WO2014091011A1 - Procédé de phosgénation de diamine de toluène (tda) en phase gazeuse dans un réacteur spécifiquement construit - Google Patents

Procédé de phosgénation de diamine de toluène (tda) en phase gazeuse dans un réacteur spécifiquement construit Download PDF

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Publication number
WO2014091011A1
WO2014091011A1 PCT/EP2013/076601 EP2013076601W WO2014091011A1 WO 2014091011 A1 WO2014091011 A1 WO 2014091011A1 EP 2013076601 W EP2013076601 W EP 2013076601W WO 2014091011 A1 WO2014091011 A1 WO 2014091011A1
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WO
WIPO (PCT)
Prior art keywords
phosgene
reactor
protective
delivered
amine
Prior art date
Application number
PCT/EP2013/076601
Other languages
English (en)
Inventor
Jerzy Baldyga
Magdalena Jasinska
Stefan Szarlik
Magdalena DZIEGIELEWSKA
Piotr LEWANDOWSKI
Arkadiusz Slawatycki
Wojciech Chrupala
Jacek Stuczynski
Lech Ruczynski
Lucjan Wojcik
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 WO2014091011A1 publication Critical patent/WO2014091011A1/fr

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/002—Nozzle-type elements

Definitions

  • the invention provides a method of conducting a reaction of TDA in a gaseous phase and an apparatus - a reactor of a specific construction which allows to obtain high selectivity in the course of the phosgenation reaction of toluenediamine (TDA) to toluene diisocyanate (TDI) and prevents accumulation of deposits on the walls.
  • TDA toluenediamine
  • TDI toluene diisocyanate
  • Polyurea (urea) thus formed can further react with phosgene, TDA and TDI to yield macromolecular compounds (so-called tars).
  • TDA can react instead with carbamoyl chloride also yielding urea.
  • a is a ratio of the diameter of the central amine pipe (2) to the external pipe (1) of the reactor, and u ⁇ and w 2 are mean gas velocities from the central and external pipe, respectively, that characterize a flow which accompanies the central one.
  • Maintaining such a value precludes formation of circulation loops, and consequently hinders the backmixing.
  • Another factor which assures plug flow and hinders the backmixing, comprises carrying out the reaction in an expanding portion of the reactor (4), which results in flattening of a velocity profile and rebuilding the pressure.
  • the pressure increase accelerates the desired reactions.
  • the velocity profile is additionally influenced by faster-flowing protective phosgene (5), which prevents retardation of the reaction mixture at the walls.
  • the problem of a mixing rate at the molecular scale is solved in the proposed system in an unconventional manner.
  • Two aspects of the problem should be considered: the first is a problem of a time constant of micromixing (the Corrsin time constant
  • 2 ⁇ is kinetic energy of the turbulence.
  • small values of the x m constant should be pursued. This could be achieved by increasing the energy dissipation rate at the smallest kinetic energy possible (and the small integral scale). This is promoted by distributing phosgene among several nozzles.
  • the second problem is mesomixing, or turbulent diffusion. Distribution among 3 (or more) nozzles reduces a distance (scale) for turbulent diffusion, and consequently, compared to the solution provided in EP 1 555 258 Al where the amine is fed from an annular nozzle, the time of
  • the technical solution employs feeding phosgene not only directly to the location of TDA dosing through converging phosgene nozzles (2) and as protective phosgene (5), but also to distal regions of reaction; phosgene dosing (6), (7), (8).
  • the technical solution thus consists of employing more than one phosgene streams, separately delivered and characterized by different properties in contrast to phosgene delivered by the convergent nozzles (2).
  • Protective phosgene takes here, likewise to the patent No. EP 1 555 258 Al, a part of a chemical shield, but additionally also a mechanical screen. This is because protective phosgene is supplied under much higher pressure (at least by 2000 Pa) and resultant high velocity (at least 3 times higher than that of amine), onto the external reactor wall.
  • the detailed process for conducting the TDA reaction in a gaseous phase in a specific reactor presented on Fig. 1 consists in supplying vapours of previously evaporated TDA, optionally with an inert gas, through a pipe connector (9).
  • the gaseous stream delivered through the amine pipe (3) to the reactor is free of liquid drops, due to use of an upstream demister and overheating the stream above the dew point.
  • Gaseous phosgene heated to the reaction temperature is supplied by more than one convergent nozzle (2) to the same location at the end of the amine pipe (3).
  • Ratios of diameters of the convergent phosgene nozzles (2) to the amine pipe (3) and the amine pipe (3) in relation to the reactor (1) diameter and in relation to the flow rates of phosgene and the amine solution were selected to provide the Craya-Curtet number greater than 1,5, and the Reynolds number (Re 3 ⁇ 4 ) greater than 200.
