CN101087743A - Process for the manufacture of 1,2-dichloroethane - Google Patents

Process for the manufacture of 1,2-dichloroethane Download PDF

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CN101087743A
CN101087743A CNA200580044789XA CN200580044789A CN101087743A CN 101087743 A CN101087743 A CN 101087743A CN A200580044789X A CNA200580044789X A CN A200580044789XA CN 200580044789 A CN200580044789 A CN 200580044789A CN 101087743 A CN101087743 A CN 101087743A
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fraction
ethene
ethylene dichloride
reservoir
reactor
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CN101087743B (en
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多米尼克·巴尔塔萨特
米歇尔·施特雷贝勒
米歇尔·朗珀勒
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Solvay SA
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Solvay SA
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Priority claimed from FR0503254A external-priority patent/FR2883871B1/en
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Priority claimed from PCT/EP2005/057045 external-priority patent/WO2006067190A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride
    • 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
    • C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
    • C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
    • C07C17/156—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/04—Chloro-alkenes
    • C07C21/06—Vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
    • C10G57/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process with polymerisation
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

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  • Organic Chemistry (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

A process which is used for preparing 1,2-dichloroethane starting with a hydrocarbon source comprises the following procedures: a) the hydrocarbon source is cracked to prepare the product mixture comprising ethene and other component; b) the product mixture comprising the ethene is conveyed to at least one container; c) the stored product mixture comprising the ethene is provided to the chloridizing reactor and/or the chlorine-oxidizing reactor, and a majority of ethene existing in the reactor is conveyed to 1,2-dichloroethane; and d) the obtained 1,2-dichloroethane is separated from the product flow from the chloridizing and the chlorine-oxidizing reactor.

Description

Preparation 1, the method for 2-ethylene dichloride
The present invention relates to a kind of preparation 1, the method for 2-ethylene dichloride (DCE), a kind of method and a kind of method for preparing polyvinyl chloride (PVC) for preparing vinylchlorid (VC).
Up to now, purity is usually used in preparing DCE above 99.8% ethene, and the latter is used to prepare VCM basically.By the various petroleum productss of cracking, then through the separating step of numerous complicated costliness so that ethene and other cracking product separation obtain the product of extreme high purity, thereby obtain the ethene of this extreme high purity.
Owing to make the expensive problem that this high-purity ethylene brings, researched and developed and used purity to prepare the whole bag of tricks of DCE less than 99.8% ethene.The advantage of these methods is, by simplifying the process of separating the product that obtains from cracking, thereby avoids complex separations that preparation DCE is no advantage, and cost is reduced.
For example, patent application WO 00/26164 has put down in writing a kind of by simplifying the method that ethane cracking and ethylene chlorination prepare DCE.For this reason, carry out in the presence of the impurity that the ethylene chlorination step obtains in cracking ethane process.
The part of patent application WO 03/48088 has been put down in writing the method for a kind of DCE of preparation, comprises making ethane dehydrogenation, forms the cut that comprises ethane, ethene and hydrogen containing foreign, makes cut chlorination and/or oxychlorination then.
Although prepare in the conventional unit of DCE at the ethene that surpasses 99.8% by chlorination and/or oxychlorination purity, usually from piping network supply ethene, piping network itself has important surge capability, can regulate the flow velocity of ethene, thereby guarantee the excellent operation of chlorination and/or oxychlorination reactor, but control by the operation of the stove in cracking hydrocarbon source basically in the above-mentioned speed for preparing ethene in the method for making than the ethene of low-purity that is included in integrated unit itself.The production of these stoves is polluted by it and continuous solution is removed the influence of operating.Quality and the fluctuation quantity for the treatment of the cracking load also are the reasons of ethene quantitative changeization.For this reason, be difficult to carry out cracking, therefore need regulate its production in real time therefrom to obtain stable ethylene production rate.Consequently, the excellent operation of restive direct connected chlorination and/or oxychlorination reactor.
Therefore, the purpose of this invention is to provide a kind of method of using purity less than 99.8% ethene, its advantage is, by the complex separations of abandoning preparation DCE is no advantage that makes ethene and other cracking product separation, thereby cost is reduced, and it is also advantageous in that, can regulate the ethene flow velocity when having avoided the problems referred to above, thereby guarantee the excellent operation of chlorination and/or oxychlorination reactor.
