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WO2008031755A1 - Procédé de fabrication d'isocyanate - Google Patents

Procédé de fabrication d'isocyanate Download PDF

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Publication number
WO2008031755A1
WO2008031755A1 PCT/EP2007/059339 EP2007059339W WO2008031755A1 WO 2008031755 A1 WO2008031755 A1 WO 2008031755A1 EP 2007059339 W EP2007059339 W EP 2007059339W WO 2008031755 A1 WO2008031755 A1 WO 2008031755A1
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WO
WIPO (PCT)
Prior art keywords
methanol
urethane
dimethyl carbonate
synthesis gas
carbonate
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.)
Ceased
Application number
PCT/EP2007/059339
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German (de)
English (en)
Inventor
Eckhard Stroefer
Wolfgang Mackenroth
Martin Sohn
Carsten KNÖSCHE
Olaf Schweers
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2008031755A1 publication Critical patent/WO2008031755A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B43/00—Formation or introduction of functional groups containing nitrogen
    • C07B43/10—Formation or introduction of functional groups containing nitrogen of isocyanate groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the invention preferably relates to integrated processes for the preparation of isocyanates by cleavage of urethane, the process comprising the following process steps:
  • WO 02/24634 describes the reaction starting from the formamide of the amine, which is reacted with diphenyl carbonate directly over the intermediately formed urethane to the isocyanate. Disadvantages are the moderate yield and the handling of toxic phenol melts.
  • the formamide is likewise reacted with diaryl carbonate in a one-pot reaction with the isocyanate.
  • the formamide is reacted with dimethyl carbonate (DMC) to urethane, which is then cleaved.
  • DMC dimethyl carbonate
  • Another dialkyl carbonate based process is described in WO 01/56977. This z. B.Toluylendiamin with DMC with the addition of salts such.
  • B. zinc acetate is reacted as a catalyst for Toluylendiurethan (TDU). TDU is then split in a system of two pyrolysis reactors, the first reactor being a film evaporator.
  • the object of the present invention was thus to develop a chlorine-free process for the preparation of isocyanates which is economically competitive and, moreover, is operated simply and robustly.
  • the present invention also provides a process for the preparation of isocyanates by cleavage of urethane, the process comprising the following process steps:
  • step (v) the recombination of the alcohol formed in the cleavage of the urethane ethane is inhibited when a higher alcohol is used.
  • higher alcohols there is the risk of fragmentation of the urethane under the high cleavage temperatures of the cleavage reactor in which the urethane is determined. intended to be cleaved in isocyanate and alcohol. Fragmentation produces amine, CO2 and olefin.
  • the amine interferes, however, since it reacts with the isocyanate in rapid reaction to ureas and biurets. These reduce the yield and reduce the availability of the system due to the formation of solids. Therefore, the use of DMC is the preferred variant.
  • the inventive method is characterized not only by an optimization of the individual stages, but also represents an integrated method that only in its entirety allows economic operation.
  • the synthesis gas used for the preparation of the methanol is produced on the basis of natural gas, preferably natural gas, which is referred to as "flared gas” or “stranded gas” z. B. is economically available in oil production areas, or on the basis of coal, the synthesis gas is preferably produced in world-scale coal gasification facilities.
  • natural gas preferably natural gas
  • stranded gas stranded gas
  • the synthesis gas is preferably produced in world-scale coal gasification facilities.
  • the use of heavy oils and biomass is possible.
  • Preference is given to the provision of synthesis gas from natural gas.
  • the provision of synthesis gas from coal is also preferred.
  • Preference is also the provision of synthesis gas from heavy oils or biomass.
  • synthesis gas is understood as meaning a gas mixture containing carbon monoxide and hydrogen.