  • the amount of phosgene delivered by the divergent nozzles (2) should be slightly higher than a stoichiometric amount in relation to the amine groups. Preferably, the excess amounts to 10%.
  • the additional gaseous protective phosgene delivered to the reactor through the feed connectors (5), (6), (7) and (8) is supplied from a source of the pressure higher by at least 2000 Pa than gaseous phosgene delivered by the nozzles (2).
  • This phosgene is dosed into the reactor through an annular slit of a diameter selected to provide an outlet velocity from the slit that is three times higher than the one of amine. This ensures a value of shear stresses in the stream at the wall of not lower than 3 Pa.
  • the number of delivery points of the protective phosgene streams is a result of necessity of providing the protective effect along the entire reactor length. It was found that for the flow parameters listed above the protective effect is effective at the length of up to do 50 cm. Therefore, the number of the delivery is determined by the residence time of reagents in the reactor and a length of the reactor essential for providing such time.
  • a reactor of a geometry fulfilling a criterion of the Craya-Curtet number of above 2 at the region of mixing the streams of evaporated TDA and inert nitrogen with gaseous phosgene was charged with the gaseous stream at 350°C containing 29 kg/h of TDA and 13,5 kg/h of N 2 , through the central amine pipe and 52,5 kg/h of gaseous phosgene at 350°C, through three phosgene nozzles located centrally inside the amine pipe.
  • gaseous phosgene was delivered at 350°C and under the pressure higher by 2200 Pa from the pressure of phosgene in the central nozzles, at the rate of 17 kg/h through the annular slit into the main reaction area. Gaseous phosgene of the same temperature and pressure parameters was also delivered to the three feed points located every 50 cm along the reactor length at the rate of 2,4 kg/h of phosgene at each point.
  • the temperature at the end of the reactor was 420°C.
  • the gaseous product obtained was cooled in a known manner according to a method of P-393214 by spraying with an o-DCB solvent at 114 kg/h, and a liquid product was obtained which comprised 73,2% of TDI, 23,7% of DCB, 0,1% of HC1, 0,6% of COCl 2 , 2,4% of tars, and flue gases comprising 42,3% of HC1, 40% of COCl 2 , 17,3% of N 2 , 0,4% of DCB, which were further condensed in a surface condenser. Finally, the product was obtained at the 95% yield.

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

Abstract

La présente invention concerne un procédé de phosgénation de diamine de toluène (TDA) en phase gazeuse dans un réacteur spécifiquement construit. Le procédé, qui, grâce à un mélange approprié de réactifs permet d'obtenir une sélectivité élevée lors de la réaction de phosgénation de TDA en diisocyanate de toluène (TDI). Le procédé consiste en la sélection de tels débits de phosgène et d'une solution d'amine avec un gaz inerte par la distribution de la solution amine et du gaz inerte à travers une conduite de diamètre approprié, et la distribution de phosgène à travers des buses de tels diamètres que le nombre de Craya-Curtet est supérieur à 0,75, de préférence supérieur à 2, et le nombre de Reynold Reλ est supérieur à 200. Le réacteur utilise également le dosage du phosgène protecteur distribué sur la paroi du réacteur au niveau de l'élévation de l'orifice de sortie de vapeur d'amine et au moins deux flux de phosgène protecteur additionnel distribué sur la paroi du réacteur, sous l'orifice de sortie de vapeur d'amine. Le phosgène protecteur est distribué au réacteur à travers des fentes annulaires, qui entraînent un élargissement du diamètre du réacteur. Le phosgène protecteur est distribué au réacteur dans la zone réactionnelle à travers la fente annulaire d'un diamètre sélectionné pour fournir une vitesse qui est trois fois supérieure à la vitesse du flux d'amine. Les points de distribution des flux additionnels de phosgène protecteur et les intensités de ces flux sont sélectionnés pour fournir des valeurs de contraintes de cisaillement d'au moins 3Pa au niveau de la paroi interne du réacteur, et des distances entre points de distribution individuels de distribution supérieures à 50 cm. Une telle solution empêche l'accumulation de dépôts aux parois du réacteur, étant donné que le phosgène protecteur joue le rôle d'un blindage mécanique et chimique.
PCT/EP2013/076601 2012-12-14 2013-12-13 Procédé de phosgénation de diamine de toluène (tda) en phase gazeuse dans un réacteur spécifiquement construit WO2014091011A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PL402054A PL402054A1 (pl) 2012-12-14 2012-12-14 Sposób fosgenowania toluilenodiaminy (TDA) w fazie gazowej w specjalnej konstrukcji reaktorze
PLP.402054 2012-12-14

