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EP1846358A1 - Procede de production de bis(3-aminopropyl)amine (dipropylene-triamine, dpta) - Google Patents

Procede de production de bis(3-aminopropyl)amine (dipropylene-triamine, dpta)

Info

Publication number
EP1846358A1
EP1846358A1 EP06707954A EP06707954A EP1846358A1 EP 1846358 A1 EP1846358 A1 EP 1846358A1 EP 06707954 A EP06707954 A EP 06707954A EP 06707954 A EP06707954 A EP 06707954A EP 1846358 A1 EP1846358 A1 EP 1846358A1
Authority
EP
European Patent Office
Prior art keywords
column
pda
reaction zone
reaction
dpta
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06707954A
Other languages
German (de)
English (en)
Inventor
Johann-Peter Melder
Thomas Krug
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1846358A1 publication Critical patent/EP1846358A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/64—Preparation of compounds containing amino groups bound to a carbon skeleton by disproportionation

Definitions

  • the present invention relates to a process for the preparation of bis (3-amino-propyl) amine (dipropylenetriamine, DPTA) by continuous reaction of 1, 3-propylenediamine (1, 3-PDA) in the presence of a heterogeneous catalyst.
  • DPTA which has the following structural formula, is used as an intermediate and hardener for epoxy resins and for the synthesis of vulcanization accelerators, emulsifiers and corrosion inhibitors.
  • 3-propylenediamine [H 2 N-CH 2 -CH 2 -CH 2 -NH 2 ; 1, 3-PDA] can be prepared by known methods, for example by aminative hydrogenation of 1, 3-propanediol or 1-amino-3-propanol or by hydrogenation of malononitrile.
  • Symmetrical secondary amines can be prepared by catalytic amination of corresponding alcohols, aldehydes or ketones with corresponding primary amines to release one molar equivalent of water.
  • metallic amination catalysts e.g., Ni, Co, Cu
  • Examples include the dimerization (conversion) of ethyleneamine (EDA) to diethylenetriamine (DETA) and the dimerization of 3- (N, N-dimethylamino) propylamine (DMAPA) to bis [(3-dimethylamino) propyl] amine ( Called BisDMAPA).
  • EDA ethyleneamine
  • DETA diethylenetriamine
  • DMAPA dimerization of 3- (N, N-dimethylamino) propylamine
  • Called BisDMAPA bis [(3-dimethylamino) propyl] amine
  • EP-A1-1 431 273 (BASF AG) relates to a process for the preparation of a symmetric see secondary amine by reacting a primary amine in the presence of hydrogen and a catalyst, wherein a catalyst is used in whose Production of a precipitation of catalytically active components on monoclinic, tetra- gonal or cubic zirconium dioxide was carried out.
  • EP-A1-1 270 543 (BASF AG) describes a process for the preparation of certain secondary amines from primary amines in the presence of hydrogen and a catalyst which comprises at least one element or compound of an element from Groups VIII and IB of the Periodic Table.
  • DE-A1-3248 326 (BASF AG) relates to a process for the preparation of polyamines from 2-cyanoethylamines on a cobalt catalyst.
  • German Patent Application No. 10359811.1 dated 19.12.03 (BASF AG) relates to a method for increasing the space-time yield (RZA) in a process for producing a symmetrical secondary amine by reacting a primary amine in the presence of hydrogen and a catalyst a temperature in the range of 50 to 250 ° C and an absolute pressure in the range of 5 to 350 bar, by lowering the absolute pressure while maintaining the temperature.
  • RZA space-time yield
  • Reactive distillation applications also include esterification, saponification and transesterification, acetal production and saponification, alkoxide production, aldol condensation, alkylation, epoxide hydrolysis, olefin hydration, isomerization, and hydrogenation.
  • German Patent Application Nos. 10336003.4 of 01.08.03 and 102004030645.1 of 24.06.04 relate to processes for the preparation of ethylene amines by continuous reaction of ethylene diamine (EDA) in the presence of a heterogeneous catalyst, wherein the reaction is carried out in a reaction column ,
  • the ethylene amines produced are, in particular, diethylenetriamine (DETA), piperazine (PIP) and / or triethylenetetramine (TETA).
  • DETA diethylenetriamine
  • PIP piperazine
  • TETA triethylenetetramine
  • the object of the present invention was to find an improved economical process for the selective preparation of DPTA in high yield and space-time yield (RZA).
  • the reaction column preferably has a region in which the conversion of 1, 3-PDA to DPTA takes place (reaction zone), a rectifying section above the reaction zone and a stripping section below the reaction zone.
