution of R1a, and it is as described below in this embodiment to obtain with the materials flow 3a from the vaporizer section B5 in the step (5),

(5) 3.7kg/h infeeds nickel (0) catalyst solution of R1a, it is as obtaining to take out materials flow from the bottom of the tower K4 of embodiment 2 steps (4) as described in German patent application (B03/0525) embodiment 3 that is entitled as " preparation of dintrile " of BASF AG, this materials flow contains 45% pentenenitrile altogether, 1.1%Ni (0), 38% ligand mixture and about 12%ADN.

Reactor R1c uses the effluent of autoreactor R1b to operate under 353K as post-reactor.

The materials flow 8 (37kg/h) of being taken out by reactor R1c contains 1%BD, corresponding to the BD transformation efficiency is 98%, also contain 82% pentenenitrile altogether, wherein 36% is T3PN, 44% is 2M3BN and on a small quantity for Z2M2BN and E2M2BN, and catalyst component and catalyst degradation products, MGN and other pentenenitrile isomers.

In step (2) materials flow 8 is infeeded among the vaporizer section B1, this section is equipped with circulating evaporator.Vaporizer section B1 at the top by the condenser operation of using from the flushing of the condensed material of reflux vessel.Vaporizer section B1 gets under the material temperature in the bottom of the condensing temperature of top absolute pressure, the 253K of 0.6 crust and 363K and operates.

Be metered into the commercially available BD that 19.5kg/h contains 0.25%C2BU in the phlegma collection container of vaporizer section B1, this commercially available BD handles by contacting with molecular sieve, and wherein the water-content of used BD has been reduced to and has been lower than 10 ppm by weight water.

Phlegma collection container by vaporizer section B1 is discharged materials flow 9 and be recycled to as mentioned above among the reactor R1a as the summation of recirculation and the fresh divinyl that is metered into.

Bottom via vaporizer section B1 obtains 37kg/h materials flow 11b, and this materials flow contains 1%BD, 82% pentenenitrile and additionally contain catalyst component.

In step (4) materials flow 11b is sent among the reactor R2, this reactor is heated to 383K and is designed to have the stirring tank that the downstream postpones section, and in the presence of nickel catalyzator 2M3BN is isomerizated into T3PN.

Pentenenitrile recycle stream 5 is sent into reactor R2 (10kg/h), its in step (6) in tower 6 with contain 60%2M3BN, the bottoms of 10%T3PN and other pentenenitrile isomers and VCH and a small amount of BD obtains altogether.

Obtain materials flow 1 (45kg/h) by reactor R2, it contains 62%T3PN and 14%2M3BN, is 70% corresponding to 2M3BN to the transformation efficiency of T3PN, and catalyst component.

Materials flow 1 sent into vaporizer section B5 in step (5), this section is equipped with falling-film evaporator and condenser and gets under the material temperature in the bottom of 50 millibars absolute pressure and 393K to be operated.

Condenser by vaporizer section B5 obtains materials flow 2 (38kg/h), and it contains 91% pentenenitrile isomers and about 1%BD and a small amount of E2M2BN, Z2M2BN and VCH.

Bottom via vaporizer section B5 obtains catalyst stream 3 (7.2kg/h), and it contains 1.2%Ni (0), 0.1%2M3BN and 15% residual pentenenitrile.(materials flow 3a) is recycled to (4.1kg/h) among the reactor R1 with materials flow 3 parts.Remainder (materials flow 3b) is infeeded according in the regeneration of DE-A-103 51 002 and can for example be used for after regeneration as in the hydrocyanation of the 3 pentene nitrile of DE-A-102 004 004 683 embodiment 2 or be used as the catalyzer of hydrocyanation divinyl in the methods of the invention once more, and suitable words are after removing zinc chloride.

In step (3), distillation tower K3 is sent in materials flow 2, the column internals that this tower is equipped with pump feed evaporator and evaporator overhead condenser and produces 30 blocks of theoretical trays.This tower K3 gets under the material temperature in the bottom of the head temperature of 120 millibars top absolute pressure, 334K and 352K and operates.