For this reason, the present invention relates to a kind ofly begin to prepare 1 from the hydrocarbon source, the method for 2-ethylene dichloride comprises:
A) make the source cracking of described hydrocarbon, make the product mixtures that contains ethene and other compositions;
B) product mixtures that will contain ethene is transported at least one reservoir;
C) product mixtures that contains ethene with aforementioned storage is fed to chlorination reactor and/or oxychlorination reactor, and the most of ethene that exists in reactor is converted to 1, the 2-ethylene dichloride;
D) make obtain 1,2-ethylene dichloride and the product flow point that comes from chlorination and oxychlorination reactor from.
The hydrocarbon source of being considered can be any known hydrocarbon source.Preferably, (the hydrocarbon source of step a) is selected from petroleum naphtha, gas oil, natural gas liquids, ethane, propane, butane, Trimethylmethane and its mixture to carry out cracking.In particularly preferred mode, the hydrocarbon source is selected from ethane, propane and propane/butane mix.The hydrocarbon source that use is selected from propane and propane/butane mix obtains good result.Propane/butane mix can former state exists or can be made of the mixture of propane and butane.
In the present invention, statement ethane, propane, butane and propane/butane mix should be understood as that and refer to the commercially available product that gets, promptly by main straight product (ethane, propane, butane or propane/butane are as mixture) and accessory other saturated or unsaturated hydrocarbons formations, the latter can be lighter or heavier than straight product itself.
In the present invention, (step a) should be understood as that and refer to be used for institute that the processing hydrocarbons source causes forming the product mixtures that contains ethene and other compositions in steps in statement cracking.
Described cracking can be carried out according to any known technology, as long as can prepare the product mixtures that contains ethene and other compositions.Advantageously, described cracking is included in the third compound such as water, oxygen, sulfur derivatives and/or catalyzer exist or do not exist down, the first step in pyrolysis (that is to say, transform under heat effect) hydrocarbon source.Preferably carry out following steps after the first step: the step of the heat of recovery of heat splitting gas, separate step, compression and the dry gas of heavy product (for example quenching) by organic quenching and water-based step, remove and exist or the step of most of carbonic acid gas of adding and most of sulphur compound (for example by means of neutralizing treatment), the undesirable derivative of the hydrogenation step of acetylene for example randomly, and the step of randomly removing part hydrogen and/or methane, for example by PSA (transformation absorption) method or pass through embrane method.
Advantageously, in the method for the invention, the product mixtures that contains ethene and other compositions that comes from step a) comprises hydrogen, methane, contains compound, carbon monoxide, nitrogen and the oxygen of 2～7 carbon atoms.With respect to the cumulative volume of described product mixtures, hydrogen, methane and except that acetylene, contain the amount that the compound of 2～7 carbon atoms preferably exists and be at least 200 volume ppm.With respect to the cumulative volume of described product mixtures, the amount of carbon monoxide, nitrogen, oxygen and acetylene is to be at least 200 volume ppm less than 200 volume ppm or amount.With respect to the cumulative volume of described product mixtures, containing compound, carbonic acid gas, hydrogen sulfide and other sulfocompounds and the amount of water in above-mentioned product mixtures that surpass 7 carbon atoms is less than 200 volume ppm.
In the present invention, the statement reservoir should be understood as that finger wherein stores product mixtures and any container to be used that contains ethene.
According to preferred variant, method of the present invention is characterized in that, after step a) and before the step d):
B1) product mixtures that will contain ethene is separated into the cut (fraction A) that contains being rich in of the part ethene compound lighter than ethene, the cut (fraction B) that is rich in ethene and last running (cut C);
B2) fraction A and fraction B are transported to independent reservoir (being respectively reservoir A or storage tank A and reservoir B or storage tank B); And
C) fraction A of preserving among the reservoir A is transported to chlorination reactor, the fraction B of preserving among the reservoir B is transported to chlorination reactor and/or oxychlorination reactor, the most of conversion of ethylene that exists in reactor becomes 1, the 2-ethylene dichloride.