  • the absolute pressure in the column is preferably in the range of> 0 to 20 bar, e.g. in the range of 1 to 20 bar, in particular 5 to 10 bar.
  • the temperature in the region of the column in which the reaction of 1, 3-held PDA to DPTA is preferably in the range of 100 to 200 ° C, in particular 140 to 160 0 C.
  • the number of theoretical plates in the column as a whole is preferably in the range from 5 to 100, particularly preferably 10 to 20.
  • the number of theoretical plates in the reaction zone is preferably in the range of 1 to 30, especially 1 to 20, especially 1 to 10, e.g. 5 to 10.
  • the number of theoretical plates in the rectifying section above the reaction zone is preferably in the range from 0 to 30, especially 1 to 30, more particularly 1 to 15, in particular 1 to 5.
  • the number of theoretical plates in the stripping section below the reaction zone is preferably in the range from 0 to 40, especially 5 to 30, in particular 10 to 20.
  • 1, 3-PDA in the column can be carried out below the reaction zone in liquid form or in gaseous form.
  • 1, 3-PDA in the column can also be carried out in liquid form above the reaction zone.
  • the reaction is particularly preferably carried out in the presence of hydrogen, in particular in the presence of 0.0001 to 1 wt .-%, preferably 0.001 to 0.01 wt .-%, hydrogen, each based on the feed amount of 1, 3-PDA performed ,
  • the addition of hydrogen into the column is preferably carried out below the reaction zone.
  • a mixture of ammonia, other components having a boiling point lower than DPTA (at the same pressure) (low boilers) and optionally hydrogen is preferably removed from the top of the column.
  • the mixture withdrawn overhead the column may also contain aliquots of unreacted 1, 3-PDA.
  • the top-removed mixture can also be partially condensed while ammonia and optionally hydrogen taken mainly separated in gaseous form (separated) and the liquefied portion can be added as reflux to the column.
  • the weight ratio of the reflux amount of the column (column return amount) to the amount of the feed to the column is preferably in the range of 0.1 to 30, particularly preferably 0.5 to 10, in particular 0.5 to 2.
  • a mixture of DPTA and other components having a boiling point higher than DPTA (at the same pressure) (heavies), such as e.g. Tripropylenetetramine (TPTA),
  • the mixture withdrawn from the bottom of the column may also contain aliquots of unreacted 1,3-PDA or the total amount of unreacted 1,3-PDA.
  • the column below the reaction zone is subdivided by a side draw.
  • 3-PDA is preferably removed via the side take-off.
  • the product removed via the side trigger may also contain DPTA.
  • the product obtained via the side take-off is removed in liquid form or in gaseous form.
  • the catalyst used in the reaction zone is preferably a catalyst comprising Ni, Co, Cu, Ru, Re, Rh, Pd and / or Pt or a shape-selective zeolite catalyst or a phosphate catalyst.
  • the one or more metals of the transition metal catalyst are preferably on an oxidic support material (eg Al 2 O 3 , TiO 2 , ZrO 2 , SiO 2 ) or on a zeolite or activated carbon as Applied carrier material.
  • an oxidic support material eg Al 2 O 3 , TiO 2 , ZrO 2 , SiO 2
  • a zeolite or activated carbon as Applied carrier material.
  • the catalyst used in the reaction zone is a catalyst comprising Pd and zirconium dioxide as support material.
  • the total metal content of the supported transition metal catalysts is preferably in the range of> 0 to 80 wt .-%, especially 0.1 to 70 wt .-%, more particularly 5 to 60 wt .-%, more particularly 10 to 50 wt. -%, in each case based on the weight of the support material.
  • the total noble metal content is in particular in the range of> 0 to 20 wt .-%, particularly 0.1 to 10 wt .-%, especially 0.2 to 5 wt .-% , further particularly 0.3 to 2 wt .-%, each based on the weight of the carrier material.
  • the heterogeneous catalysts can be accommodated in the form of solid catalyst beds inside the column or in separate containers outside the column. They can also be used as beds, e.g. as a bed in a distillation pack, are used, are shaped into random packings or shaped bodies, for example pressed into Raschig rings, introduced into filter cloths and formed into rolls (so-called bales) or column packs, applied to distillation packs (coating) or as a suspension in the column, in this case preferably used as a suspension on column trays.
  • Multi-channel packages or cross-channel packages allow easy filling and discharge of catalysts which are in particulate form (e.g., spheres, stringers, tablets) with little mechanical stress on the catalyst.
