EP1966216A1 - Traitement pour la fabrication de triethylene diamine ultra pur - Google Patents

Traitement pour la fabrication de triethylene diamine ultra pur

Info

Publication number
EP1966216A1
EP1966216A1 EP06830449A EP06830449A EP1966216A1 EP 1966216 A1 EP1966216 A1 EP 1966216A1 EP 06830449 A EP06830449 A EP 06830449A EP 06830449 A EP06830449 A EP 06830449A EP 1966216 A1 EP1966216 A1 EP 1966216A1
Authority
EP
European Patent Office
Prior art keywords
teda
extractant
adsorption
raffinate phase
products
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Withdrawn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
EP06830449A
Other languages
German (de)
English (en)
Inventor
Ortmund Lang
Jürgen CIPRIAN
Matthias Rauls
Matthias Frauenkron
Gunther Van Cauwenberge
Jan Nouwen
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 EP1966216A1 publication Critical patent/EP1966216A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/08—Bridged systems

Definitions

  • the present invention relates to a process for the processing of a raffinate phase, which is obtained in the preparation and workup of triethylenediamine (abbreviated to TEDA hereinafter).
  • TEDA is a major catalyst for the production of polyurethane foams.
  • various methods are known which are comparatively associated with a high effort to meet the requirement for quality, in particular color and color stability, odor and purity of the TEDA.
  • TEDA TEDA
  • product mixtures which, in addition to TEDA, also contain water, by-products such as piperazine and high molecular weight compounds, and also, if appropriate, solvents used in the reaction.
  • TEDA is usually separated by fractional, batch or continuous distillation or rectification and usually further purified in a subsequent step by crystallization and / or recrystallization.
  • crystalline TEDA The handling of crystalline TEDA is hampered by its hygroscopic and toxic properties. The fact that TEDA solidifies slightly may cause blockages in the equipment and piping used. However, the formation of TE DA / water hydrate with existing water leads to deposits in the apparatus used.
  • the application DE 101 00 943.7 describes a process for the preparation of pure TEDA in which TEDA from a product mixture comprising a solvent or a diluent which has a boiling point in the range of 175 to 250 ° C at atmospheric pressure, evaporates and the gaseous TEDA in a solvent is introduced and recovered by subsequent crystallization as pure TEDA high quality, which is subsequently obtained by a solid-liquid separation as a high purity, crystalline TEDA.
  • the mother liquor obtained contains, in addition to TEDA, desired by-products and decomposition products so that the mother liquor can not be recycled directly to the process and the TEDA present in the mother liquor can be recovered.
  • the mother liquor is further worked up, in which an extractant is used, which is not or only slightly miscible with the solvent of the mother liquor and in which TEDA dissolves well.
  • an extractant is used, which is not or only slightly miscible with the solvent of the mother liquor and in which TEDA dissolves well.
  • predominantly TEDA and unwanted by-products and decomposition products have accumulated.
  • the resulting raffinate phase a mother liquor which has been purified to a certain extent, contains predominantly solvents and possibly further constituents which prevent the desired recirculation in the course of the process.
  • the object of the present invention is to provide an economical process for working up a raffinate phase resulting from the preparation and workup of pure TEDA, which makes it possible to reduce the need for fresh solvent by almost completely recycling a solvent used in the process Increase operating time.
  • the object is achieved by a process for working up TEDA in which TEDA is evaporated and the gaseous TEDA is introduced into a solvent, then crystallized from it and separated, and the resulting mother liquor is extracted with an extractant. Moreover, it is characterized in that the raffinate phase obtained after the extraction is further worked up by adsorption. The raffinate phase thus worked up can optionally be recycled to the process without the aforementioned disadvantages. In a preferred embodiment, the extraction / adsorption is carried out so that complete recycling is possible.
  • the first step of the process according to the invention comprises the process steps of working up TEDA which are described in the applications DE 199 33 850.7, DE 199 62 455.0, DE 101 00 943.7 and DE-A 101 22 502.4 of the Applicant.
  • the processes of working up TEDA described in the aforementioned applications are an integral part of the process according to the invention and are incorporated by reference into the present application. The procedures are shown again below.
