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EP1866282A1 - Production de mdi au moyen d'une phosphogenation en phase liquide et en phase gazeuse - Google Patents

Production de mdi au moyen d'une phosphogenation en phase liquide et en phase gazeuse

Info

Publication number
EP1866282A1
EP1866282A1 EP06725224A EP06725224A EP1866282A1 EP 1866282 A1 EP1866282 A1 EP 1866282A1 EP 06725224 A EP06725224 A EP 06725224A EP 06725224 A EP06725224 A EP 06725224A EP 1866282 A1 EP1866282 A1 EP 1866282A1
Authority
EP
European Patent Office
Prior art keywords
reaction
mmda
pmda
mixture
separated
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Withdrawn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
EP06725224A
Other languages
German (de)
English (en)
Inventor
Christian Müller
Eckhard Stroefer
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 EP1866282A1 publication Critical patent/EP1866282A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00—Derivatives of isocyanic acid
    • C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton

Definitions

  • the invention relates to a process for the preparation of isocyanates, comprising the steps
  • Aromatic isocyanates are important and versatile raw materials for polyurethane chemistry. MDI in particular is one of the most important technical isocyanates.
  • the general term "MDI" is used in the field and within the scope of this application as a generic term for methylene (diphenyldiisocyanate) and polymethylene polyphenylene polyisocyanate Methylene (diphenyld ⁇ socyanat) includes the isomers 2,2'-methylene (d ⁇ phenyld ⁇ socyanat) (2,2'-MDI), 2,4'-methylene (d ⁇ phenyld ⁇ socyanat)
  • MD In usual industrially relevant manufacturing processes, MD! The synthesis takes place in a two-stage process.
  • aniline is treated with formaldehyde to form a mixture of monomeric methylene (diphonydiname) - referred to in the art and within the scope of this invention as "MMDA” - and polymethylene polyphenylene polyamines - referred to in the art and within the scope of this invention as "PMDA” - condensed into the so-called crude MDA
  • the crude MDA usually produced by prior art processes contains about 70% MMDA and is preferred for an amine to formaldehyde behaviors of about 2.0 to 2.5
  • the object of the invention was to provide a process for the preparation of isocyanates which has a better space-time yield compared to the process known in the prior art. Furthermore, a process should be provided which has a lower phosgene hold-up in the In addition, a process should be provided that allows a smaller reactor volume in the phosgenation Finally, a method should be provided that is advantageous from an energetic point of view
  • the product mix of MMDI and PMDI should remain essentially unchanged from the processes known from the prior art Amount of discharged PMDI and MMDI understood
  • the invention thus relates to a process for the preparation of isocyanates, comprising the steps
  • step (1) described reaction of aniline with formaldehyde to monomeric methylene (d ⁇ phenyld ⁇ am ⁇ nen) (referred to in the context of this invention as "MMDA") and polymethylene polyphenylene polyamines (referred to in the context of this invention as “PMDA”) wherein this mixture of Methylene (d ⁇ phenyld ⁇ am ⁇ nen) and Polytymy- len polyphenylenepolyamines is called “crude MDA”
  • the reactants are usually mixed in a suitable mixing device Suitable mixing devices are, for example, mixing pumps, nozzles or static mixers
  • the reactants in a suitable reaction device such as For example, in tubular reactors, Ruhrreaktoren and Christskolo ⁇ nen or combinations thereof, reacted
  • the reaction temperature is generally between 20 and 200 0 C 1, preferably between 30 and 140 ° C.
  • step (1) is carried out in the presence of an acid as a catalyst, wherein the catalyst is preferably added in admixture with aniline.
  • Preferred catalysts are mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid. Mixtures of acids can also be used. Hydrochloric acid is particularly preferred If hydrogen chloride is used as the catalyst, then it can also be used in gaseous form.
  • the amount of catalyst can preferably be chosen so that a molar ratio of acid / aniline (S / A) of 0.05 to 0 T 5, particularly preferably of 0 , 08 to 0.3.
  • the reaction of step (1) is carried out in aqueous medium with HCl as catalyst. Further, the reaction can be carried out in the presence of a solvent. Particularly suitable are ethers, water and mixtures thereof. Examples of these are dimethylformamide (DMF), tetra hydrofuran (THF) and diethyl isophthalate (DEIP)
  • DMF dimethylformamide
  • THF tetra hydrofuran
  • DEIP diethyl isophthalate
  • Formaldehyde can be added to the process according to the invention in the form of monomeric formaldehyde and / or in the form of higher homologs, so-called poly (oxymethylene) glycols