  • reaction column e.g., number of stages in the column sections, enrichment section, stripping section and reaction zone, reflux ratio, etc.
  • design of the reaction column can be carried out by methods familiar to those skilled in the art.
  • the process according to the invention is carried out in accordance with WO-A1-03 / 047,747 in a column for carrying out reactive distillations in the presence of a heterogeneous particulate catalyst, with a packing or packing which forms interspaces in the column interior, the column being first and second has second subregions which are arranged alternately and differ by the specific surface of the packing or packing, in such a way that in the first partial ranges the quotient of the hydraulic diameter for the gas flow through the packing or packing and the equivalent diameter of the catalyst particles is in the range of 2 to 20, preferably in the range of 5 to 10, the catalyst particles being loose under the influence of Gravity introduced into the interstices, distributed and discharged and that in the second part of the quotient of the hydraulic diameter for the gas flow through the packing or the packing and the equivalent diameter of the catalyst is less than 1 and in that no catalyst particles introduced into the second portions become.
  • the column is preferably operated so that a maximum of 50 to 95%
  • the workup of the product streams obtained in the process according to the invention which contain, above all, the desired DPTA, but also optionally TPTA and optionally higher polyamines and optionally unreacted 1, 3-PDA, can be carried out by distillation processes known to the person skilled in the art. (See, e.g., PEP Report No. 138, "Alkyl Amines", SRI International, 03/1981, pp. 81-99, 117).
  • distillation columns needed for the distillative recovery of the desired product DPTA can be designed by methods familiar to a person skilled in the art (for example number of separation stages, reflux ratio, etc.).
  • the side draw stream consisting predominantly of unreacted 1, 3-PDA, contains only small amounts of DPTA and heavies.
  • Subsets or the entire amount of the side stream can also be recycled to the reaction column itself. This is particularly advantageous when the side stream contains predominantly 1, 3-PDA and little or no DPTA.
  • the bottom draw stream of the reaction column contains less low boilers (1, 3-PDA) in this procedure, so that the column for the separation of the low-boiling components of DPTA and high boilers is relieved.
  • the reactive distillation is carried out at low pressures, for example 1 to 3 bar, it is also possible to obtain the bottom draw stream at bottom temperatures of about 200 to 240 ° C free from 1, 3-PDA.
  • the bottom draw stream can be fed directly to the purifying distillation of DPTA.
  • the process according to the invention makes it possible to prepare DPTA with a selectivity of> 70%, in particular> 75%, very particularly> 80%, in each case based on reacted 1, 3-PDA, with a 1,3-PDA conversion of> 30%. , in particular> 40%, especially> 50%.
  • Figure 1 in Appendix 1 shows an embodiment of the inventive method in which pure 1, 3-PDA is fed together with hydrogen the reaction column continuously below the catalytic packing and a mixture containing DPTA, unreacted 1, 3-PDA and high boilers (SS, ie components having a boiling point higher than DPTA, eg TPTA, TPPA) over sump.
  • SS unreacted 1, 3-PDA and high boilers
  • LS low boilers
  • Figure 2 in Appendix 2 shows an embodiment of the inventive method in which pure 1, 3-PDA together with hydrogen of the reaction column continuously borrowed below the catalytic packing is fed and a mixture containing DPTA and high boilers (SS, ie components having a boiling point higher than DPTA, eg TPTA, TPPA) is obtained via sump.
  • SS DPTA and high boilers
  • LS low boilers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé permettant de produire de la bis(3-aminopropyl)amine(dipropylène-triamine, DPTA) par réaction continu de 1,3-propylène-diamine (1,3-PDA), en présence d'un catalyseur hétérogène, qui se caractérise en ce que la réaction est effectuée dans une colonne de réaction.
EP06707954A 2005-02-01 2006-02-01 Procede de production de bis(3-aminopropyl)amine (dipropylene-triamine, dpta) Withdrawn EP1846358A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005004854A DE102005004854A1 (de) 2005-02-01 2005-02-01 Verfahren zur Herstellung von Bis(3-aminopropyl)amin (Dipropylentriamin, DPTA)
PCT/EP2006/050592 WO2006082203A1 (fr) 2005-02-01 2006-02-01 Procede de production de bis(3-aminopropyl)amine (dipropylene-triamine, dpta)