Top via tower K3 obtains 10kg/h materials flow 13, and it contains 5%T3PN, 60%2M3BN, and 4%Z2M2BN, and 4% BD and C2BU altogether, rest part is mainly VCH.Reflux ratio among the adjusting tower K3 is to obtain 5%T3PN at the top.

Bottom via tower K3 obtains 27kg/h materials flow 12, and it contains 98%T3PN altogether, C3PN and 4PN, and about 1000ppm 2M3BN and about 2%E2M2BN.

In step (6), materials flow 13 is sent among the distillation tower K6 column internals that this tower is operated and pump feed evaporator, evaporator overhead condenser, reflux splitter is housed and has the structured packing that produces 15 blocks of theoretical trays as rectifying tower.This tower K6 gets under the material temperature in the bottom of the head temperature of 380 millibars top absolute pressure, 361K and 365K and operates.

Obtain liquid stream 4 (0.6kg/h) by the top in tower K6, it contains 4% BD and C2BU altogether, 54%2M3BN, 38%Z2M2BN and 2.5% vinyl cyclohexene (VCH).Adjusting exists 30% Z2M2BN and VCH altogether by the speed of the materials flow 4 that take out at tower K6 top so that take out at the top of tower K3 in the materials flow 13.Gaseous stream (the 195L (STP)/h) that in tower K6, is comprised BD substantially at evaporator overhead condenser place with the fractional distillating tube operation.

Obtain materials flow 5 (9.4kg/h) via the bottom in tower K6, this materials flow is included in the isomerization unconverted 2M3BN substantially and is recycled among the isomerization reactor R2 except 3 pentene nitrile.

Embodiment 5:

With reference to Fig. 7 embodiment 5 is described.

In embodiment 5, will be used for the hydrocyanation of BD based on the catalyst system of the nickel with ligand mixture (0) title complex.This ligand mixture that is used for hydrocyanation contains the 80mol% tricresyl phosphite of having an appointment (/ right-tolyl) ester and 20mol% chelating phosphinate 1 (seeing embodiment 1).

In step (1), following materials flow sent into by two capacity that are connected in series and respectively does for oneself among the continuous stirred tank R1a and system that R1b forms of 50L, each stirring tank is heated to 363K:

(1) 18kg/h infeeds the not stabilization liquid hydrogen cyanide of passing through dephlegmate among reactor R1a and the R1b with equal proportion,

(2) 62kg/h infeeds conduct among the reactor R1a from the BD of the materials flow 9 at vaporizer B1 top in the step (2), this materials flow contains 87%BD, 3%T3PN, 6%2M3BN and about 2%C2BU, (3) 61kg/h infeeds nickel (0) catalyst solution as obtaining with the materials flow 3a from vaporizer section B5 in the step (5) as described in below among this embodiment among the reactor R1a

(4) 6.7kg/h infeeds nickel (0) catalyst solution among the R1a, it is as obtaining to take out materials flow from the bottom of the tower K4 of embodiment 2 steps (4) as described in German patent application (B03/0525) embodiment 1 that is entitled as " preparation of dintrile " of BASF AG, this materials flow contains 45% pentenenitrile altogether, 1.1%Ni (0), 38% ligand mixture and about 12%ADN, wherein butadiene stream and catalyst stream with premix before prussic acid contacts.

The materials flow 8 (177kg/h) of being taken out by reactor R1b contains 11%BD, this is 66% corresponding to the BD transformation efficiency, and the pentenenitrile that is total up to 64%, wherein 32% is T3PN, 30% is 2M3BN and on a small quantity for Z2M2BN and E2M2BN and other pentenenitrile isomers, also has catalyst component and catalyst degradation products.

In step (2), materials flow 8 is infeeded among the vaporizer section B1 that falling-film evaporator is housed.Vaporizer section B1 is with the condenser operation at the top, and this condenser uses the condensed material from reflux vessel to wash.Vaporizer section B1 gets under the material temperature in the bottom of the condensing temperature of top absolute pressures, the 278K of 1.3 crust and 403K and operates.