The method according to this invention, sign fraction B and the defined amount of fraction A are the amounts before they enter chlorination/oxychlorination and chlorination respectively below.
According to the preferred variants of the inventive method, the fraction B that contains part ethene is rich in ethene.Advantageously, with respect to the cumulative volume of fraction B, fraction B is characterized in that hydrogen richness by volume for being less than or equal to 2%, preferably is less than or equal to 0.5%, is less than or equal to 0.1% in particularly preferred mode.
Advantageously, cumulative volume with respect to fraction B, fraction B is characterized in that containing the content of compound of at least 3 carbon atoms by volume for being less than or equal to 0.01%, preferably is less than or equal to 0.005%, is less than or equal to 0.001% in particularly preferred mode.
Advantageously, with respect to the cumulative volume of fraction B, it is 40%～99.5% ethene by volume that fraction B contains.Advantageously, with respect to the cumulative volume of fraction B, fraction B contains by volume and is at least 40%, and preferably at least 50%, at least 60% ethene in particularly preferred mode.Advantageously, with respect to the cumulative volume of fraction B, fraction B contains by volume and to be at the most 99.5%, and preferably at the most 99.2%, 99% ethene at the most in particularly preferred mode.
In the hydrocarbon source is under the preferable case of ethane, and advantageously, with respect to the cumulative volume of fraction B, fraction B comprises by volume and be at least 60%, preferably at least 70%, and at least 75% ethene in particularly preferred mode.Advantageously, with respect to the cumulative volume of fraction B, fraction B comprises by volume and to be at the most 99.5%, preferably at the most 99.2%, and 99% ethene at the most in particularly preferred mode.
In the hydrocarbon source is under the preferable case of propane/butane mix, and advantageously, with respect to the cumulative volume of fraction B, fraction B comprises by volume and be at least 40%, preferably at least 50%, and at least 60% ethene in particularly preferred mode.Advantageously, with respect to the cumulative volume of fraction B, fraction B comprises by volume and to be at the most 99.5%, preferably at the most 99.2%, and 99% ethene at the most in particularly preferred mode.
Advantageously, with respect to the cumulative volume of fraction B, its feature of fraction B is that also acetylene content by volume for being less than or equal to 0.01%, preferably is less than or equal to 0.005%, is less than or equal to 0.001% in particularly preferred mode.
According to the preferred variants of the inventive method, fraction B is transported to chlorination reactor and/or oxychlorination reactor, preferably is attended by energy recovery.
According to the preferred variants of the inventive method, the fraction A that contains part ethene is rich in the compound lighter than ethene.These compounds are methane, nitrogen, oxygen, hydrogen and carbon monoxide normally.Advantageously, fraction A contains at least 70%, and preferably at least 80%, at least 85% the contained light compound of ratio ethene in the product mixtures that step b) is handled in particularly preferred mode.Advantageously, fraction A contains at the most 99.99%, and preferably at the most 99.97%, 99.95% the contained light compound of ratio ethene in the product mixtures that step b) is handled at the most in particularly preferred mode.
In the hydrocarbon source is that fraction A contains at least 90% under the preferable case of ethane, preferably at least 95%, and at least 98% the contained light compound of ratio ethene in the product mixtures that step b) is handled in particularly preferred mode.Advantageously, fraction A contains at the most 99.99%, and preferably at the most 99.98%, 99.97% the contained light compound of ratio ethene in the product mixtures that step b) is handled at the most in particularly preferred mode.
In the hydrocarbon source is that fraction A contains at least 70% under the preferable case of propane/butane mix, preferably at least 80%, and at least 85% the contained light compound of ratio ethene in the product mixtures that step b) is handled in particularly preferred mode.Advantageously, fraction A contains at the most 99.99%, and preferably at the most 99.95%, 99.9% the contained light compound of ratio ethene in the product mixtures that step b) is handled at the most in particularly preferred mode.
Advantageously, cumulative volume with respect to fraction A, fraction A is characterized in that containing the content of compound of at least 3 carbon atoms by volume for being less than or equal to 0.01%, preferably is less than or equal to 0.005%, is less than or equal to 0.001% in particularly preferred mode.