Publications (1)

Publication Number Publication Date
EP1846358A1 true EP1846358A1 (fr) 2007-10-24

Family

ID=36406022

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06707954A Withdrawn EP1846358A1 (fr) 2005-02-01 2006-02-01 Procede de production de bis(3-aminopropyl)amine (dipropylene-triamine, dpta)

Country Status (6)

Country Link
US (1) US20080132725A1 (fr)
EP (1) EP1846358A1 (fr)
JP (1) JP2008528558A (fr)
CN (1) CN101111468A (fr)
DE (1) DE102005004854A1 (fr)
WO (1) WO2006082203A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005004853A1 (de) * 2005-02-01 2006-08-03 Basf Ag Verfahren zur Herstellung von Bis-[(3-Dimethylamino)propyl]amin (BisDMAPA)
CN101817753B (zh) * 2010-04-01 2012-09-12 大连理工大学 一种n-(3-氨基丙基)-1,3-丙二胺的制备方法
BR112013011669A2 (pt) 2010-11-10 2019-09-24 Dow Global Technologies Llc método para fazer uma mistura de produtos contendo poliamina de alto peso molecular linear, método para fazer uma mistura de congeneres de poliaminas de alto peso molecular e método para fazer uma mistura de poliaminas acíclicas de alto peso molecular
JP2014516342A (ja) * 2011-03-22 2014-07-10 ビーエーエスエフ ソシエタス・ヨーロピア ニトリルの水素化法
KR102024404B1 (ko) 2011-12-29 2019-09-23 다우 글로벌 테크놀로지스 엘엘씨 환식 아민 화합물로부터 제조된 아민 폴리에테르 폴리올 및 폴리우레탄 포움 조성물
WO2013102097A2 (fr) 2011-12-29 2013-07-04 Dow Global Technologies Llc Composés amines cycliques, compositions et mousses de polyuréthane obtenues par ces compositions
CN104169262B (zh) 2011-12-29 2017-04-26 陶氏环球技术有限责任公司 从环状多胺化合物形成较高分子量的环状多胺化合物
CN102614894B (zh) * 2012-03-04 2013-11-13 浙江建业化工股份有限公司 用于异丙胺合成二异丙胺的负载型催化剂及其制法和用途
EP3077444B1 (fr) 2013-12-02 2018-04-25 Dow Global Technologies LLC Préparation de polyalkylénamines acycliques, ramifiées, de poids moléculaire élevé et mélanges de celles-ci
WO2015128021A1 (fr) 2014-02-26 2015-09-03 Basf Se Procédé de fabrication de polyamines

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0478428B1 (fr) * 1990-09-25 1995-03-08 Institut Français du Pétrole Procédé de préparation d'oxyde borique par hydrolyse du borate de méthyle et sa mise en oeuvre dans l'oxydation d'hydrocarbures saturées en alcools
KR960022419A (ko) * 1994-12-29 1996-07-18 김준웅 반응증류를 이용하여 메틸아세테이트로부터 초산과 메탄올을 제조하는 방법 및 장치
DE10129908A1 (de) * 2001-06-21 2003-01-02 Basf Ag Verfahren zur Herstellung von sekundären Aminen aus primären Aminen
US7098366B2 (en) * 2001-12-06 2006-08-29 Basf Aktiengesellschaft Supported metal oxides as catalysts for aldol condensations
DE10159821A1 (de) * 2001-12-06 2003-06-18 Basf Ag Vorrichtung und Verfahren zur Durchführung von heterogen katalysierter Reaktivdestillationen, insbesondere zur Herstellung von Pseudoionen
DE10261195A1 (de) * 2002-12-20 2004-07-01 Basf Ag Verfahren zur Herstellung eines symmetrischen sekundären Amins
WO2005012223A1 (fr) * 2003-08-01 2005-02-10 Basf Aktiengesellschaft Procede de production d'ethylene-amines

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006082203A1 *

Also Published As

Publication number Publication date
WO2006082203A1 (fr) 2006-08-10
JP2008528558A (ja) 2008-07-31
CN101111468A (zh) 2008-01-23
US20080132725A1 (en) 2008-06-05
DE102005004854A1 (de) 2006-08-17

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