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WO1990008118A1 - Production de dichlorobenzene presentant des rapports para/ortho eleves - Google Patents

Production de dichlorobenzene presentant des rapports para/ortho eleves Download PDF

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Publication number
WO1990008118A1
WO1990008118A1 PCT/US1989/005708 US8905708W WO9008118A1 WO 1990008118 A1 WO1990008118 A1 WO 1990008118A1 US 8905708 W US8905708 W US 8905708W WO 9008118 A1 WO9008118 A1 WO 9008118A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
reagent
reactor
chlorobenzene
dichlorobenzene
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/US1989/005708
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English (en)
Inventor
Melville E. D. Hillman
James D. Browning
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.)
Battelle Memorial Institute Inc
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Battelle Memorial Institute Inc
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 Battelle Memorial Institute Inc filed Critical Battelle Memorial Institute Inc
Priority to KR1019900701884A priority Critical patent/KR910700217A/ko
Publication of WO1990008118A1 publication Critical patent/WO1990008118A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/02—Monocyclic aromatic halogenated hydrocarbons
    • C07C25/08—Dichloro-benzenes
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0278—Feeding reactive fluids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds

Definitions

  • the present invention relates to the production of p- dichlorobenzene by an improved vapor phase process that results in a product mixture with a para/ortho (P/0) ratio in the range of 20/1 to 30/1 or a P/P+0 ratio of 95 to 97 percent para at higher efficiency.
  • Sequential, alternating pulses of chlorine gas, inert gas, and chlorobenzene (or benzene) vapors with or without a carrier gas are continuously passed over a catalyst/reagent composition.
  • a novel catalyst/reagent composition is prepared for improved production of p- dichlorobenzene.
  • P-dichlorobenzene is an important raw material for production of polyphenylene sulfide.
  • Various processes for production of p- dichlorobenzene have been developed, however, a simpler process that results in lower costs and high yields is still needed.
  • Conventional commercial processes for chlorinating benzene or monochlorobenzene to dichlorobenzene produce about 3/2 para/ortho (P/0) isomer ratio, and so the efficiency of the processes suffer from inherent limitations because of the large amount of unwanted o-dichlorobenzene produced.
  • An improved process with greater efficiency in which the para/ortho (P/0) isomer ratio is 9/1 or greater is of great utility.
  • 1,963,761 teaches a process of makin chlorobenzene from benzene where dichlorobenzene is also produced; vaporized benzene, hydrogen chloride and oxygen with or without carrier gas are passed over a contact substance of copper, metals o their compounds (e.g. FeCl3, CuCl).
  • G. A. Webb, in U.S. 2,527,606, teaches the production of p dichlorobenzene from benzene.
  • the process uses catalysts such a aluminum chloride, zinc chloride, iron chloride, or metal ic fluorides Approximately equal parts of benzene and monochlorobenzene are added The benzenes and catalyst flow countercurrent to chlorine in a reactor W.
  • Adolf Wissner et al in U.S. 4,300,004, teach the separation o ortho-, meta-, and para-dichlorobenzene from an isomeric mixtur thereof.
  • Japanese patent Kokai 74/76,828 teaches the batch and continuou production of monochlorotoluene.
  • the reaction is in the vapor phase
  • vaporized toluene contacts with ferric chloride t produce chlorotoluene.
  • chlorine gas i introduced to regenerate the ferric chloride.
  • ferric chloride i regenerated toluene is again introduced.
  • chlorine gas and toluene are simultaneously reacted over ferri chloride. The process is stated to be applicable to chlorobenzene.