The commercially available BD of 37kg/h is metered in the phlegma collection container of vaporizer section B1, this commercially available BD contains 0.25%C2BU and has handled by contacting with molecular sieve, and the water-content of used BD has removed to go to and has been lower than the TBP stablizer that exists among 5 ppm by weight water and the used BD and arrives phlegma collection container and condenser flush loop with the concentration of ppm level.

Take out materials flow 9 as the summation of recirculation and the fresh BD that is metered into and as mentioned above it is recycled among the reactor R1a by the phlegma collection container of vaporizer section B1.

Bottom via vaporizer section B1 obtains 152kg/h materials flow 11b, and it contains 0.9%BD, 16%2M3BN, and 51%T3PN and other pentenenitrile isomers, and additionally contain catalyst component.The composition of the bottom effluent of vaporizer section makes that be 50% at the bottom of vaporizer B1 2M3BN to the degree of conversion of T3PN.

In step (5) materials flow 11b is sent among the vaporizer section B5, this section is equipped with falling-film evaporator and condenser and gets under the material temperature in the bottom of 260 millibars absolute pressure and 383K to be operated.

Obtain materials flow 2 (83kg/h) by vaporizer section B5 with gas form, it contains 93% pentenenitrile isomers, and 1%BD and a small amount of E2M2BN, Z2M2BN and VCH also have an appointment.Materials flow 2 is sent among the distillation tower K3 in the step (3).

Bottom via vaporizer section B5 obtains catalyst stream 3 (69kg/h), and it contains 0.6%Ni (0), 2%2M3BN and 42% residual pentenenitrile.Materials flow 4 major parts are recycled to (61.4kg/h) among the reactor R1 (materials flow 3a).(materials flow 3b) infeeds in the regeneration according to DE-A-103 51 002 with rest part, and can be for example as being used for the hydrocyanation of 3 pentene nitrile as described in DE-A-102 004 004 683 embodiment 1.

In step (3), materials flow 2 is sent among the distillation tower K3 structured packing that this tower is equipped with pump circulation flasher and evaporator overhead condenser and produces 30 blocks of theoretical trays with gas form.This tower K3 gets under the material temperature in the bottom of the head temperature of 80 millibars top absolute pressure, 375K and 343K and carries out.

Top via tower K3 obtains 36kg/h materials flow 13, and it contains 15%T3PN, 64%2M3BN, and 3%Z2M2BN, and 4% BD and C2BU altogether, rest part mainly comprises VCH.The reflux ratio of regulating tower K3 is to obtain 15%T3PN at the top.

Bottom via tower K3 obtains 47kg/h materials flow 12, and it contains 98% T3PN altogether, C3PN and 4PN and 100ppm 2M3BN and about 1%E2M2BN.

In step (6), materials flow 13 is sent among the distillation tower K6 column internals that this tower is operated and pump feed evaporator, evaporator overhead condenser, reflux splitter is housed and has the structured packing that produces 45 blocks of theoretical trays with rectifying tower.This tower is got under the material temperature in the bottom of the condensing temperature of 320 millibars top absolute pressure, 288K and 363K and is operated.

Obtain liquid stream 4 (6.8kg/h) via the top in tower K6, it contains 10% BD and C2BU altogether, 80%2M3BN, 8%Z2M2BN, and 0.5% vinyl cyclohexene (VCH).Materials flow 4 is taken out in adjusting from tower K6 top speed exists 15% Z2M2BN and VCH altogether so that take out at the top of tower K3 the materials flow 3.Gaseous stream (the 263L (STP)/h) that in tower K6, is mainly comprised BD at evaporator overhead condenser place with the fractional distillating tube operation.

Obtain materials flow 5 (28.7kg/h) via the bottom in tower K6, it mainly is included in the isomerization unconverted 2M3BN and is recycled among the hydrocyanation reaction device R1 except 3 pentene nitrile.

Embodiment 6:

With reference to Fig. 8 embodiment 6 is described.