  • composition of the prepared polyamine mixture (crude MDA) is influenced, in addition to the acid concentration and the temperature, decisively by the molar use ratio of aniline molecules to formaldehyde molecules (A / F properties) within the MDA process, which can be operated both continuously and discontinuously
  • a / F ratio chosen, the greater the MMDA content in the resulting crude MDA solution.
  • MMDA 2-core Ante ⁇ l
  • the 4-core MDA content decreases by -80%, if the A / F ratio increased from 2.4 to 5.9
  • the molar ratio of aniline formaldehyde in the context of this invention is generally from 1.8 to 10 l, preferably from 2 to 6 l, more preferably from 2.1 to 5.5 l, in particular from 2.2 to 5 l
  • reaction of aniline with formaldehyde can be carried out both continuously and discontinuously in a batch or semibatch process
  • the separation of the crude MDA from step (2) can be carried out by conventional methods known in the art.
  • the separation is carried out by distillation.
  • the separation is carried out by two rectification columns in which one after the other in the first column aniline and in the second column MMDA is obtained as top product and PMDA accumulates in the second column as the bottom product
  • the separation of the amine mixture is carried out in a so-called dividing wall column, wherein preferably a separation into the following three fractions takes place
  • a crude MDA which contains PMDA in such small amounts that the amine workup in one apparatus, eg a rectification column, into the two fractions aniline (overhead product) and MMDA (bottom product ) can be carried out
  • the purity (in terms of PMDA proportions) of the MMDA mixture separated in step (2) (fraction I) should be selected so that the MMDA mixture (fraction I) can be converted into the gas phase
  • the resulting crude MDA can be converted from liquid to gaseous state of matter It is preferred that the MMDA separated off in step (2) can be completely converted into the gas phase.
  • complete it is meant that a maximum of a residue of 2% by weight, preferably of at most 1% by weight, in particular of max 0.1 % By weight, which can not be converted into the gas phase
  • the separation of the crude MDA mixture in step (2) is such that the separated MMDA (fraction I) has a PMDA content of from 0 to less than 12 weight percent (wt%), more preferably from 0, 1 to less than 6% by weight, more preferably from 0.5 to less than 3.5% by weight, based on the total weight of MMDA and PMDA.
  • the purity (in terms of MMDA content) of the PMDA mixture separated in step (2) (fraction II) is not critical since the PMDA mixture does not have to be gasified.
  • the purity (in terms of MMDA proportions) of the separated in step (2) PMDA mixture (fraction II) can be selected from an economic point of view
  • the separation of the crude MDA mixture in step (2) takes place such that the separated PMDA (fraction II) has a content of MMDA of 0 to less than 50% by weight (% by weight), more preferably 0, From 5 to less than 30% by weight, more preferably from 1 to less than 20% by weight, in particular from 2 to less than 10% by weight, based on the total weight of PMDA and MMDA
  • step (3) After separation of the crude MDA mixture in step (2), there are 2 fractions, firstly a fraction containing essentially PMDA (fraction II) and a fraction essentially containing MMDA (fraction I) fraction (II) is now in the process step (3a) phosgenated in the Flussigphase, (ie there is a reaction of the amine groups with phosgene to isocyanate groups) and fraction (I) is phosgenated in process step (3b) in the gas phase
  • the separate phosgenations can be carried out in one plant or in different plants. If carried out in different facilities, these can also be located in different locations
  • the isocyanates are usually prepared by reacting the corresponding primary amines from fraction (a) with phosgene, preferably an excess of phosgene. This process takes place in the liquid phase.
  • phosgene preferably an excess of phosgene.
  • This process takes place in the liquid phase.
  • reaction in the liquid phase it is to be understood that at least one of the educt streams is in liquid Condition in the reaction is present.
  • an additional inert solvent can be added.
  • This additional inert solvent is usually an organic solvent or mixtures thereof.
  • Chlorobenzene, dichlorobenzene, t-chlorobenzene, toluene, hexane, diethyl isophthalate (DEIP), tetrahydrofuran (THF), dimethylformamide (DMF), benzene and mixtures thereof are particularly preferred Solvent chlorobenzoi
  • the content of amine based on the mixture amine / solvent is usually between 1 and 50% by mass, preferably between 2 and 40% by mass, particularly preferably between 3 and 30% by mass.
  • step (3a) can be carried out in the customary state of the art reactors. It is preferably carried out in a tubular reactor