  • the invention includes a method for producing p-dichlorobenzen that comprises the steps of providing a reactor containing catalyst/reagent adapted to convert chlorobenzene (or benzene) to p dichlorobenzene, wherein the reactor has an inlet and an outlet fo introducing reactants and removing product; introducing a pulse o vaporized chlorobenzene (or benzene) into the reactor and reacting th chlorobenzene (or benzene) with the catalyst/reagent whereby p dichlorobenzene is formed; introducing a pulse of inert gas into th reactor; introducing a pulse of chlorine gas into the reactor an reacting the chlorine with the catalyst/reagent; introducing a pulse o inert gas into the reactor; repeating the pulsing steps in a sequentia manner; and continuously removing product containing p-dichlorobenzen from the outlet of the reactor.
  • the reactor is maintained at temperature between about 100 C and about 190 C, and preferably
  • a yet further embodiment of the invention includes a method fo producing a composition useful for producing p-dichlorobenzen comprising: Dissolving FeCl3 or a mixture of FeCl3 and AICI3 in acetone to form a solution; contacting the solution with a porous inert substrate; and depositing the FeCl3 or the mixture of FeCl3 and AICI3 on the substrate by removing the acetone.
  • a further embodimen includes the step of activating the FeCl3, or FeU3 and A1C13 deposite on the substrate by treating the composition with chlorine gas.
  • a catalyst/reaction composition for producin p-dichlorobenzene comprising a porous inert substrate having catalyst/reagent adapted to convert chlorobenzene (or benzene) to p dichlorobenzene deposited thereon.
  • the porous inert substrate i preferably a resilient material such as vermiculite.
  • Th catalyst/reagent is preferably a mixture of FeCl3 and A1C13 althoug FeCl3 alone may be used.
  • a specific embodiment of the invention includes a method fo producing an improved cataTyst/reagent that comprises dissolving catalyst/reagent selected from the group consisting of anhydrous ferri chloride, or a mixture of anhydrous ferric chloride and anhydrou aluminum chloride in acetone to form a solution; preparing a slurry o powdered porous inert substrate and acetone; mixing the slurry an solution; and evaporating the acetone from the mixture.
  • Another embodiment encompasses apparatus for producing p dichlorobenzene from chlorobenzene that includes a gas supply tha provides a source of gaseous chlorine, inert gas, and chlorobenzene; control and pulse-meter for receiving gases from the gas supply tha switches between the sources of gaseous chlorine, inert gas, an chlorobenzene so as to provide pulses of each gas to the input of reactor column; one or more reactor columns each having an input and a output and a catalyst/reagent composition disposed therein adapted t convert chlorobenzene to p-dichlorobenzene that accepts pulses of gase from the control and pulse-meter at the input; and a separator fo separating product gases from the output of the reactor.
  • a gas supply tha provides a source of gaseous chlorine, inert gas, and chlorobenzene
  • control and pulse-meter for receiving gases from the gas supply tha switches between the sources of gaseous chlorine, inert gas, an chlorobenzen
  • FIG 1 illustrates an apparatus used for the experiment herein.
  • Figure 2 illustrates an apparatus useful for practicing th invention.
  • FeU3 can be dissolved in chlorobenzene and does not react until it is heated to about 125 C or higher. However, if chlorine is added to FeCl3 dissolved in chlorobenzene (CB) solution, immediate reaction occurs at room temperature or lower.
  • the bulky iron group is much closer to the chlorobenzene molecule in formula (3) than in formula (4).
  • the iron atom in formula (3) is additionally co plexed to at least one other iron atom, that is not shown in the diagram, so the steric hindrance is much greater than indicated.
  • FeCl3 and A1C13 are actually complexed to other FeCl3 and AICI3 molecules, the complex of catalyst/reagent will be referred to as FeCl3, and a mixture of FeU3 and AICI3 for purposes of discussion herein.
  • the flow rate (30 mls/min) of the carrier gas (N2) and the column temperature (130 C isothermal for 30 mins) were optimized to provide baseline resolution for the simultaneous analyses o chlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o- dichlorobenzene and trichlorobenzene.