  • the production of synthesis gas from natural gas or coal is well known. The technology used depends in particular on the production of coal on the type, composition and dosage form of the raw material. Summaries put next to Ullmann's Encyclopedia of Industrial Chemistry (1986 Ullmann's Encyclopedia of Industrial Chemistry 1986 volume A7 "Coal liquefaction” and Ullmann's Encyclopedia of Industrial Chemistry 1976 Volume 14 "coal, gas generation”) z.
  • EP 0 533 231 B1 directly describes such a process for the production of synthesis gas for the synthesis of methanol.
  • the aim is to produce a synthesis gas, which Has the appropriate stoichiometry and therefore can be fed to the methanol synthesis without further treatment.
  • the residual conversion of methane is preferably with pure or enriched oxygen in a similar pressure range as above.
  • the main exothermic reactions are:
  • the temperatures are preferably from 2000 to 800 ° C.
  • the reaction is generally conducted adiabatically in a fixed catalyst bed reactor. Preference is given to using Ni, Rh and / or Ru-based catalysts.
  • the reaction in the production of synthesis gas from coal
  • the reaction is preferably operated at pressures in the range of 1 to 80 bar.
  • the outlet temperatures of the reaction gas are preferably 700 to 1500 0 C.
  • the gasification processes for coal can be transferred in principle to the gasification of biomass.
  • the gasification of coal is preferably part of a larger network that includes the production of electrical energy, wherein the synthesis gas is used as fuel in turbines for power generation (eg., So-called "Integrated Gasification Combined-cycle IGCC" method) at
  • the production preferably large-scale production of methanol from the synthesis gas, which was preferably generated according to the above step.
  • the production of methanol from synthesis gas is well known and widely described.
  • the methanol is preferably prepared using the process described in EP 067 491 B1, that in Energia 166 (2002), 63-68 or one of the processes described in JP Lange, Chimie antibiotic 13 (1995), 1433-6 comes.
  • the capacities of these methanol plants amount to 2500 to 10000 tons per day and can thus make CO and methanol particularly advantageous due to the use of the so-called economies of scale.
  • EP-A 1 348 685 discloses a particular embodiment of this process, which has low carbon dioxide emissions. Recently, there is also the possibility of converting natural gas directly into methanol in a single-step synthesis. Such a method is described in M. Golombok, W. Teunissen; Industrial & Engineering Chemistry Research 42 (2003), 5003-5006 and in M. Golombok, T. Nijbaker, M. Raimondi; Industrial & Engineering Chemistry Research 43 (2004), 6001-6005.
  • the Liquid Phase Methanol LPMEOH TM process links an IGCC process to methanol production.
  • the synthesis of methanol from synthesis gas is carried out in one or more stages, preferably in two stages on a fixed bed contact, wherein in several stages at each stage the same or specially adapted catalysts are used.
  • the underlying exothermic equilibrium reactions are:
  • tube bundle reactors or fixed beds with internal heat exchangers are preferably used. Also several adiabatic fixed beds in series with intermediate heat exchangers or feeds of cold quenching gas between see the fixed beds are used.
  • the main sales take place in the first stage.
  • the approximation to the thermodynamic equilibrium conditions takes place.
  • the first stage is preferably from 180 to 350 0 C, and has operated in the reaction part via a tube bundle reactor, a first rising then falling profile.
  • the second stage advantageously has a falling temperature profile with the lowest temperature at the reactor outlet.
  • Pd, rare earths, Zn, Al and / or Cr-based catalysts are also possible to use Pd, rare earths, Zn, Al and / or Cr-based catalysts.
  • the synthesis gas and the methanol stage can be in a heat combination.
  • dimethyl carbonate is preferably prepared by oxidative carbonylation of methanol over copper chloride catalysts, by oxidative carbonylation of methanol with nitrogen oxide as redoxagent to copper chloride catalysts or by reacting urea with methanol.
  • the oxidative carbonylation of methanol over copper chloride catalysts with nitrogen oxide as redox agent (US Pat. No. 5,885,917) and the reaction of urea with methanol are preferred (US Pat. No. 5,902,894, WO 95/17369).