  • the TEDA to be worked up can be prepared by known processes, for example by reacting monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, triethylenetetramine, piperazine, N- (2-hydroxyethyl) piperazine, N, N'-bis- (2-hydroxyethyl -piperazine, N- (2-aminoethyl) piperazine, N, N'-bis (2-aminoethyl) piperazine, morpholine or mixtures thereof on a catalyst, for example metal pyrophosphates, metal phosphates, for example alkaline earth monohydrogen phosphate, zeolite, Zirconium phosphates, Al 2 O 3 , SiO 2 , phosphorus-containing TiO 2 or ZrO 2 at elevated temperature, generally 250 to 450 ° C.
  • a catalyst for example metal pyrophosphates, metal phosphates, for example alkaline earth monohydrogen phosphate, zeo
  • the pressure here is 0.1 to 50 bar, in particular 0.1 to 5 bar.
  • an inert polar aprotic solvent such as N-alkylpyrrolidones, for example N-methylpyrrolidone, dioxane, THF, dialkylformamides, for example dimethylformamide, dialkylacetamides, for example dimethylac etamide and an inert carrier gas, for example N 2 or Ar.
  • the TEDA prepared by a known method is evaporated from the present product mixture and the gaseous TEDA is immediately introduced into a suitable solvent (TEDA quench).
  • a suitable solvent TEDA quench
  • Suitable solvents for the TEDA quench are a variety of organic solvents.
  • organic solvents include aliphatic, cyclic or acyclic hydrocarbons, in particular cyclic and acyclic, branched or unbranched alkanes or alkane mixtures, for example n-pentane, i-pentane, cyclopentane, hexane, cyclohexane, heptane, octane and petroleum ether, chlorinated aliphatic hydrocarbons, in particular chlorinated alkanes, for example dichloromethane, trichloromethane, dichloroether, trichloroether, aromatic hydrocarbons, for example benzene, toluene and xylene, chlorinated aromatic hydrocarbons, for example chlorobenzene, alcohols, for example methanol, ethanol, ethylene glycol, 1,4-butanediol and poly etherealcohols, in
  • the solvent used for the TEDA quench is preferably an aliphatic hydrocarbon or a polyalkylene glycol, in particular a saturated cyclic or acyclic aliphatic hydrocarbon having 5 to 8 C atoms, for example pentane, hexane, cyclohexane or heptane, or dipropylene glycol.
  • the introduction of the gaseous TEDA into the liquid solvent takes place in a quench apparatus, preferably a falling-stream condenser (thin-film, trickle-bed or falling-stream condenser) or in a nozzle apparatus.
  • a quench apparatus preferably a falling-stream condenser (thin-film, trickle-bed or falling-stream condenser) or in a nozzle apparatus.
  • the gaseous TEDA can be conducted in cocurrent or countercurrent with the liquid solvent. It is advantageous to introduce the gaseous TEDA from above into the quenching apparatus. Further advantageous is the tangential supply of the solvent at the head of the falling film capacitor or the supply of the liquid solvent through one or more nozzles in order to achieve complete wetting of the inner wall of the quench apparatus.
  • the amount of the solvent used is selected from the point of view of convenience.
  • the procedure is such that, depending on the type of solvent, solutions having a TEDA content of about 1 to 50% by weight, preferably 20 to 40% by weight, are obtained.
  • the temperature in the TEDA quench is adjusted by tempering the solvent used and / or the quenching apparatus to 20 to 100 ° C, preferably 30 to 60 ° C.
  • the absolute pressure in the TEDA quench is generally 0.5 to 1.5 bar.
  • the TEDA is crystallized from the resulting solution.
  • the crystallization of the TEDA can be carried out by a method known to the person skilled in the art.
  • the TEDA crystals obtained by a subsequent multistage, preferably single-stage crystallization are highly pure and are obtained by a solid-liquid separation.
  • the mother liquor present after this is intensively brought into contact with an extraction agent in an extraction stage in order to both recover TEDA still present and to separate off any impurities present.
  • the extractant is selected in such a way that the TEDA and the by-products and decomposition products responsible for the reduction in quality of the TEDA almost completely pass into the extract phase. As a result, the mother liquor is freed from these by-products and decomposition products, which is a prerequisite for the return to the process.
  • the extractant forms a large miscibility gap with the solvent used for the TEDA quench, the mutual solubility of the extraction solvent and solvent being ⁇ 10% by weight, preferably ⁇ 1% by weight.
  • TEDA dissolves much better in the extractant than in the solvent used in the crystallization step.