  • Standard curves were established by plotting concentration (g/ml) versus peak area and slopes for the resulting straight lines were determined. Additionally, standards were analyzed at the same time as the reaction mixtures since no internal standard was incorporated. This permitted correction for variation in flame ionization detecto response with time. Typically, aliquots of reaction mixtures were taken at about 3 minute intervals throughout the course of the reaction and analyzed by chromatography. The resulting areas for the compounds obtained from the integrator were entered onto an IBM-PC with 20 megabyte hard disc. A program was developed using Lotus 1-2-3, to convert the peak areas obtained from the integrator into mole percent of reactants and products formed during the chlorination reactions.
  • the laboratory scale vapor phas reactor 100 used in proving the efficacy of the invention includes input means 110, oil bath 120, vaporizer 130, reactor 140, and produc separator 150.
  • input gases chlorobenzene, inert carrie gas, and chlorine enter by pipes 111, 113, 115 respectively.
  • Flow fo these gases is controlled by valves 112, 114, and 116.
  • Stopper 11 provided support for piping and sealed the apparatus.
  • the oil bath 12 consisted of a large beaker 121 filled with silicone oil 122 an provided for heat for the vaporizer 130 to assure that any liquid i vaporized and that only gas was inputed at reactor 140.
  • Anothe function of the oil bath was to regulate the temperature of th reaction in reactor 140.
  • the reactor 140 was filled wit catalyst/reagent comprising FeCl2 and A1C12 preferably deposited o vermiculite or a like inert substrate as further described below t form a catalyst bed 142.
  • Elbow 144 connects the output 143 of the reactor 140 to a T fitting 146 that connects to a product collector 150.
  • Produc collector 150 comprises a beaker 151 containing an ice bath 152 an round bottom flask 160 connected to the bottom of T-fitting 146. Gase such as inert gas and HC1 that are not collected in flask 160 exit a outlet 170.
  • a reagent quantity (25-80 g) o catalyst i.e., FeCl3
  • the reactor 140 was immersed in a hot oil bath 120 an equilibrated to the desired reaction temperature (160 C, nominal)
  • chlorobenzene Prior to entering the reaction zone chlorobenzene is pumped (vi syringe pump) through a vapor tube under a stream of argon to enhanc chlorobenzene vaporization.
  • the argon stream also serves to carry th reaction products up through the catalyst bed 142 into an ice-bat cooled receiver 160 (see Figure 1).
  • the catalyst bed 142 was flushe with argon and rechlorinated with Cl2 by passing the gases throug calibrated rotometers and up through the catalyst bed for specific tim periods.
  • Experiment 1 consisted of a series of initial vapor phase experiments.
  • the catalyst bed was neat anhydrous, FeCl3 fine crystals 98 percent (Aldrich Cat. No. 15,7740) (71.2 g, 0.439 moles).
  • the chlorobenzene was vaporized by dripping it down onto a 2 cm thick layer of glass beads in the top part of the reactor (above the catalyst bed).
  • Tables 1A and IB The results for Experiment 1 are summarized in Tables 1A and IB.
  • chlorine gas and chlorobenzene vapors were fed simultaneously through the catalyst bed.
  • the catalyst bed had been exhaustively chlorinated prior to the reaction to assure that it was in the FeU3 form.
  • the conversion was about 76 percent and the P/P+0 ratio was about 82 percent.
  • the catalyst bed had not been regenerated and was predominantly in the FeCl2 form. In this case, the conversion was only about 36 percent and the P/P+0 only 67 percent.
  • This drop in both conversion and P/P+0 ratio indicates that in example 1 catalytic (Cl2 gas) and reagent (FeCl3) reactions are both occurring simultaneously.
  • the chlorine and chlorobenzene were fed at different times (not simultaneously) and the most important observation to make is that the P/P+0 ratio increased to the range of 92.3 to 97 percent.
  • the next five examples had an average P/P+0 value of 96.3 percent; this is a P/0 ratio of 26/1.
  • a novel catalyst was made by depositing an acetone solution o FeCl3 and AICI3 on vermiculite.
  • the catalyst/reagent was prepared b dissolving 50 grams of anhydrous ferric chloride (FeCl3), 98 percent fine crystals (Aldrich Cat. No. 15,7740) and anhydrous aluminu chloride (5 grams) in 400 mis of acetone.
  • FeCl3 anhydrous ferric chloride
  • Aldrich Cat. No. 15,7740 98 percent fine crystals
  • anhydrous aluminu chloride 5 grams
  • a slurry of regula vermiculite, packing grade, 1-4 mm particle size, (50 grams) an acetone 300 is was prepared.