  • step (ii) it is also possible to prepare the dimethyl carbonate in step (ii) by reacting methanol with carbon monoxide and oxygen in the presence of copper-containing catalysts, as described, for example, in US Pat. B. in US 5,210,269 is described.
  • the dimethyl carbonate in step (ii) is preferably prepared by reacting methanol with carbon monoxide and oxygen in the presence of catalysts containing NO and copper.
  • dimethyl carbonate is prepared by reacting urea with methanol
  • the process product in addition to dimethyl carbonate and methyl carbamate and Contain alcohol.
  • This process product containing methyl carbamate can also be used according to the invention in step (iv) and, if appropriate, (iii).
  • WO 2003/106393 claims the simultaneous production of raw materials for methanol synthesis, ammonia synthesis, urea synthesis and CO. On this basis, methanol can be reacted very advantageously with urea either as described above to DMC or DMC / Methylcarbamatmischept. Methods of this type are z. As described in WO 2005/028414, WO 2005/06611 1 and part of EP-A 0 566 925 and EP-A 0 643 042.
  • WO 2005/051939 describes the preparation of dimethyl carbonate as coproduct of 1,2-propanediol production. This way of producing DMC is, in principle conceivable, but not directly preferred, since a co-product is formed, so that the advantage depends on the use and marketing of the same
  • the dimethyl carbonate can be reacted with alcohol, preferably monoalcohol to the corresponding dialkyl carbonate.
  • alcohol preferably monoalcohol to the corresponding dialkyl carbonate.
  • methanol is replaced by the corresponding alkanol in the dialkyl carbonate.
  • Suitable alcohols are preferably alkanols having between 2 and 6 carbon atoms, preferably ethanol, propanol, isopropanol, n-butanol, more preferably n-butanol and / or ethanol. More specifically, in the step (iv), the dimethyl carbonate is reacted with n-butanol or ethanol to dibutyl carbonate or diethyl carbonate.
  • This reaction can be carried out in conventional processes, as described for the transesterification of DMC production. Such are exemplified in US 4,181,676, US 4,307,032, US 4,661,609.
  • the transesterification takes place in a catalytic reactive distillation, wherein the low-boiling methanol goes off overhead and the high boilers dialkyl carbonate is withdrawn from the bottom.
  • a reactive distillation can be carried out analogously to that, as it is exemplified in EP 126,288.
  • the urethane can be in the reaction with the dialkyl, z.
  • dimethyl carbonate generally for the production of isocyanates known amines, preferably use diamines. Preference is given to the amines which are or have already been used for the preparation of isocyanates.
  • step (iv) Preference is given in step (iv) as the amine 2,2'-, 2,4'- and / or 4,4'-diamino-diphenylmethane (MDA), 2,4- and / or 2,6-toluenediamine (TDA), 1-amino-3,3,5-trimethyl-5-amino-methylcyclohexane (isophorone diamine, IPDA) and / or hexamethylenediamine (HDA) ,
  • MDA 2,2'-, 2,4'- and / or 4,4'-diamino-diphenylmethane
  • TDA 2,4- and / or 2,6-toluenediamine
  • IPDA 1-amino-3,3,5-trimethyl-5-amino-methylcyclohexane
  • HDA hexamethylenediamine
  • the reaction of amine with dimethyl carbonate is generally known and described in detail, for example, in WO 01/056977, page 4, line 11 to page 11, line 15.
  • the reaction takes place in a continuous process.
  • the amine is preferably reacted with the DMC in the presence of a catalyst at from 120 to 300 ° C.
  • the catalyst used may be those mentioned in EP 0 566 925 and EP 0 643 042 (page 7, column 40 and page 8, column 38), WO 01/056977, preferably in amounts of from 100 ppm to 5% by weight of the used amine.
  • the molar ratio of the DMC to the amine is preferably 5: 1 to 50: 1.
  • the design of the stirred tank is carried out according to the expert's known criteria, but preferably as
  • Boiler with external Umpump Vietnamese and heat exchanger wherein the mixing energy is preferably introduced into the boiler via a jet or
  • Flow tube which is preferably segmented by the installation of diaphragms, wherein the space between two diaphragms is considered technically as a stirred tank analog, wherein the mixing energy is introduced by one or more upstream pumps and wherein the flow tube is followed by a column in which Reaction product methanol can be separated, and to which the next section (flow tube + column) can connect in series.