  • the extractant has a sufficient density difference from the mother liquor, which facilitates separation of the extract and raffinate phases.
  • the density difference is preferably> 50 kg / m 3 , in particular> 100 kg / m 3 .
  • the solvents preferably used according to the invention as extractants have hydroxyl groups and are in particular water or water-miscible solvents, such as lower alcohols or dihydric or polyhydric alcohols.
  • suitable alcohols include methanol, ethanol, n-propanol, i-propanol, ethylene glycol, polyethylene glycol and glycerol.
  • the alcohols can be used individually or as a mixture, if appropriate also in a mixture with water.
  • the most preferred extractant is water.
  • decomposition products mentioned may be referred to both as decomposition products and as intermediates.
  • the mother liquor (raffinate phase) depleted of TEDA, by-products and decomposition products and the extractant (extract phase) enriched with TEDA and the by-products and intermediates are separated in a suitable manner.
  • the raffinate phase contains portions of the extractant, whereby a direct recycling of this raffinate phase into the process sequence is not possible.
  • the presence of impurities can reduce the quality of TEDA and can lead to the formation of unwanted by-products that reduce the operating time of the work-up process.
  • the process according to the invention separates the contaminating constituents, in particular the dissolved extractant, from the raffinate phase.
  • This work-up step may be designed as a distillation, as a membrane process or as adsorption. According to the invention, preference is given to adsorption which can be easily integrated into the overall process for the preparation and processing of TEDA in the form of a continuously or discontinuously operated adsorption stage.
  • the amount of extractant contained in the raffinate phase is reduced to values of ⁇ 1 ppm by weight, preferably ⁇ 0.1 ppm by weight, more preferably ⁇ 0.01 ppm by weight.
  • Suitable adsorbents are those which are suitable for use in the liquid phase.
  • Preferred adsorbents are furthermore distinguished by the fact that the extractant present only in small amounts in the raffinate phase is removed as completely as possible or up to a tolerable fraction of ⁇ 1 ppm by weight.
  • the molecular groups contained in the preferred substance system ie saturated hydrocarbon as solvent and an extractant with one or more hydroxyl groups, more preferably pentane and water, have comparable molecular sizes.
  • the adsorbent should therefore in particular have hydrophilic properties in order to adsorb the extractant, which preferably has hydroxyl groups. Suitable adsorbents under these circumstances are silica gel or molecular sieves.
  • a molecular sieve preferably crystalline zeolite, having a suitable pore radius distribution and favorable hydrophilic properties. Particular preference is given to using a molecular sieve having a pore radius width of 3 angstroms, a specific surface area of 1000 m 2 / g.
  • the adsorbent according to the invention should particularly preferably remove up to a proportion of 0.01 ppm by weight of the extractant water from the solvent pentane, wherein the refinery flow is fed to the adsorption at a rate of 1 to 10 m / h.
  • the temperature at which the treatment according to the invention of the raffinate phase with the adsorbents is carried out is at values of 10 to 100 ° C., preferably at 20 to 40 ° C., the pressures at values of 0.1 to 5 bar, preferably 0.5 to 1, 5 bar.
  • the adsorbents are arranged in the form of a fixed bed, and the raffinate phase to be worked up is passed over the fixed bed.
  • the adsorbents can also be used in the form of a suspension bed.
  • the process can be carried out continuously, semicontinuously or discontinuously.
  • the adsorbed components can be removed at elevated temperature and / or by stripping with an inert gas.
  • the preferred embodiment is selected according to economic point of view.
  • the molecular sieve according to the invention is characterized by a long active phase, whereby regeneration steps are necessary only after a long period of operation.
  • the raffinate phase worked up by the process according to the invention can be almost completely recycled to the process stage of the TEDA quench and thus reduces the required amount of fresh solvent.
  • the formation of undesired by-products, in particular the formation of sparingly soluble TEDA / water hydrate caused by the use of water as the extraction agent, which leads to a reduction in the operating time of the workup plant, is avoided.
