CN1049208C - Method for preparing 1,4-butanediol - Google Patents
Method for preparing 1,4-butanediol Download PDFInfo
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- CN1049208C CN1049208C CN94108096A CN94108096A CN1049208C CN 1049208 C CN1049208 C CN 1049208C CN 94108096 A CN94108096 A CN 94108096A CN 94108096 A CN94108096 A CN 94108096A CN 1049208 C CN1049208 C CN 1049208C
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- reaction
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- butyleneglycol
- alkyl ester
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Abstract
The present invention relates to a method for preparing 1, 4-butanediol. Dialkyl maleate and/or dialkyl succinate is used as raw materials, and 1, 4-butanediol is prepared by a gas-phase catalytic hydrogenation reaction under the condition of the existence of a catalyst with the general formula of CnaZnCrbMcOx. In the general formula, a is equal to 0.1 to 10, b is equal to 0.1 to 5, and c is equal to 0.5 to 5; a, b and c respectively represent the atomic numbers of Cu, Cr and M; X is the number of oxygen atoms required for meeting the requirements of the chemical valences of other elements; and M is one element in an IVB group, particularly Zr. The method has the technical conditions that the reaction pressure is from 1 to 8MPa, and the reaction temperature is from 190 to 300 DEG C; the volume feeding space velocity of liquid raw materials for reaction is from 0.2 to 2.0 h<-1>; and the molar ratio of H2 to ester is 100 to 500: 1. The method has the characteristics of simple process, high space time yield, high selectivity of 1, 4-butanediol, high stability, etc.
Description
The present invention relates to 1, the preparation method of 4-butyleneglycol is that raw material carries out gas phase catalytic hydrogenation prepared in reaction 1 with maleic acid alkyl ester and/or succinic acid dialkyl ester specifically, the method for 4-butyleneglycol.
1, the 4-butyleneglycol is a kind of important basic Organic Chemicals, is mainly used in production polybutyl terapthalate (PBT), urethane, gamma-butyrolactone and tetrahydrofuran (THF).Usually, 1, the 4-butyleneglycol is to be raw material with acetylene and formaldehyde, and is under high pressure synthetic, also can make by gamma-butyrolactone or by the tetrahydrofuran (THF) hydrolysis.The development for preparing the MALEIC ANHYDRIDE technology along with butane oxidation, since the eighties, adopting the base metal mixed oxide is catalyzer, make 1 from the maleate vapour phase hydrogenation, the development of the method for 4-butyleneglycol is very fast, and disclosing a kind of as EP0143634 is catalyzer at 150-240 ℃, 25-75 crust, H with Cu-Cr-Ba or Cu-Cr-Mn mixed oxide
2/ ester mol ratio is 150-800: 1, and raw material liq volume charging air speed (LHSV) is 0.1-0.6 hour
-1, adopt two sections vapour phase hydrogenation methods to make 1 by diethyl maleate and/or diethyl succinate, the method for 4-butyleneglycol, this method result preferably was: 170-190 ℃, 4MPa, LHSV 0.34 hour
-1, H
2/ ester mol ratio is under 300: 1 conditions, ester conversion rate＞90 mole %, and 1.4-butyleneglycol selectivity just can reach 70 moles more than the %.WO 9101961 discloses the gas phase catalytic hydrogenation reactor of two parallel connections of a kind of employing, makes 1 by maleate, and the method for 4-butyleneglycol, this method are compared the resistance that has reduced reactor with tandem reactor, simplified technology, but not mentioned air speed problem.
The purpose of this invention is to provide a kind of is raw material with maleic acid alkyl ester and/or succinic acid dialkyl ester, uses non-precious metal catalyst, carries out one section gas phase catalytic hydrogenation prepared in reaction 1, the method for 4-butyleneglycol.This method has overcome the deficiency of prior art, can obtain 1 of high yield under bigger raw material liq volume charging air speed condition, the 4-butyleneglycol, and have good reaction stability.
The used catalyzer of the present invention is to be that the general formula that 94105927.8 the described method of Chinese patent application makes is Cu according to application number
aZnCr
bM
cO
xNon-precious metal catalyst, wherein a=0.1-10, b=0.1-5, c=0.1-5 represent the atomicity of Cu, Cr, M respectively, X is for satisfying the needed oxygen atomicity of other element valence requirement, M is a kind of element that is selected from the IVB family, Zr element preferably, and its preparation process comprises:
(1) Cu, Zn, Zr salt and the chromic trioxide proportion of composing according to this catalyzer is dissolved in the deionized water, make the solution that mixture concentration is 20～50m%, under agitation mix with alkali, co-precipitation takes place, pH value=the 5-7 of control solution filters, washs, in 100-120 ℃ of dry 10-15 hour, at 350-500 ℃ of roasting 20-30 hour, moulding then, make catalyst Precursors;
(2) negate is seated in the fixed-bed reactor in requisition for the catalyst Precursors of amount, in the presence of hydrogen or the hydrogen with inert gas dilution, reduces 5-40 hour in 150-300 ℃ under 0.1-2.0MPa pressure.