In embodiment 6, will be used for the hydrocyanation (seeing embodiment 1) of BD based on catalyst system with chelating phosphinate 1 nickel (0) title complex as part.

In step (1) volume being sent in following materials flow is among 30L and the operate continuously stirring tank R1 that is heated to 363K:

(1) 16kg/h passes through the not stabilization liquid hydrogen cyanide of dephlegmate,

(2) the 55kg/h conduct is from the BD of the materials flow 9 at vaporizer B1 top in the step (2), and it contains 87%BD, 3%T3PN, and 6%2M3BN and about 2%C2BU,

(3) 10kg/h nickel (0) catalyst solution that obtains with materials flow 3a as described below in this embodiment from vaporizer section B5 in the step (5), it contains 42% pentenenitrile altogether, 23% part, 0.9% nickel (0) and about in each case 10% ADN and MGN

(4) 4kg/h infeeds nickel (0) catalyst solution among the R1, and it contains 45% pentenenitrile altogether, 1.5%Ni (0) and 48% part.

The materials flow 8 (89kg/h) of being taken out by reactor R1 contains 17%BD, corresponding to the BD transformation efficiency is 71%, and 73% pentenenitrile altogether, and wherein 32% is T3PN, 36% is 2M3BN and on a small quantity for Z2M2BN and E2M2BN, and catalyst component and catalyst degradation products.

In step (2), materials flow 8 is infeeded among the vaporizer section B1 that falling-film evaporator is housed.This vaporizer section B1 is with the condenser operation at the top, and this condenser uses the condensed material from reflux vessel to wash.Vaporizer section B1 gets under the material temperature in the bottom of the condensing temperature of top absolute pressures, the 278K of 1.3 crust and 403K and operates.

The commercially available BD that 34kg/h is contained 0.25%C2BU is metered in the phlegma collection container of vaporizer section B1, and this commercially available BD handles by contacting with aluminum oxide, and the water-content of used BD is brought down below 10 ppm by weight water and TBP content is brought down below 10ppm.

Discharging materials flow 9 by the phlegma collection container of vaporizer section as the summation of recirculation and the fresh divinyl that is metered into also is recycled to it among reactor R1a as mentioned above.

Bottom via vaporizer section B1 obtains 76kg/h materials flow 5, and this materials flow contains 0.8%BD, 12%2M3BN, and 69%T3PN and other pentenenitrile isomers also additionally contain catalyst component.The composition of the bottom effluent of vaporizer section is corresponding to being 75% at the bottom 2M3BN of vaporizer section B1 to the degree of conversion of T3PN.

In step (5), materials flow 5 is sent among the vaporizer section B5, but this vaporizer section is equipped with falling-film evaporator and condenser and get under the material temperature in the bottom of 220 millibars absolute pressure and 381K and to operate.

Obtain materials flow 2 (58kg/h) by vaporizer section B5 with gas form, it contains 97% pentenenitrile isomers, about 1%BD and a small amount of E2M2BN, Z2M2BN and VCH.

Bottom via vaporizer section B5 obtains catalyst stream 3 (17kg/h), and it contains 0.9%Ni (0), 0.3%2M3BN and 42% residual pentenenitrile.Materials flow 3 major parts are recycled to (10kg/h) among the reactor R1 (materials flow 3a).Rest part (materials flow 3b) is infeeded according in the regeneration of US 2003/0100442 and can be used for the hydrocyanation of 3 pentene nitrile or be recycled in the BD hydrocyanation step of the inventive method after regeneration.

Condensate stream 2 is also sent among the distillation tower K3 structured packing that this tower is equipped with pump feed evaporator and evaporator overhead condenser and produces 50 blocks of theoretical trays with liquid form in step 3.This tower K3 gets under the material temperature in the bottom of the head temperature of 200 millibars top absolute pressure, 342K and 366K and operates.

Obtain materials flow 4 at tower K3 top, it contains 10%BD, 18%Z2M2BN, 68%2M3BN and other pentenenitrile isomers and VCH.The reflux ratio of regulating tower K3 contains 18%Z2M2BN so that materials flow is taken out at the top.