  • the FeCl3/AlCl3 solution was added t the vermiculite slurry in a 2 liter round bottom flask with a groun glass joint.
  • the flask was attached to a rotor evaporator (Rotovac® and the acetone was stripped off with a water aspirator. When most o the acetone was removed the flask was heated in a hot water bath t about 85 C to give 126.3 grams of the catalyst. Some of this catalys (66.2 grams containing 26.2 grams of FeU3) was charged to the reacto that was immersed in a silicone oil bath heated to about 160 C. Argo (20 ccs/min) was passed through the hot reactor for about 24 hours
  • Lowering the temperature may require an increase in pulse time for the inert gas.
  • the appropriate length can easily be determined by those skilled in the art.
  • the short pulse of inert gas can effectively separate the chlorine and benzene or chlorobenzene so as to obtain the benefits of the invention.
  • Examples 1-8 demonstrated the need for a porous inert or a porous inert resilient (e.g. compressible and expandable) catalyst/reagent substrate.
  • This substrate can be any material such as vermiculite that is porous and has a high surface area, is inert to the reactants used in the process and accepts and retains the catalyst/reagent.
  • the substance preferably compresses and expands when pressure is increased and reduced.
  • the substrate should preferably have a high loading capacity. This loading capacity is enhanced by porosity of the substrate or by rough surface texture.
  • the presently preferred substrate is vermiculite. Further, the vermiculite is preferably a powder having an average particle size of about 1 mm to about 6 mm. Most preferred is an average particle size of about 3 mm.
  • vermiculite and the like An advantage of vermiculite and the like is that a high degree of loading of catalyst/reagent can be obtained. For example, about 50 weight percent of the catalyst/reagent composition when using vermiculite was catalyst/reagent. This is attributed to the high porosity of the vermiculite. While an acetone solvent has been used herein, other like solvents may be used. For example lower alcohols such as ethyl alcohol, methyl alcohol, propyl alcohol, and butyl alcohol; and ethers such as diethyl ether and the like may be used.
  • Example 13 Chlorination with excess chlorine converted the material to an active catalyst bed that gave a P/P+0 ratio of 95.8 percent and a 33 percent conversion of 10 ml of chlorobenzene.
  • Example 13 was carried out without reactivation with chlorine but less than 1 percent conversion was obtained. This indicates that all of the available FeCl3 was consumed in example 12. Similar sequences were carried out for the remaining three examples as summarized in Tables 2A and 2B.
  • Example 22 illustrate optimized catalyst bed regeneration.
  • Examples 22-26 were run to determine the optimum (minimum) amount of chlorine required to regenerate the catalyst bed.
  • the chlorine flow estimated at 6 millimoles per minute, was decreased in steps from 362 to 45 millimoles.
  • the corresponding chlorine flow times were 60, 45, 30, 15 and 7.5 minutes.
  • the mole percent conversion of chlorobenzene remained relatively constant at 80- 81 percent for these experiments but dropped to 67 percent when the chlorine was reduced to 45 millimoles (7.5 mins).
  • Note that the P/P+0 ratio remained at the high level of 95.3 percent to 96.4 percent during this series of experiments.
  • the results show that between 45 and 90 millimoles of chlorine are required to regenerate the catalyst bed when the chlorobenzene pulse is 49.1 millimoles. This is good agreement with the theoretical stoichiometric requirement.
  • example 39 Five separate cycles of the reactor were carried out with all samples collected in the same receiver.
  • the values in Table 3E, example 39 are cumulative values for the five separate cycle samples. For this series the conversion was a high value of 88.5 mole percent or 91.1 weight percent and product recovery weight was good (107.1 percent) but the P/P+0 ratio had dropped to 92.9 percent. The reason for this slight drop off is not known.
  • example 40 At the end of example 40 the sample receiver was changed and example 41 was started.
  • the argon flow rate was 100 ml/min.
  • the carrier gas flow rate (argon) was 50, 25, 10 and 0 ml/min respectively.