  • the tube reactor is preferably heated either via its jacket surface or by means of heating elements contained in the tubular reactor, for example heating coils or heating tubes.
  • the tubular reactor can be segmented through the perforated bottom.
  • the tube reactor is defined by a length (L) to diameter ratio (D) of L / D> 6, preferably by L / D> 10.
  • step (3a) of the process according to the invention the mixing of the reactants preferably takes place in a mixing device which is characterized by a high shear of the reaction stream passed through the mixing device.
  • a mixing device is a rotary mixing device, a mixing pump or a mixing nozzle which precedes the reactor More preferably, a mixing nozzle is used.
  • the mixing time in this mixing device is usually 0.0001 s to 5 s, preferably 0.0005 to 4 s, more preferably 0 T 001 s to 3 s
  • the mixing time is to be understood as the time to be used by the mixer Beginning of the mixing process passes until 97.5% of the fluid elements of the resulting mixture have a mixing fraction which, based on the value of the theoretical final value of the mixture breakage of the resulting mixture on reaching the state of perfect mixture less than 2.5% of this final value of Mixture break deviate (to the concept of the Mixture Bruc hes see z BJ Warnatz, U Maas, RW dibble combustion, Springer Verlag, Berlin Heidelberg New York 1997, 2 edition, S 134)
  • the reaction of amine with phosgene is carried out at absolute pressures of 0 9 bar to 400 bar, preferably from 3 to 35 bar
  • the molar ratio of phosgene to amino groups used is generally 1, 1 1 to 12 1, preferably from 1, 25 1 to 8 1
  • the total residence time in the reactors amounts in general from 10 seconds to 15 hours, preferably 3 minutes is generally from 25 to 260 0 C (degrees Centigrade) to 12 h
  • the reaction temperature preferably from 35 to 240 0 C
  • the step (3a) in the process according to the invention is preferably carried out in one stage.
  • This is to be understood as meaning that the mixing and reaction of the reactants is carried out in one step in a temperature range from 60 to 200 ° C.
  • many processes known from the prior art are used carried out in two stages, ie the starting materials are mixed at about 30.degree. C. (here carbamyl chloride forms, this stage is often referred to as cold phosgenation) and then the mixed starting materials are heated at about 120.degree. to 200.degree. bamyl chloride is cleaved to isocyanate, this step is often referred to as hot phosgenation)
  • the step (3a) of the process according to the invention can be carried out continuously, semicontinuously or batchwise. It is preferably carried out continuously
  • the mixture of substances is preferably separated by rectification into isocyanate (s), solvent, phosgene and hydrogen chloride. Small amounts of by-products remaining in the isocyanate can be separated from the desired isocyanate by means of additional rectification or else crystallization
  • the product may contain inert solvent, carbamoyl chloride and / or phosgene and be further processed by the known methods (see, for example, WO 99/40059).
  • the preparation of the isocyanates is usually carried out by reacting the corresponding primary amines from fraction (b) with phosgene, preferably an excess of phosgene. This process takes place in the gas phase. Under reaction in the gas phase, it is to be understood that the educt streams in the gaseous state are mitem- react differently
  • reaction space which is generally arranged in a reactor, ie the reaction space is understood as meaning the space where the reaction of the reactants takes place.
  • reaction space is understood to mean the technical apparatus which contains the Reaction space containing these can be all customary, known from the prior art Reaktsonsraume that for non-catalytic, single-phase gas reaction, preferably to the continuous non-catalytic Suitable materials for contact with the reaction mixture include metals such as steel, tantalum, silver or copper, glass, ceramics, enamels, or homogeneous or heterogeneous mixtures thereof
  • the walls of the reactor can be smooth or profiled. For example, scratches or corrugations are suitable as profiles
  • the mixing of the reactants in a mixing device which is characterized by a high shear of the guided through the mixer reaction stream are preferably used as Mischei ⁇ nchtung a static mixing device or Mischduse, which is the reactor vorge is particularly preferred a Mischduse is used
  • the reaction of phosgene with amine in the reaction space is usually carried out at absolute pressures of more than 1 bar to less than 50 bar, preferably at more than 2 bar to less than 20 bar, more preferably between 3 bar and 15 bar, more preferably between 3, 5 bar and 12 bar, in particular from 4 to 10 bar
  • the pressure in the feed lines to the mixing device is higher than the above-mentioned pressure in the reactor.