Advantageously, fraction A contains ethylene content by volume, make its account for fraction B ethylene content by volume 10%～90%.Advantageously, fraction A contains ethylene content by volume, make its account for fraction B ethylene content by volume be less than or equal to 90%, preferably be less than or equal to 85%, in particularly preferred mode, be less than or equal to 80%.Advantageously, fraction A contains ethylene content by volume, make its account for fraction B ethylene content by volume at least 10%, preferably at least 15%, in particularly preferred mode at least 20%.
In the hydrocarbon source is under the preferable case of ethane, advantageously, fraction A contains ethylene content by volume, make its account for fraction B ethylene content by volume be less than or equal to 90%, preferably be less than or equal to 85%, in particularly preferred mode, be less than or equal to 80%.Advantageously, fraction A contains ethylene content by volume, make its account for fraction B ethylene content by volume at least 15%, preferably at least 20%, in particularly preferred mode at least 22%.
In the hydrocarbon source is under the preferable case of propane/butane mix, advantageously, fraction A contains ethylene content by volume, make its account for fraction B ethylene content by volume be less than or equal to 80%, preferably be less than or equal to 75%, in particularly preferred mode, be less than or equal to 70%.Advantageously, fraction A contains ethylene content by volume, make its account for fraction B ethylene content by volume at least 10%, preferably at least 15%, in particularly preferred mode at least 20%.
Advantageously, with respect to the cumulative volume of fraction A, its feature of fraction A is that also acetylene content by volume for being less than or equal to 0.01%, preferably is less than or equal to 0.005%, is less than or equal to 0.001% in particularly preferred mode.
According to the preferred variants of the inventive method, fraction A is transported to chlorination reactor, preferably after expanding with the energy that reclaims.
The first seed variant according to the inventive method preferred variants, consider prepare DCE method advantageously equilibrated (promptly by chlorination and oxychlorination of ethylene and pyrolysis make 1, the method of 2-ethylene dichloride (DCE) can produce the HCl of this method aequum), advantageously, fraction A and B in each the weight fraction of ethene output account for ethene and make 45～55% of total amount (fraction A+fraction B).Preferably, the weight fraction of ethene output accounts for and makes the about 55% of total amount in the fraction A, and the weight fraction of ethene output is about 45% in the fraction B.In particularly preferred mode, the weight fraction of ethene output accounts for and makes the about 52.5% of total amount in the fraction A, and the weight fraction of ethene output is about 47.5% in the fraction B.
The second seed variant according to the inventive method preferred variants, consider the method for preparing DCE advantageously unbalanced (promptly for example external source HCl oxychlorination that the part supply can be provided is not carried out pyrolysis with HCl or the DCE cut that makes), advantageously, fraction A and B in each the weight fraction of ethene output account for ethene and make 20～80% of total amount (fraction A+fraction B).Preferably, the weight fraction of ethene output accounts for ethene and makes 25～75% of total amount (fraction A+fraction B) in the fraction A.
First embodiment according to the inventive method preferred variants second seed variant, consider that the method for preparing DCE is advantageously unbalanced by external source HCl, advantageously, in the fraction A molar fraction of ethene output account for contained ethene integral molar quantity of the product mixtures handled through step b) and external source HCl molar weight difference 45～55%, preferred 50～54%, in particularly preferred mode, be about 52.5%.
Second embodiment according to the inventive method preferred variants second seed variant, consider the method that the prepares DCE DCE by coproduction advantageously (therefore, some DCE do not carry out pyrolysis) unbalanced, advantageously, ethene output molar fraction in the fraction B account for contained ethene integral molar quantity of the product mixtures handled through step b) and coproduction the DCE molar weight difference 45～55%, preferred 46～50%, in particularly preferred mode, be about 47.5%.
According to the preferred variants of the inventive method, at step b1) in, described product mixtures preferable separation becomes fraction A, fraction B and last running (cut C).Advantageously, cut C contains ethane and the compound that contains at least 3 carbon atoms.Advantageously, these compounds that contain at least 3 carbon atoms from the product mixtures that contains ethene and other compositions that comes from step a) obtain or by step b1) side reaction produce.In containing the compound of at least 3 carbon atoms, that can mention has propane, propylene, butane and its undersaturated derivative and all saturated or undersaturated heavier compounds.