  • Example 45 the chlorobenzene and chlorine gas were fed simultaneously with disastrous results (see Table 4B) .
  • the catalyst bed was obviously contaminated so the bath was heated to 180 C with an argon flush of 100 ml/min for 3 hours to remove higher chlorinated aromatics.
  • the bath temperature was reduced to normal and example 46 was carried out. This resulted in a good P/P+0 of 95.8 percent but low conversion (49 percent) and product recovery (47 percent).
  • Example 47 a further check, exhibited the sam behavior.
  • Examples 48 and 49 demonstrate that HC1 gas can be used as th carrier or flush gas with no deterioration of the P/P+0 ratio (about 95 percent) as shown in Table 4B.
  • Inert gases useful in the present invention include argon, helium, neon, nitrogen, and mixtures thereof. Additionally, HCl produced in the reaction can substitute for part of the inert gas as it does not enter into the reaction. For purposes of the process herein HCl gas although not an inert gas will be defined and treated as an inert gas since it is inert to the reaction. It can be fully substituted for the other inert gases herein. Use of HCl will aid in reducing overall costs.
  • Figure 2 depicts in flow sheet form an apparatus useful for the improved process of the invention. Gas supply means include inert gas source 212, chlorine source 214, chlorobenzene source 210 and vaporizer 216.
  • the apparatus provides for a source of chlorobenzene 210 that flows as a liquid to evaporator 216 by line 211.
  • Gaseous chlorobenzene from evaporator 216 passes to metering unit 218 by line 217 and then to the input of reaction column 220 by l ne 219.
  • Control means comprising metering control 280 and pulse-meter 218 control the flow of gases to the reactor.
  • Metering Control 280 provides appropriate signals to pulse-meter 218 for switching between gases provided at lines 213, 215, 217, 273, and 275 from other gas sources: inert gas 212, chlorine 214, evaporator 216, and scrubber 270 respectively.
  • the gases may be provided in the following sequence for flow through column 220: Chlorobenzene 222, inert gas 224, chlorine 226, and inert gas 224 after which this sequence is repeated.
  • inert gas and/or HCl may be added as a carrier to the chlorobenzene and/or chlorine metered gases to provide a mixture of appropriate concentrations. If needed an initial long pulse of chlorine is provided to activate the catalyst/reagent composition in reactor 220. This is then followed by a pulse of inert gas and then the sequence outlined above.
  • Reactor means illustrated by reactor column 220 may comprise one or more columns in parallel.
  • a reactor column 220 is shaped so as to facilitate the flow of multiple pulses of gases therethrough and to facilitate the distribution of gas as it is introduced to the reactor so that a wavefront of each gas sweeps th previous gas before it.
  • Such a reactor preferably has a length muc longer than the width.
  • the diameter of reactor column 220 is in th range of about 2 to about 20 cm to facilitate flow and allow control o reaction temperatures. Preferably, the diameter is about 2 to about cm.
  • a temperature control means (not shown) that is analogous to th oil bath 120 of Figure 1 may be used.
  • a circulating liquid such a silicone oil, or the like, for keeping the temperature within th desired range is preferred.
  • Separation means comprising distillation columns 230, 240 stripper 250, condenser 260 and, scrubber 270 separate the produc stream from line 221 into constituent components.
  • the separation mean may use any appropriate equipment known in the art to accomplish it purpose.
  • the first distillation column 230 separates the output gases containing principally dichlorobenzenes from trichlorobenzene and higher poly-chlorinated benzenes. Trichlorobenzene and polychlorinated benzenes are removed as residue at line 233.
  • the distillate is introduced via line 231 to a second distillation column 240 where dichlorobenzenes are separated from inert gases, HCl, and unreacted chlorobenzene.
  • Dichlorobenzenes are removed as residue at line 243.
  • the residue may be withdrawn at line 245 or separated further by separator/crystallizer 250 via line 247 to produce separated o- dichlorobenzene and p-dichlorobenzene that can be removed via lines 251 and 253 respectively.