  • the pressure in the feed lines is preferably from 20 to 1000 mbar, more preferably from 30 to 200 mbar higher than in the reaction space.
  • the pressure in the Auusedstungsvor ⁇ chtung lower than in the reaction chamber is preferably the pressure by 50 to 500 mbar, more preferably 80 to 150 mbar, lower than in the reaction space
  • step (3b) of the process according to the invention can be carried out in the presence of an additional inert medium.
  • the inert medium is a medium which is gaseous in the reaction space at the reaction temperature and does not react with the educts.
  • the inert medium generally undergoes reaction
  • nitrogen, noble gases such as helium or argon or aromatics such as chlorobenzene, dichlorobenzene or xylene can be used.
  • Nitrogen is preferably used as the inert medium. Particular preference is given to monochlorobenzene or a mixture of monochlorobenzene and nitrogen
  • the inert medium is used in an amount such that the molar ratio of inert medium to amine is more than 2 to 30, preferably 2.5 to 15.
  • the inert medium is introduced into the reaction space together with the amine
  • the temperature in the reaction space is chosen so that it is below the boiling point of the most heavily used amine, based on the pressure conditions prevailing in the reaction space.
  • the Am ⁇ n used (gem ⁇ sch) and set pressure usually results in a favorable temperature Reaction space of more than 200 0 C to less than 600 ° C, preferably from 28O 0 C to 400 0 C.
  • step (3b) it may be advantageous to preheat the stream of Reaktan- th prior to mixing, usually at temperatures of 100 to 600 0 C, preferably from 200 to 400 0 C.
  • the average contact time of the reaction mixture in step (3b) of the process according to the invention is generally between 0.1 second and less than 5 seconds, preferably from more than 0.5 seconds to less than 3 seconds, particularly preferably more than 0.6 seconds to less than 1, 5 seconds.
  • Mean contact time is understood to be the time from the start of the mixing of the starting materials until they leave the reaction space
  • the dimensions of the reaction space and the flow rates are such that a turbulent flow, ie a flow having a Reynolds number of at least 2300, preferably at least 2700, is present, the Reynolds number with the hydraulic diameter of Reaction space is formed.
  • the gaseous reactants pass through the reaction space at a flow rate of 3 to 180 meters / second, preferably from 10 to 100 meters / second
  • the molar ratio of phosgene to amino groups used is usually 1: 1 to 15: 1, preferably 1.2: 1 to 10: 1, more preferably 1.5: 1 to 6: 1
  • the reaction conditions are selected so that the reaction gas at the outlet from the reaction space has a phosgene concentration of more than 25 mol / m 3 , preferably from 30 to 50 mol / m 3 .
  • an inert medium concentration of more than 25 mol / m 3 preferably from 30 to 100 mol / m 3, is generally present at the outlet from the reaction space
  • the reaction conditions are selected so that the reaction gas at the outlet from the Reaktio ⁇ sraum a phosgene concentration of more than 25 mol / m 3 , in particular from 30 to 50 mol / m 3 , and at the same time has an inert medium concentration of more than 25 mol / m 3 , in particular from 30 to 100 mol / m 3
  • the reaction volume is usually tempered via its outer surface.
  • several reactor tubes can be connected in parallel
  • the process according to the invention is preferably carried out in one stage. This is to be understood as meaning that the mixing and reaction of the educts take place in one step and in a temperature range, preferably in the abovementioned temperature range. Furthermore, the process according to the invention is preferably carried out continuously
  • the gaseous reaction mixture is preferably washed with a solvent at temperatures of greater than 150X.
  • Suitable solvents are preferably hydrocarbons which are optionally substituted by halogen atoms, for example chlorobenzene, dichlorobenzene, and toluene. It is particularly preferred as solvent Monochlorobenzene used.
  • the isocyanate is selectively converted into the wash solution.
  • the remaining gas and the resulting wash solution are then preferably separated by rectification into isocyanate (s), solvent, phosgene and hydrogen chloride. Small amounts of by-products remaining in the isocyanate (mixture) can be removed by means of additional rectification or crystallization of the desired isocyanate (gem ⁇ sch) are separated
  • the products of MMDI and PMDI may be mixed (in whole or in part) and marketed as a mixture and / or they may be marketed as individual products.
  • FIG. 1 A preferred embodiment of the method according to the invention is illustrated in FIG. 1,
  • aqueous saline solution e.g., NaCl, using HCl and NaOH as the base