Material taking mouth obtains 8kg/h materials flow 13 in the hydraulic fluid side of tower K3, and it contains 0.5%T3PN, 85%2M3BN, 5%Z2M2BN, 10%BD.Materials flow 13 is recycled among the vaporizer section B1.

Bottom via tower K3 obtains 47kg/h materials flow 12, and it contains 98%T3PN altogether, C3PN and 4PN, and 100ppm 2M3BN and about 1%E2M2BN.

All following tests are carried out in protective gas atmosphere.

Nickel (0) [phosphorous acid isopropyl phenyl _0.8Between-/p-methylphenyl _3.2Ester] ₁₈(being called for short the sec.-propyl catalyzer) is corresponding to 1.0 weight % nickel (0) and 19 weight %3PN and the adjacent cumyl of 80 weight % phosphorous acid _0.8Between/right-tolyl _3.2The solution of ester.

The continuous hydrocyanation of BD is become the embodiment of 2M3BN/3PN

(BD/HCN is than=1.4: 1) for embodiment 7 (contrast)

Per hour with 2.11mol humidity and stabilization divinyl (100ppm water, 100ppm TBP), the Ni of 1.55mol HCN and 14mmol sec.-propyl catalyst mode infeeds pressurized reactor (pressure: 15 crust, internal temperature: 105 ℃, the residence time: about 40 minutes/reactor).According to volumetry, it is quantitative (Vollhard titration) that HCN transforms.The 2M3BN/3PN ratio of reaction effluent is by GC chromatography determination (GC area %).The 2M3BN/3PN ratio is 1.95/1.Based on the valuable product that forms, the loss of Ni (0) is 0.58kg Ni (0)/valuable product of t (3PN/2M3BN).(BD/HCN is than=1.4: 1) for embodiment 8

Per hour the Ni of 2.13mol exsiccant divinyl, 1.53mol HCN and 14mmol sec.-propyl catalyst mode on 4  molecular sieve beds is infeeded pressurized reactor (pressure: 15 crust, internal temperature: 105 ℃, the residence time: about 40 minutes/reactor).According to volumetry, it is quantitative (Vollhard titration) that HCN transforms.The 2M3BN/3PN ratio of reaction effluent is by GC chromatography determination (GC area %).The 2M3BN/3PN ratio is 1.95/1.Based on the valuable product that forms, the loss of Ni (0) is 0.14kg Ni (0)/valuable product of t (3PN/2M3BN).

(BD/HCN is than=1.2: 1) for embodiment 9

Per hour the Ni of 2.09mol exsiccant divinyl, 1.67mol HCN and 14mmol sec.-propyl catalyst mode on bed of aluminium oxide is infeeded pressurized reactor (pressure: 15 crust, internal temperature: 105 ℃, the residence time: about 45 minutes/reactor).According to volumetry, it is quantitative (Vollhard titration) that HCN transforms.The 2M3BN/3PN ratio of reaction effluent is by GC chromatography determination (GC area %).2M3BN/3PN is than being the 1.95/1 valuable product based on formation, and the loss of Ni (0) is＜0.10kg Ni (0)/valuable product of t (3PN/2M3BN).

2M3BN is isomerizated into continuously the embodiment of 3PN

Embodiment 10:

Excessive BD is removed in the hydrocyanation effluent and the distillation that are collected in preparation among the embodiment 8.With the mixture heating up to 130 that obtains thus ℃ and kept 1 hour.After 0 and 30 minute and after 1 hour, get the GC sample and pass through GC chromatography analysis (GC area %) by reaction mixture.