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

Abstract

Le procédé décrit, qui sert à produire du p-dichlorobenzène, consiste à utiliser un réacteur qui contient un catalyseur/réactif servant à convertir du chlorobenzène (ou benzène) en p-dichlorobenzène et qui comporte une entrée et une sortie servant à introduire les réactants et à retirer le produit; à introduire un jet de chlorobenzène (ou benzène) gazeux dans le réacteur et à faire réagir le chlorobenzène avec le catalyseur/réactif pour former du p-dichlorobenzène; à introduire un jet de gaz inerte dans le réacteur; à introduire un jet de chlore gazeux dans le réacteur et à faire réagir le chlore avec le catalyseur/réactif; à introduire un jet de gaz inerte dans le réacteur; à répéter les étapes d'introduction des jets de façon séquentielle; et à retirer en continu le produit contenant du p-dichlorobenzène de la sortie du réacteur. Dans un autre mode de réalisation, la présente invention se rapporte à un procédé qui permet de produire une composition servant à la production de p-dichlorobenzène et qui consiste: à dissoudre un catalyseur/réactif destiné à produire du p-dichlorobenzène à partir de chlorobenzène (ou benzène) dans un solvant pour former une solution; à placer la solution en contact avec un substrat inerte poreux; et à déposer le catalyseur/réactif sur le substrat. Le substrat inerte poreux est de préférence constitué par un matériau résilient, tel que la vermiculite. Le catalyseur/réactif est de préférence constitué par un mélange de FeCl3 et de AlCl3, le FeCl3 pouvant toutefois être utilisé seul. Dans un troisième mode de réalisation, la présente invention se rapporte à un appareil, qui sert à produire du p-dichlorobenzène à partir de chlorobenzène (ou benzène) et qui comprend: une amenée de gaz fournissant une source de chlore gazeux, de gaz inerte et de chlorobenzène (ou benzène); un régulateur et un compteur de jets servant à recevoir et à réguler les gaz provenant de l'amenée de gaz et permettant une commutation entre les sources de chlore gazeux, de gaz inerte et de chlorobenzène (ou benzène), de façon à fournir des jets de chaque gaz à l'entrée d'un réacteur en colonne; un ou plusieurs réacteurs en colonne comportant chacun une entrée et une sortie et contenant une composition catalyseur/réactif destinée à convertir du chlorobenzène (ou benzène) en p-dichlorobenzène et qui reçoit les jets de gaz introduits depuis le compteur de jets au niveau de l'entrée; ainsi qu'un séparateur servant à séparer les gaz produits de la sortie du réacteur.
PCT/US1989/005708 1989-01-11 1989-12-21 Production de dichlorobenzene presentant des rapports para/ortho eleves Ceased WO1990008118A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019900701884A KR910700217A (ko) 1989-01-11 1989-12-21 고비율 파라(para)/오르소(ortho)이염화벤젠의 생성

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US29654989A 1989-01-11 1989-01-11
US296,549 1989-01-11

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WO1990008118A1 true WO1990008118A1 (fr) 1990-07-26

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JP (1) JPH02184641A (fr)
KR (1) KR910700217A (fr)
AU (1) AU4839990A (fr)
CA (1) CA2005485A1 (fr)
WO (1) WO1990008118A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995026815A1 (fr) * 1994-03-31 1995-10-12 Exxon Chemical Patents Inc. Catalyseurs a acide de lewis sur support pour reactions de conversion d'hydrocarbures
WO1995026816A1 (fr) * 1994-03-31 1995-10-12 Exxon Chemical Patents Inc. Catalyseurs d'acides de lewis sur support pour reactions de conversion d'hydrocarbures

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3029296A (en) * 1959-12-21 1962-04-10 Monsanto Chemicals Chlorination process
US4235825A (en) * 1979-11-02 1980-11-25 Ppg Industries, Inc. Production of dichlorobenzene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3029296A (en) * 1959-12-21 1962-04-10 Monsanto Chemicals Chlorination process
US4235825A (en) * 1979-11-02 1980-11-25 Ppg Industries, Inc. Production of dichlorobenzene

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995026815A1 (fr) * 1994-03-31 1995-10-12 Exxon Chemical Patents Inc. Catalyseurs a acide de lewis sur support pour reactions de conversion d'hydrocarbures
WO1995026816A1 (fr) * 1994-03-31 1995-10-12 Exxon Chemical Patents Inc. Catalyseurs d'acides de lewis sur support pour reactions de conversion d'hydrocarbures
US5561095A (en) * 1994-03-31 1996-10-01 Exxon Chemical Patents Inc. Supported lewis acid catalysts for hydrocarbon conversion reactions
US5648580A (en) * 1994-03-31 1997-07-15 Exxon Chemical Patents Inc. Supported lewis acid catalysts for hydrocarbon conversion reactions

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AU4839990A (en) 1990-08-13
CA2005485A1 (fr) 1990-07-11
JPH02184641A (ja) 1990-07-19
KR910700217A (ko) 1991-03-14

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