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

Abstract

L'invention concerne un procédé pour produire des isocyanates, comprenant les étapes suivantes : (1) production d'un mélange de MDA brut par transformation d'aniline avec du formaldéhyde ; (2) séparation dudit mélange MDA brut en MMDA et PMDA ; (3a) phosphogénation du PMDA séparé dans l'étape 2 dans la phase liquide en PMDI et ; (3b) phosphogénation du MMDA séparé dans l'étape 2 dans une phase gazeuse en MMDI.
EP06725224A 2005-03-30 2006-03-22 Production de mdi au moyen d'une phosphogenation en phase liquide et en phase gazeuse Withdrawn EP1866282A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005014846A DE102005014846A1 (de) 2005-03-30 2005-03-30 MDI Herstellung mittels Flüssigphasen- und Gasphasenphosgenierung
PCT/EP2006/060940 WO2006103189A1 (fr) 2005-03-30 2006-03-22 Production de mdi au moyen d'une phosphogenation en phase liquide et en phase gazeuse

Publications (1)

Publication Number Publication Date
EP1866282A1 true EP1866282A1 (fr) 2007-12-19

Family

ID=36599089

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06725224A Withdrawn EP1866282A1 (fr) 2005-03-30 2006-03-22 Production de mdi au moyen d'une phosphogenation en phase liquide et en phase gazeuse

Country Status (7)

Country Link
US (1) US20080200721A1 (fr)
EP (1) EP1866282A1 (fr)
JP (1) JP2008534550A (fr)
KR (1) KR20070116676A (fr)
CN (1) CN101137617A (fr)
DE (1) DE102005014846A1 (fr)
WO (1) WO2006103189A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX2009004261A (es) 2006-10-26 2009-05-05 Basf Se Proceso para preparar isocianatos.
US20100048942A1 (en) * 2006-12-11 2010-02-25 Basf Se Process for preparing isocyanates
EP2200976B1 (fr) * 2007-09-19 2011-11-23 Basf Se Procédé de fabrication d'isocyanates
DE102007061688A1 (de) 2007-12-19 2009-06-25 Bayer Materialscience Ag Verfahren und Mischaggregat zur Herstellung von Isocyanaten durch Phosgenierung primärer Amine
US10759736B2 (en) 2018-10-17 2020-09-01 Covestro Deutschland Ag Process for the preparation of di- and polyamines of the diphenylmethane series

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19804915A1 (de) * 1998-02-07 1999-08-12 Basf Ag Verfahren zur Herstellung von Methylendi(phenylamin) und Methylendi(phenylisocyanat)
DE10111337A1 (de) * 2001-03-08 2002-09-12 Basf Ag Verfahren zur Herstellung von MDI, insbesondere von 2.4'-MDI

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006103189A1 *

Also Published As

Publication number Publication date
CN101137617A (zh) 2008-03-05
DE102005014846A1 (de) 2006-10-05
KR20070116676A (ko) 2007-12-10
WO2006103189A1 (fr) 2006-10-05
US20080200721A1 (en) 2008-08-21
JP2008534550A (ja) 2008-08-28

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