Its technological process of the method for the invention is: catalyzer is after the reduction pre-treatment, temperature of reactor is reduced to temperature of reaction, feeding maleic acid alkyl ester and/or succinic acid dialkyl ester and hydrogen then in reactor carries out catalytic hydrogenation and can make 1, the 4-butyleneglycol.When being raw material with the maleic acid alkyl ester, its reaction formula is as follows:
Its processing condition are: reaction pressure 1-8MPa, 3-7MPa preferably; Temperature of reaction 190-300 ℃, preferably 200-280 ℃; Reacting material liquid volume charging air speed 0.2-2.0 hour
-1, preferably 0.4-1.0 hour
-1H
2/ ester mol ratio is 100-500: 1,150-300 preferably: 1.In addition, the hydrogen of separating from reaction product can recycle.
The method of the invention relatively has characteristics such as technology is simple, space-time yield is high, 1,4 fourth-glycol selectivity height, good stability with adopting two sections hydrogenant prior aries.As use the method for the invention, be 0.6 hour with the diethyl maleate for raw material LHSV
-1Under the condition, successive reaction 700 hours, reaction result: the ester per pass conversion remains on 90 moles more than the %, and 1,4-butyleneglycol selectivity remains on 70 moles more than the %, and existing technology is by two-stage hydrogenation, and also air speed has only 0.34 hour
-1, 1, the selectivity of 4-butyleneglycol just can reach same level.
The following examples will the invention will be further described.
Example 1
Preparation of catalysts and pre-treatment: be example 1 described method in 94105927.8 the Chinese patent application according to application number, with 261 gram cupric nitrate (chemical pure, the Beijing Chemical Plant), 298 gram zinc nitrate (chemical pure, the Beijing Chemical Plant), 116 gram chromic trioxides (chemical pure, Beijing Chemical Plant), 134 gram zirconium nitrate (chemical pure, the Beijing Chemical Plant) is dissolved in 1000 milliliters of deionized waters, then, under agitation mixes with ammoniacal liquor, generate precipitation, filter control pH=6 ± 1, washing was in 110 ± 10 ℃ of dryings 12 hours, in 400 ± 50 ℃ of roastings 24 hours, moulding then, make catalyst Precursors.Getting granularity is 2 milliliters of 40-80 purpose catalyst Precursors, the internal diameter of packing into is 5 millimeters, length is in 150 millimeters the stainless steel tubular type reactor, use the nitrogen purging reactive system, and with the reactive system pressurising to 1MPa, feed hydrogen with 35 liters/hour flow to reactive system then, simultaneously reactor is raised to 300 ℃ by room temperature, and kept 2 hours at 300 ℃ with 110 ℃/hour average heating speed.
Catalytic hydrogenation reaction: reactor being dropped to 210 ℃, feed diethyl maleate (technical pure, Ningbo insecticide factory) and hydrogen in reactor, is 210-220 ℃ in temperature of reaction, and reaction pressure is 7MPa, H
2/ ester mol ratio is that 224: 1, raw material LHSV are 0.6 hour
-1Successive reaction is 700 hours under the condition, reaction result, the ester per pass conversion remain on 90 moles of % above, 1,4-butyleneglycol selectivity remains on 70 moles more than the %, the gamma-butyrolactone selectivity remains on about 20 moles of %, all the other mainly are tetrahydrofuran (THF)s, and existing technology is by two-stage hydrogenation, and air speed has only 0.34 hour
-1, 1, the selectivity of 4-butyleneglycol just can reach same level.
Example 2
Getting 62.5 milliliters of granularities by the preparation of example 1 method is 2.5 millimeters * 2 millimeters of , compressive strength be 100 ± 50 newton/centimetre catalyst Precursors to install to internal diameter be 23 millimeters of , length is in 1000 millimeters the stainless steel tubular type reactor, use the nitrogen purging reactive system, and 0.3MPa is arrived in the reactive system pressurising, feed hydrogen with nitrogen dilution, density of hydrogen is brought up to 100Vol% gradually by 2Vol%, simultaneously, reactor is raised to 280 ℃ lentamente by room temperature, total recovery time is about 36 hours.At last temperature of reactor being dropped to temperature of reaction, is reaction raw materials (technical pure, Zhejiang Jiande Organic Chemicals Plant) with the dibutyl maleate, is 0.4 hour in liquid volume charging air speed
-1, hydrogen/ester mol ratio is 400: 1,222 ± 2 ℃ of temperature of reaction are reacted reaction result under the reaction pressure 6MPa condition: 99 moles of % of ester per pass conversion, 1,79 moles of % of 4-butyleneglycol selectivity.14 moles of % of gamma-butyrolactone selectivity, all the other are mainly tetrahydrofuran (THF).