Time	2M3BN	E，Z-2M2BN	c，t-2PN	4PN	c，t-3PN	3PN/2M3BN
Time	2M3BN	E，Z-2M2BN	c，t-2PN	4PN	c，t-3PN	3PN/2M3BN	0 hour	15.62	0.20	0.50	0.50	38.33	2.45
30 minutes	10.21	0.21	0.51	0.49	42.36	4.15	0 hour	15.62	0.20	0.50	0.50	38.33	2.45
30 minutes	10.21	0.21	0.51	0.49	42.36	4.15	1 hour	5.69	0.27	0.54	0.51	47.12	8.28

Hydrocyanation catalyst by recirculation is with the improper embodiment that is isomerizated into 2M2BN of 2M3BN

Embodiment 11:

Take out 100g sec.-propyl catalyzer continuously and in per hour, it is infeeded pressurized reactor (pressure: 15 crust with 2.14mol exsiccant divinyl and 1.67mol HCN on bed of aluminium oxide by the catalyzer storage tank that under t=0 hour, is filled with the fresh sec.-propyl catalyzer of 649g, internal temperature: 105 ℃, the residence time: about 45 minutes/reactor).According to volumetry, it is quantitative (Vollhard titration) that HCN transforms.Be recycled in the storage tank by Sambay distillation continuous return catalizer that takes out valuable product and will so obtain from catalyzer.This operation 50 hours is also discharged and is still had the active catalyzer of hydrocyanation owing to beginning to form the 2M2BN secondary component.The catalyzer that so obtains is carried out isomerization test:

Embodiment 12 (contrast):

In the 10g isomerization catalyst, replenish 2M3BN (15g) and descend heating 5 hours at 120 ℃.2M3BN transformation efficiency 89% (GC area %) forms 8.6% improper isomer (2M2BN) down.

Embodiment 13:

Normal heptane (100g) and adiponitrile (50g) are added from the isomerization catalyst (100g) of embodiment 11 and stir this mixture (15 minutes).Be separated (30 minutes) afterwards, discharging lower floor's phase.A part of upper strata phase (50g, heptane+isomerization catalyst) is concentrated on rotatory evaporator.In resistates (14g, isomerization catalyst), replenish 2M3BN (21g) and descend heating 5 hours at 120 ℃.2M3BN transformation efficiency 95% (GC area %) forms 2.0% improper isomer (2M2BN) down.

Embodiment 14:

To mix with adiponitrile (37.5g) from the resistates (embodiment 12) of the first upper strata phase that extracts and stir once more.After being separated, once more a part of upper strata is being concentrated and is replenishing 2M3BN (14g) on the rotatory evaporator in resistates (9.3g).At 120 ℃ after following 5 hours, find that the 2M3BN transformation efficiency is that 94% (GC area %) and improper isomery turn to 0.7%.

Isomerization catalyst by continuous use is with the improper embodiment that is isomerizated into 2M2BN of 2M3BN

Embodiment 15:

In the 2L reactor, add 300g continuously and 450g/h 2M3BN blended sec.-propyl catalyzer and be heated to 130 ℃.Take out reactor content also by the continuous still battery aftertreatment under 60 minutes the residence time, recirculation remains in the isomerization catalyst of bottom.This operation 50 hours is also discharged the catalyzer that still has isomerization activity owing to 2M3BN begins improper isomerization.The catalyzer that so obtains carries out isomerization test:

Embodiment 16:

In the 10g isomerization catalyst, replenish 2M3BN (15g) and descend heating 5 hours at 120 ℃.2M3BN transformation efficiency 90% (GC area %) forms 9.8% improper isomer (2M2BN) down.

Embodiment 17:

Normal heptane (100g) and adiponitrile (50g) are added from the isomerization catalyst (100g) of embodiment 16 and stir this mixture (15 minutes).(30 minutes) discharge lower floor's phase afterwards being separated.A part of upper strata phase (50g, heptane+isomerization catalyst) is concentrated on rotatory evaporator.In resistates (14g, isomerization catalyst), replenish 2M3BN (21g) and descend heating 5 hours at 120 ℃.2M3BN transformation efficiency 93% (GC area) forms 2.4% improper isomer (2M2BN) down.

Embodiment 18:

To mix with adiponitrile (37.5g) from the resistates (embodiment 17) of the first upper strata phase that extracts and stir once more.After being separated, once more a part of upper strata is being concentrated and is replenishing 2M3BN (14g) on the rotatory evaporator in resistates (9.3g).At 120 ℃ after following 5 hours, find that the 2M3BN transformation efficiency is that 93% (GC area %) and improper isomery turn to 0.6%.