Can use the product mixtures that any separation method will contain ethene to be separated into fraction A, fraction B and cut C, as long as it advantageously comprises maximum four, preferred maximum three separating steps, to obtain fraction A and B.
According to the first preferred clastotype, first separating step of the product mixtures that contains ethene through can therefrom extracting cut C that comes from step a) handled, and makes the mixture that obtains through second step process then, is separated into fraction A and fraction B.
According to the second preferred clastotype, first separating step of the product mixtures that contains ethene through can therefrom extracting fraction A that comes from step a) handled, and makes the mixture that obtains through second step process then, is separated into fraction B and cut C.
First clastotype is particularly preferred.Many variants can come from this first clastotype of the product mixtures that contains ethene of step a).
The preferred variants of first clastotype comprises makes the mixture that obtains from first separating step that is used to extract cut C be separated into fraction A and fraction B through second step process, this step is the distilation steps that carries out by means of distillation tower, wherein distillation tower is equipped with relevant utility appliance, as at least one reboiler and at least one condenser that comprises the backflow reservoir.According to this preferred variant, fraction A is advantageously left from the top of distillation tower, and fraction B is advantageously left from the bottom of distillation tower.
Distillation tower can be selected from plate tower, packed distillation column, have the distillation tower of structured packing and in conjunction with the distillation tower of above-mentioned two or more internal structures.
Advantageously, the backflow reservoir of the condenser of top of tower when needed can be as the little reservoir of fraction A.Then, advantageously, if reservoir B has big storage capacity, it preferably constitutes the ethylene reservoir that is used to supply chlorination reactor of replenishing as fraction A so, also supplies oxychlorination reactor simultaneously.
Advantageously, the reservoir B that is used to collect fraction B is arranged in after the outlet of distillation tower bottom.Advantageously, collect liquid cut therein.
According to particularly preferred variant, therefore, method of the present invention is characterized in that, after step a) and before the step d):
B1) product mixtures that will contain ethene is separated into the cut (fraction A) that contains being rich in of the part ethene compound lighter than ethene, the cut (fraction B) that is rich in ethene and last running (cut C);
B2) fraction B is transported to reservoir (reservoir B or storage tank B); And
C) fraction A is transported to chlorination reactor, the fraction B of preserving among the reservoir B is transported to chlorination reactor and/or oxychlorination reactor, the most of conversion of ethylene that exists in reactor becomes 1, the 2-ethylene dichloride.
The special characteristic that the preferred variants of the inventive method is described in detail in the above, particularly for fraction A, B and C, its sub-variant and the product mixtures that will contain ethene are separated into this three kinds of fraction separation methods, also are applicable to this particularly preferred variant of the inventive method.
Advantageously, as long as storage capacity allows, reservoir B itself can be used for supplying chlorination reactor and oxychlorination reactor where necessary.
Advantageously, containing dissolved catalyzer such as FeCl 3Or carry out chlorination reaction in the another kind of lewis acidic liquid phase (preferably mainly being DCE).Advantageously, can mix this catalyzer and promotor such as alkali metal chloride.Obtain a pair of FeCl of being of good result 3Title complex (tetrachloro ferrate-lithium-be documented among the patent application NL 6901398) with LiCl.
Advantageously, FeCl 3Consumption be about 1～10g FeCl 3/ kg liquid starting material.Advantageously, FeCl 3Be about 0.5～2 with the mol ratio of LiCl.
Advantageously, chlorination method of the present invention carries out under 30～150 ℃ temperature.How pipe pressure does not all obtain good result in temperature less than boiling temperature (overcooled chlorination) with at boiling temperature itself (fluidizing chlorination).
When chlorination method of the present invention is overcooled chlorination, obtain good result by operation under the following conditions:, but advantageously be less than or equal to 80 ℃ and preferably be less than or equal to 70 ℃ temperature advantageously more than or equal to 50 ℃ be preferably greater than or equal 60 ℃; Pressure in the gas phase is advantageously more than or equal to 1.5 be preferably greater than or equal 2 bars absolute, but advantageously is less than or equal to 20, preferably is less than or equal to 10, is less than or equal to 6 bars absolute in particularly preferred mode.