  • the TEDA quality and also the service life of the apparatuses and the pipelines of the workup are increased compared to the previous implementation of the method.
  • the method according to the invention can be carried out, for example, as follows:
  • a mixture containing TEDA for example, as a reaction in a continuous process by reaction of ethylenediamine and piperazine in a Gas phase reactor at 320 to 420 ° C and 0.5 to 1, 5 bar in the presence of a solvent (for example water), a carrier gas (for example N 2 or Ar) and a zeolite catalyst is obtained, in a distillation stage in a distillation column passed with about 15 theoretical stages.
  • a solvent for example water
  • a carrier gas for example N 2 or Ar
  • a zeolite catalyst for example, a solvent
  • low boilers for example, ammonia, ethylamine, water
  • the bottom effluent is pumped into a further distillation column with about 30 theoretical stages.
  • piperazine is separated overhead and optionally driven back to the synthesis reactor.
  • TEDA bottom effluent containing TEDA and high boiler is pumped into a further distillation column with about 25 theoretical stages. At a pressure of generally 500 mbar to 1, 5 bar in this column, the high boilers are discharged via the bottom outlet.
  • TEDA with a purity of> 95% by weight, in particular> 97% by weight, is taken off in vapor form over a partial condenser and in a falling film condenser in a solvent, preferably pentane and / or cyclohexane, at one temperature from 30 to 100 ° C, preferably 30 to 60 ° C, directly cooled in shock and simultaneously dissolved (TEDA quench).
  • TEDA quench TEDA from the resulting solution in a crystallization stage by evaporation of the solvent at a temperature of 10 to 100 ° C, preferably 20 to 40 ° C, and at a pressure of 0.1 to 5 bar, preferably 0, 5 to 1, 5 bar or by cooling at a temperature of generally -10 to 40 ° C, preferably 0 to 10 ° C crystallized out.
  • the withdrawn from the crystallization stage suspension is separated in a solid-liquid separation, for example in a centrifuge, in high purity, crystalline TEDA and mother liquor.
  • the mother liquor which still contains residues of the desired product as well as by-products and intermediates, is now in an extraction stage, for example a mixer / settler or an extraction column at a temperature of 10 to 100 ° C, preferably 20 to 40 ° C, and at one pressure from 0.1 to 5 bar, preferably 0.5 to 1, 5 bar intensively contacted with the extractant, preferably water.
  • the extract phase exiting the extraction stage after the mass transfer and subsequent phase separation which contains the major portion of the TEDA and the undesired by-products and decomposition products which may lead to a deterioration of the TEDA, is now either directly back to the reactor or via a Destillationsgraphic returned to the purification process.
  • the raffinate phase which, in addition to the solvent, removes the dissolved extractant and only traces of the TE DA and by-products and decomposition products, is at a temperature of 10 to 100 ° C, preferably 20 to 40 ° C, and a pressure of 0.1 to 5 bar, preferably 0.5 to 1, 5 bar, in an adsorption step via an adsorbent, preferably a 3 A molecular sieve, passed.
  • the solution obtained after the mass transfer from the adsorption stage which contains up to a fraction of preferably ⁇ 1 ppm by weight of extraction agent, is passed back to the TEDA quench.
  • the product obtained from a crystallization step with TEDA and secondary components for example ethylpiperazine, piperazine and aminoethylpiperazine, cyclohexane solution, is extracted continuously with water in a mixer / settler apparatus.
  • the residence time is 10 minutes, the temperature 20 ° C and atmospheric pressure.
  • the extract phase contains water, TEDA and most of the minor components.
  • the resulting raffinate phase has the following composition (in% by weight):
  • the high proportion of water in the raffinate phase prevents immediate recycling of the raffinate phase in the process.
  • the obtained from a crystallization step, with TEDA and minor components, for example, ethylpiperazine, piperazine and aminoethylpiperazine, pentane solution is extracted with water.
  • the resulting raffinate phase has the following composition (in% by weight):
  • the raffinate phase is passed from below through a vertical adsorption column, with a diameter of 30 mm and a length of 1 m, which is filled with a molecular sieve with a pore radius of 3 A, and analyzed afterwards.
  • the adsorption is carried out at a temperature of 20 ° C and atmospheric pressure.
  • the empty tube velocity of the raffinate phase in the adsorption column is 5 m / h.
  • the solution at the outlet of the adsorption column shows the following composition:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