Claims

1. method for preparing 3 pentene nitrile is characterized in that following process steps:

2. according to the process of claim 1 wherein that educt flow obtains by following process steps:

(f) with materials flow 8 distillation once or more than once, obtain comprising the materials flow 9 of 1,3-butadiene, comprise the materials flow 10 of this at least a hydrocyanation catalyst and comprise 3 pentene nitrile and the materials flow 11 of 2-methyl-3-crotononitrile,

3. according to the method for claim 2, wherein processing step (d) carries out in identical distillation plant with (g), this moment materials flow 6 with 12 and materials flow 7 identical with 13.

4. according to the method for claim 2 or 3, processing step (c) and (g) in the common distillation tower, carry out wherein, save processing step (d) this moment, to send into processing step (g) from the materials flow 2 of processing step (b) with from the materials flow 11 of processing step (f), and in processing step (g), comprised the materials flow 4 of (Z)-2-methyl-2-butene nitrile, the materials flow 13 that obtains comprising the materials flow 12 of 3 pentene nitrile and obtain comprising 2-methyl-3-crotononitrile to side stream with bottoms with top product.

5. according to each method among the claim 1-4, wherein at least a isomerization catalyst that will obtain in materials flow 3 in processing step (b) is recycled to processing step (a).

6. according to each method among the claim 1-5, processing step (b) and (c) in a distillation plant, carry out together wherein, obtain comprising the materials flow 3 of at least a isomerization catalyst at this moment with bottoms, comprised the materials flow 4 of (Z)-2-methyl-2-butene nitrile and the materials flow 5 that obtains comprising 3 pentene nitrile and 2-methyl-3-crotononitrile with sideing stream of this tower with top product.

7. according to each method among the claim 1-5, processing step (a) and (b) and (c) in a distillation plant, carrying out together wherein, comprised the materials flow 4 of (Z)-2-methyl-2-butene nitrile this moment with top product, obtain comprising the materials flow 5 of 3 pentene nitrile and 2-methyl-3-crotononitrile with sideing stream of distillation plant, and isomerization catalyst remains in the distillation tower bottom.

8. according to each method among the claim 1-7, wherein isomerization catalyst contains nickel (0), contains phosphorous compound and suitable speech channel Lewis acid as what part cooperated nickel (0).

9. according to each method among the claim 1-8, wherein set in the processing step (b) pressure and temperature so that isomerization catalyst not as active in the processing step (a), or torpescence.

10. according to each method among the claim 1-8, wherein hydrocyanation catalyst is identical with isomerization catalyst.

11. according to each method among the claim 1-10, wherein educt flow obtains by following process steps:

(k ^*) always distillation removes dealkylation in the catalyst component of materials flow 22, produces the materials flow 25 of the catalyst component that comprises main ratio and suitable, and materials flow 25 partially or completely is recycled to processing step (a ^*) or (e ^*) in,

12. according to the method for claim 11, wherein nickel (0) catalyst content replenishes by the reductibility catalyst regeneration and at the h of workshop section ^*) in carry out.

13. according to the method for claim 11 or 12, wherein catalyst system is with two separated catalyst circuit operation, one of them loop comprises the e of workshop section ^*) and f ^*), and another loop comprises a of workshop section ^*), b ^*) and c ^*).

14. according to each method among the claim 11-13, the divinyl that wherein will contain stablizer is as e ^*) incoming flow.

15. according to each method among the claim 11-14, wherein catalyst system therefor is the phosphorous acid ester of formula Ib:

P(O-R ¹) _x(O-R ²) _y(O-R ³) _z(O-R ⁴) _p (Ib)

Wherein

X:1 or 2,

Y, z, p are 0,1 or 2 independently of one another, and condition is x+y+z+p=3.

16. according to each method among the claim 11-15, wherein catalyst system therefor is the phosphorous acid ester of formula Ib:

P(O-R ¹) _x(O-R ²) _y(O-R ³) _z(O-R ⁴) _p (Ib)