The fluidizing chlorination method is particularly preferred, can usefully reclaim the heat of reaction when suitable.In this case, be reflected under the following conditions and carry out: advantageously more than or equal to 60 ℃, be preferably greater than or equal 90 ℃, in particularly preferred mode,, but advantageously be less than or equal to 150 ℃ and preferably be less than or equal to 135 ℃ temperature more than or equal to 95 ℃; Pressure in the gas phase advantageously, more than or equal to 0.2, be preferably greater than or equal 0.5, in particularly preferred mode more than or equal to 1.2 and in the most particularly preferred mode more than or equal to 1.5 bars absolute, but advantageously be less than or equal to 10 and preferably be less than or equal to 6 bars absolute.
Chlorination method also can be to be circulated throughout the refrigerative mixed chlorinated method of seething with excitement.Statement is circulated throughout the refrigerative mixed chlorinated method of seething with excitement should be understood as that finger wherein for example by means of being immersed in the interchanger in the reaction medium or carrying out the cooling of reaction medium by the circulation of circulating in interchanger, produces the method for at least one quantitative DCE simultaneously in gas phase.Advantageously, the conditioned reaction temperature and pressure makes the DCE of preparation stay gas phase, and removes surplus heat by means of exchange surface from reaction medium.
In addition, advantageously, in the chlorating organic liquid medium, carry out chlorination method.Preferably, described chlorating organic liquid medium is also referred to as liquid starting material, mainly is made up of DCE.
The fraction A (itself be pure or through dilution) that contains ethene and chlorine can be introduced in the reaction medium together or individually by any known devices.Be dividing potential drop that increases fraction A and the dissolving of quickening often to constitute this method conditioning step, it may be favourable being introduced separately into.
The add-on of chlorine is enough to make most of conversion of ethylene, and does not need to add excessive unconverted chlorine.Chlorine/ethylene ratio of using is preferably 1.2～0.8, is 1.05～0.95mol/mol in particularly preferred mode.
The chlorating product that obtains mainly contains the chlorizate of DCE and minor by-products such as vinyl trichloride or a small amount of ethane or methane.According to known pattern make the DCE that obtains and the product flow point that comes from chlorination reactor from, and can utilize the heat of chlorination reaction usually.
Then, advantageously, unconverted product (methane, carbon monoxide, nitrogen, oxygen and hydrogen) is made than begin to separate the required easier separation of pure ethylene from original mixture.
Advantageously, carry out oxi-chlorination comprising in the presence of the catalyzer that is deposited on the active element on the inert support, wherein active element comprises copper.Advantageously, inert support is selected from the carrier of aluminum oxide, silica gel, mixed oxide, clay and other natural origins.Aluminum oxide constitutes preferred inert support.
Preferably include the catalyzer of active element, it advantageously has at least two kinds of elements, and wherein a kind of is copper.In the active element outside copper, that can mention has basic metal, alkaline-earth metal, rare earth metal and is selected from nail, rhodium, palladium, osmium, iridium, platinum and golden metal.The catalyzer that contains following active element is particularly advantageous: copper/magnesium/potassium, copper/magnesium/sodium; Copper/magnesium/lithium, copper/magnesium/caesium, copper/magnesium/sodium/lithium, copper/magnesium/potassium/lithium and copper/magnesium/caesium/lithium, copper/magnesium/sodium/potassium, copper/magnesium/sodium/caesium and copper/magnesium/potassium/caesium.The catalyzer of being put down in writing in patent application EP-A 255 156, EP-A 494 474, EP-A-657 212 and the EP-A 657 213 that this is incorporated herein by reference is the most particularly preferred.
Advantageously, press the metal form and calculate, copper content accounts for 30～90g/kg of catalyzer, preferred 40～80g/kg, 50～70g/kg in particularly preferred mode.
Advantageously, press the metal form and calculate, Mg content accounts for 10～30g/kg of catalyzer, preferred 12～25g/kg, 15～20g/kg in particularly preferred mode.