By example 1,2, as can be seen: the method for the invention with adopt two sections hydrogenant prior aries relatively, have characteristics such as technology is simple, space-time yield height.
Annotate: compressive strength assay method: RIPP 25-90 (referring to " the petrochemical complex analytical procedure " that people such as Yang Cuiding write, Science Press).
Claims (6)
1. one kind 1, the preparation method of 4-butyleneglycol is to be raw material with maleic acid alkyl ester and/or succinic acid dialkyl ester, carries out gas phase catalytic hydrogenation prepared in reaction 1, the 4-butyleneglycol, and it is characterized in that this method comprises following process: with general formula is Cu
aZnCr
bM
cO
xCatalyst loading in fixed-bed reactor, after pre-treatment, reduce to temperature of reaction, feed maleic acid alkyl ester and/or succinic acid dialkyl ester and hydrogen and carry out catalytic hydrogenation preparation 1, the 4-butyleneglycol, its processing condition are: reaction pressure 3-7MPa, temperature of reaction 200-280 ℃, reacting material liquid volume charging air speed 0.4-1.0 hour
-1, H
2/ ester mol ratio is 150-300: 1, and the hydrogen of separating from reaction product can recycle.
2. according to the said preparation method of claim 1, it is characterized in that the alkyl ester in maleic acid alkyl ester and/or the succinic acid dialkyl ester is C
1-C
4Alkyl ester.
3. according to the said preparation method of claim 1, it is characterized in that at catalyzer general formula Cu
aZnCr
bM
cO
xIn, a=0.1-10, b=0.1-5, c=0.1-5 represent that respectively the atomicity of Cu, Cr, M, x are for satisfying the needed oxygen atomicity of other element valence requirement, M is a kind of element that is selected from the IVB family.
4. according to claim 1 or 3 said preparation methods, it is characterized in that M is the Zr element.
5. according to the said preparation method of claim 1, it is characterized in that the pre-treatment of catalyzer is meant: with general formula is Cu
aZnCr
bM
cO
xCatalyst Precursors under 0.1-2.0MPa pressure in 150-300 ℃ the reduction 5-40 hour.
6. according to the said preparation method of claim 1, the succinic acid dialkyl ester that reaction generates when it is characterized in that unreacted succinic acid dialkyl ester or maleic acid alkyl ester for raw material can recycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108096A CN1049208C (en) | 1994-08-10 | 1994-08-10 | Method for preparing 1,4-butanediol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108096A CN1049208C (en) | 1994-08-10 | 1994-08-10 | Method for preparing 1,4-butanediol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1116616A CN1116616A (en) | 1996-02-14 |
| CN1049208C true CN1049208C (en) | 2000-02-09 |
Family
ID=5033355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94108096A Expired - Fee Related CN1049208C (en) | 1994-08-10 | 1994-08-10 | Method for preparing 1,4-butanediol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1049208C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2007012298A (en) * | 2005-04-05 | 2007-10-16 | Firmenich & Cie | Hydrogenation of esters with ru/tetradentate ligands complexes. |
| US9168509B2 (en) | 2011-11-09 | 2015-10-27 | China Petroleum & Chemical Corp. | Hydrogenation catalysts and the preparation processes thereof |
| CN104892363A (en) * | 2015-06-15 | 2015-09-09 | 江苏常州酞青新材料科技有限公司 | Method for preparing butanediol |
| CN107778145B (en) * | 2016-08-30 | 2020-11-13 | 中国石油化工股份有限公司 | Method for producing 1, 4-butanediol and/or sec-butanol |
| EP3483138A1 (en) * | 2017-11-09 | 2019-05-15 | Fundacion Tecnalia Research & Innovation | Method for continuous production of 2,3-butanediol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02233630A (en) * | 1989-03-08 | 1990-09-17 | Tonen Corp | Production of 1,4-butanediol and tetrahydrofuran |
| WO1991001961A1 (en) * | 1989-08-04 | 1991-02-21 | Davy Mckee (London) Limited | Process |
| EP1043634A1 (en) * | 1997-12-25 | 2000-10-11 | Seiko Instruments Inc. | Timepiece equipped with display correction device |
-
1994
- 1994-08-10 CN CN94108096A patent/CN1049208C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02233630A (en) * | 1989-03-08 | 1990-09-17 | Tonen Corp | Production of 1,4-butanediol and tetrahydrofuran |
| WO1991001961A1 (en) * | 1989-08-04 | 1991-02-21 | Davy Mckee (London) Limited | Process |
| EP1043634A1 (en) * | 1997-12-25 | 2000-10-11 | Seiko Instruments Inc. | Timepiece equipped with display correction device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1116616A (en) | 1996-02-14 |
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