La présente invention concerne un procédé de traitement de triéthylène diamine (TEDA), le TEDA étant vaporisé et le TEDA gazeux étant introduit dans un solvant, puis cristallisé et séparé de ce solvant, la liqueur mère obtenue étant extraite avec un agent d'extraction, ledit procédé étant caractérisé en ce que la phase de raffinat obtenue après l'étape d'extraction est traitée par une adsorption, l'agent d'extraction et/ou les produits secondaires et intermédiaires présents dans la phase de raffinat étant alors éliminés.
EP06830449A 2005-12-23 2006-12-07 Traitement pour la fabrication de triethylene diamine ultra pur Withdrawn EP1966216A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005061956A DE102005061956A1 (de) 2005-12-23 2005-12-23 Aufarbeitung bei der Herstellung von hochreinem Triethylendiamin
PCT/EP2006/069445 WO2007074034A1 (fr) 2005-12-23 2006-12-07 Traitement pour la fabrication de triethylene diamine ultra pur

Publications (1)

Publication Number Publication Date
EP1966216A1 true EP1966216A1 (fr) 2008-09-10

Family

ID=37865692

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06830449A Withdrawn EP1966216A1 (fr) 2005-12-23 2006-12-07 Traitement pour la fabrication de triethylene diamine ultra pur

Country Status (5)

Country Link
US (1) US20080312439A1 (fr)
EP (1) EP1966216A1 (fr)
CN (1) CN101321764A (fr)
DE (1) DE102005061956A1 (fr)
WO (1) WO2007074034A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009027791A1 (de) 2009-07-17 2011-01-27 Basf Se Zusammensetzung enthaltend Triethylendiamin, Monethylenglykol und Borhydrid

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102584833B (zh) * 2011-12-20 2015-03-18 山西玉龙化工有限公司 一种三乙烯二胺和乙醇胺混合物的分离方法
CN103664964B (zh) * 2013-12-18 2016-03-02 西安近代化学研究所 三乙烯二胺生产精馏气体的吸收方法及装置

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3960910A (en) * 1975-01-06 1976-06-01 Tenneco Chemicals, Inc. Process for the purification of gas streams
US5565066A (en) * 1994-10-07 1996-10-15 Uop Single vessel distillation and adsorption apparatus
ES2173064T3 (es) * 1999-07-23 2002-10-16 Basf Ag Procedimiento para la obtencion de trietilendiamina pura.
DE10100943A1 (de) * 2001-01-10 2002-07-11 Basf Ag Verfahren zur Herstellung von reinem Triethylendiamin(TEDA)
DE10122502A1 (de) * 2001-05-10 2002-11-14 Basf Ag Aufarbeitung der bei der Herstellung von hochreinem Triethylendiamin anfallenden Mutterlauge

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007074034A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009027791A1 (de) 2009-07-17 2011-01-27 Basf Se Zusammensetzung enthaltend Triethylendiamin, Monethylenglykol und Borhydrid

Also Published As

Publication number Publication date
US20080312439A1 (en) 2008-12-18
WO2007074034A1 (fr) 2007-07-05
DE102005061956A1 (de) 2007-07-05
CN101321764A (zh) 2008-12-10

Similar Documents

Publication Publication Date Title
EP1575906B1 (fr) Division d'un melange de gaz chlorhydrique et de phosgene
EP1575908B1 (fr) Procede de separation et de purification d'un solvant contenu dans un melange reactionnel resultant d'une synthese d'isocyanate
EP1575905B1 (fr) Procede de separation d'isocyanates a partir d'un melange reactionnel
EP0636620B1 (fr) Procédé d'obtention d'éthylène glycol-carbonate purifié
EP1223172B1 (fr) Procédé de préparation de triéthylènediamine (TEDA) pure
EP1070717B1 (fr) Procédé de préparation de triéthylènediamine pure
DE19625284A1 (de) Verfahren zur Trennung von Gemischen aus Dimethylether und Chlormethan
EP1749009B1 (fr) Procede de production d'une solution de triethylenediamine (teda) pure
EP1966216A1 (fr) Traitement pour la fabrication de triethylene diamine ultra pur
DE602005002922T2 (de) Verfahren zur Herstellung von Cyclohexanonoxim
EP1258485B1 (fr) Procédé de recyclage de la solution-mère issue du processus de production de la triéthylènediamine de haute pureté
EP1427731B1 (fr) Procede de preparation de triethylenediamine tres pure
EP2706045B1 (fr) Procédé de traitement d'un flux d'eaux usées formé lors du traitement d'un mélange réactif contenant de la triacétonamine
WO2009027434A2 (fr) Procédé pour séparer de l'acide formique contenu dans un mélange renfermant du trioxane
WO2007107557A1 (fr) Procede de fabrication de n,n-dimethylaminoethoxyethanol
DE19962455A1 (de) Verfahren zur Herstellung von reinem Triethylendiamin
EP1443048B1 (fr) Décoloration et stabilsation de la couleur de solutions TEDA

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20080723

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20110701