  • the discharge from the stirred tank cascade is preferably flashed and the excess DMC and the alcohol are removed by means of suitable measures known to the person skilled in the art.
  • the urethane is fed as a melt or in a mixture with a high-boiling solvent of the cleavage.
  • MDA urethanes can still be subjected to condensation with formaldehyde after this stage, as described for aniline in EP-A 1 270 544.
  • the oligomers thus obtained are then fed to the cleavage.
  • (v) Cleavage of urethane to isocyanate and alcohol
  • the cleavage of urethane as a product of step (v) is well known and diverse z.
  • the cleavage is usually carried out in the liquid phase and / or in the gas phase optionally in the presence of solvent at temperatures of generally 200 to 400 0 C and a pressure between 2 mbar and 2000 mbar.
  • the cleavage of the urethane in step (v) is performed such that a
  • Fluidized bed process (DE 199 07 648) or a helical tube reactor (DE 198 55 959) are used.
  • the oligomers of MDA preferred the helical tube in question.
  • these methods have the advantage of cheaper investment and simpler construction. Due to the high flow rates and short residence times in the helical tube, caking and fouling are prevented.
  • the fluidized bed deposits on the fluidized material can be eliminated by discharging and burning. Falling film evaporators require the shutdown of the system and cleaning or parallel construction of the aggregates. However, it is also possible to carry out the cleavage in this or in the liquid phase with or without a solvent.
  • step (vii) the alcohol having more than 2 carbon atoms, which is formed during the preparation and decomposition of the urethane, is fed into step (iii), i. H. used for the reaction with the dimethyl carbonate.
  • each of the six boilers has a volume of 50 l and has a pumped circulation with heat exchanger and an attached pressure column, in which methanol and DMC are separated. The methanol is removed from the system and a mixture of DMC, possibly with small amounts of methanol, runs back into the kettle.
  • the first three boilers are operated in series at approx. 160 ° C and approx. 7 bar each.
  • the boilers are arranged so that the liquid phase flows gravimetrically from the first to the second into the third.
  • the hold up of the liquid phase in each vessel is 30 to 34 liters.
  • the drain from the third boiler is radiometrically controlled with a pump in the fourth boiler promoted.
  • the fourth, fifth and sixth boilers are operated in series at approx. 180 ° C and approx. 10 bar each.
  • the boilers are arranged so that the liquid phase flows gravimetrically from the fourth to the fifth to the sixth.
  • the hold up of the liquid phase in each vessel is 30 to 34 liters.
  • the discharge from the sixth kettle is flashed into a column. The bottom of the column is maintained at about 175 0 C and contains the TDU (91%) high-boiling components (> 8%) and the catalyst.
  • the methanol / DMC mixture goes off overhead and can be worked up by distillation, but this did not take place in the present experimental case. It can also be traced back to the DMC system.
  • the melt including the high-boiling components and the catalyst is conveyed with a small residence time of 20 min via a gear pump directly into a fluidized bed and injected.
  • the fluidized bed contains fine steatite, which is held by a heat exchanger at a temperature of 350 0 C.
  • the steatite is held in suspension by nitrogen at 1 bar.
  • the molar ratio of nitrogen to TDU flow through the reactor is about 4: 1.
  • At a downstream condenser which is operated at 80 0 C, 73% of the TDU used are 's taken off as TDI.
  • TDU and TDI are withdrawn semi-urethane.
  • the latter arise from partial recombination of the TDI with the alcohol.
  • TDU and TDI semi-urethane By separation of the methanol and recycling of TDU and TDI semi-urethane, the yield of cleavage can be increased to 95%.
  • the fluidized material is removed at regular intervals in small batches from the fluidized bed and burned in a second fluidized bed reactor with air supply.
  • the overall yield of the process is about 86% based on TDA and thus below that of phosgenation.
  • this disadvantage can be compensated for by providing the CO building block via inexpensive DMC via the low-cost synthesis gas building block carbon monoxide by coupling with a world-scale synthesis gas plant.