Publications (1)

Publication Number Publication Date
WO2014091011A1 true WO2014091011A1 (fr) 2014-06-19

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PCT/EP2013/076601 WO2014091011A1 (fr) 2012-12-14 2013-12-13 Procédé de phosgénation de diamine de toluène (tda) en phase gazeuse dans un réacteur spécifiquement construit

Country Status (2)

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PL (1) PL402054A1 (fr)
WO (1) WO2014091011A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108246235A (zh) * 2016-12-29 2018-07-06 重庆长风生物科技有限公司 一种光气气相法连续生产hdi的喷嘴
JP2022515701A (ja) * 2018-10-31 2022-02-22 ダウ グローバル テクノロジーズ エルエルシー 有機溶液からモノイソシアネートを除去するための方法
EP4378576A1 (fr) * 2022-11-29 2024-06-05 Basf Se Appareil et procédé de préparation d'isocyanates

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839435A (en) * 1972-01-13 1974-10-01 Maruzen Oil Co Ltd Process for producing fiber grade terephthalic acid
EP1935876A1 (fr) * 2006-12-13 2008-06-25 Bayer MaterialScience AG Procédé destiné à la fabrication d'isocyanates en phase gazeuse
WO2010015667A1 (fr) * 2008-08-07 2010-02-11 Basf Se Procédé de fabrication d'isocyanates aromatiques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839435A (en) * 1972-01-13 1974-10-01 Maruzen Oil Co Ltd Process for producing fiber grade terephthalic acid
EP1935876A1 (fr) * 2006-12-13 2008-06-25 Bayer MaterialScience AG Procédé destiné à la fabrication d'isocyanates en phase gazeuse
WO2010015667A1 (fr) * 2008-08-07 2010-02-11 Basf Se Procédé de fabrication d'isocyanates aromatiques

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J.M. KHODADADI ET AL.: "Experimental and numerical study of confined coaxial turbulent jets", AIAA JOURNAL, vol. 27, no. 5, 1 January 1989 (1989-01-01), pages 532 - 541, XP002722093 *
JOHN M. DEALY: "Momentum exchange in a confined circular jet with turbulent source", 1 January 1964, UNIVERSITY OF MICHIGAN, Michigan, pages: FP,ii-ix,1 - 144, XP002722094 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108246235A (zh) * 2016-12-29 2018-07-06 重庆长风生物科技有限公司 一种光气气相法连续生产hdi的喷嘴
JP2022515701A (ja) * 2018-10-31 2022-02-22 ダウ グローバル テクノロジーズ エルエルシー 有機溶液からモノイソシアネートを除去するための方法
JP7397865B2 (ja) 2018-10-31 2023-12-13 ダウ グローバル テクノロジーズ エルエルシー 有機溶液からモノイソシアネートを除去するための方法
EP4378576A1 (fr) * 2022-11-29 2024-06-05 Basf Se Appareil et procédé de préparation d'isocyanates
WO2024115132A1 (fr) * 2022-11-29 2024-06-06 Basf Se Appareil et procédé de préparation d'isocyanates

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