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

Abstract

L'invention concerne un procédé de fabrication d'isocyanate par décomposition d'uréthane. Selon l'invention, le procédé comprend les étapes suivantes : (i) utilisation d'un gaz de synthèse à base de gaz naturel, de charbon, de fioul ou gazéification d'une biomasse et fabrication de méthanol à partir du gaz de synthèse, (ii) réaction du méthanol par carbonylation oxydative ou avec de l'urée pour former du diméthylcarbonate (DMC), (iv) fabrication d'uréthane par réaction d'amine avec le diméthylcarbonate, (v) décomposition de l'uréthane en isocyanate et méthanol, (vi) recirculation du méthanol pour la fabrication du diméthylcarbonate.
PCT/EP2007/059339 2006-09-12 2007-09-06 Procédé de fabrication d'isocyanate Ceased WO2008031755A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP06120495 2006-09-12
EP06120495.4 2006-09-12

Publications (1)

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WO2008031755A1 true WO2008031755A1 (fr) 2008-03-20

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109467520A (zh) * 2018-11-15 2019-03-15 关爱丽 一种合成医用聚氨酯所需二异氰酸酯的新方法
CN112661670A (zh) * 2019-10-15 2021-04-16 中国科学院过程工程研究所 一种非催化制备1,6-六亚甲基二氨基甲酸酯的方法
CN113774412A (zh) * 2020-05-20 2021-12-10 深圳有为技术控股集团有限公司 异氰酸酯的电化学脱氢氧化制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE942145C (de) * 1953-04-12 1956-04-26 Bayer Ag Verfahren zur Herstellung aromatischer Di- und Polyisocyanate
WO1995017369A1 (fr) * 1993-12-20 1995-06-29 Exxon Chemical Patents Inc. Procede de fabrication de carbonate de dialkyle a partir d'uree et d'alcool.
US5885917A (en) * 1995-05-22 1999-03-23 Ube Industries, Ltd. Porous lithium aluminate carrier of spinel structure for catalyst
US5902894A (en) * 1998-08-26 1999-05-11 Catalytic Distillation Technologies Process for making dialkyl carbonates
WO2001056977A1 (fr) * 2000-02-03 2001-08-09 Enichem S.P.A. Procede integre de preparation d'isocyanates aromatiques et procedures utilisees pour effectuer les phases intermediaires associees
WO2002024634A2 (fr) * 2000-09-19 2002-03-28 Arco Chemical Technology, L.P. Procede sans phosgene destine a produire des isocyanates organiques
JP2004262835A (ja) * 2003-02-28 2004-09-24 Mitsui Chemicals Inc 芳香族イソシアネートの製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE942145C (de) * 1953-04-12 1956-04-26 Bayer Ag Verfahren zur Herstellung aromatischer Di- und Polyisocyanate
WO1995017369A1 (fr) * 1993-12-20 1995-06-29 Exxon Chemical Patents Inc. Procede de fabrication de carbonate de dialkyle a partir d'uree et d'alcool.
US5885917A (en) * 1995-05-22 1999-03-23 Ube Industries, Ltd. Porous lithium aluminate carrier of spinel structure for catalyst
US5902894A (en) * 1998-08-26 1999-05-11 Catalytic Distillation Technologies Process for making dialkyl carbonates
WO2001056977A1 (fr) * 2000-02-03 2001-08-09 Enichem S.P.A. Procede integre de preparation d'isocyanates aromatiques et procedures utilisees pour effectuer les phases intermediaires associees
WO2002024634A2 (fr) * 2000-09-19 2002-03-28 Arco Chemical Technology, L.P. Procede sans phosgene destine a produire des isocyanates organiques
JP2004262835A (ja) * 2003-02-28 2004-09-24 Mitsui Chemicals Inc 芳香族イソシアネートの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200467, Derwent World Patents Index; AN 2004-681033, XP002468491 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109467520A (zh) * 2018-11-15 2019-03-15 关爱丽 一种合成医用聚氨酯所需二异氰酸酯的新方法
CN112661670A (zh) * 2019-10-15 2021-04-16 中国科学院过程工程研究所 一种非催化制备1,6-六亚甲基二氨基甲酸酯的方法
CN113774412A (zh) * 2020-05-20 2021-12-10 深圳有为技术控股集团有限公司 异氰酸酯的电化学脱氢氧化制备方法

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