Advantageously, press the metal form and calculate, alkali metal content accounts for 0.1～30g/kg of catalyzer, preferred 0.5～20g/kg, 1～15g/kg in particularly preferred mode.
Advantageously, Cu: Mg: alkali-metal atomic ratio is 1: 0.1-2: 0.05-2, and preferred 1: 0.2-1.5: 0.1-1,5, in particularly preferred mode 1: 0.5-1: 0.15-1.
According to the specific surface area of the B.E.T. method measurement catalyzer that uses nitrogen, advantageously be 25m 2/ g～300m 2/ g, preferred 50～200m 2/ g, 75～175m in particularly preferred mode 2/ g, this catalyzer is particularly advantageous.
Catalyzer can be used in fixed bed or the fluidized-bed.Second kind of selection is preferred.Under the condition and range of recommending at this reaction usually, use oxychlorination process.Advantageously, temperature is 150～300 ℃, preferred 200～275 ℃, and most preferably 215～255 ℃.Advantageously, pressure is greater than normal atmosphere.The value of 2～10 bars absolute obtains good result.The scope of 4～7 bars absolute is preferred.Pressure can be regulated effectively, obtaining the optimum residence time in reactor, and keeps various operating speeds to pass through with constant speed.Usually the residence time is 1～60 second, preferred 10～40 seconds.
The oxygen source that oxychlorination is used can be air, pure oxygen or its mixture, preferred pure oxygen.A kind of scheme in back allows easily to make unconverted reagent recirculation, thereby is preferred.
Can each reagent be introduced in the bed by any known devices.For security reasons, advantageously oxygen and other reagent are separated introducing separately usually.These also require under the pressure and temperature of considering, leave or gaseous mixture that recirculation is advanced in the reactor remains on outside the inflammableness scope.Preferably keep so-called rich mixture, it contains very few oxygen with respect to fuel and can not light.In this, if this compound has wide inflammableness scope, a large amount of hydrogen that exist (＞2%, preferred＞as 5%vol) will to constitute shortcoming.
Advantageously, the ratio of used hydrogenchloride (HCl)/oxygen is 3～6mol/mol.Advantageously, the ratio of ethylene/hydrogen chloride is 0.4～0.6mol/mol.
The chlorizate that obtains mainly contains DCE and minor by-products such as vinyl trichloride.According to known pattern make the DCE that obtains and the product flow point that comes from oxychlorination reactor from.The heat of oxi-chlorination reclaims with vapor form usually, and it can be used for separating or any other purpose.
Then, unconverted product such as methane and ethane are through than begin to separate the required easier separation of pure ethylene from original mixture.
Then, the DCE that obtains by chlorination and oxychlorination of ethylene changes into VC.
Therefore, the invention still further relates to a kind of method for preparing vinylchlorid.For this reason, the present invention relates to a kind of method for preparing vinylchlorid, it is characterized in that, make by the inventive method obtain 1, the 2-ethylene dichloride carries out pyrolysis.
It is well known by persons skilled in the art can carrying out the pyrolytic important document.Advantageously, obtain pyrolysis by the gas-phase reaction in tube furnace.Usually pyrolysis temperature is 400～600 ℃, is preferably 480 ℃～540 ℃.Advantageously, the residence time is 1～60s, is preferably 5～25s.Advantageously, the transformation efficiency of DCE is restricted to 45～75%, with the formation of restriction by product with to the pollution of boiler tube.Step subsequently can use any known devices to collect the VC and the hydrogenchloride of purifying, and preferably carries out the oxychlorination upgrading.Behind purifying, advantageously, unconverted DCE is transported to pyrolysis oven.
In addition, the invention still further relates to the method for a kind of PVC of preparation.For this reason, the present invention relates to the method that a kind of VC that obtains according to the inventive method by polymerization prepares PVC.
The method for preparing PVC can be body, solution or aqueous dispersion polymerization process, preferably aqueous dispersion polymerization process.
Expression aqueous dispersion polymerization should be understood as that radical polymerization and radical polymerization in water-based emulsion and the polymerization in aqueous microsuspension of finger in waterborne suspension.
The radical polymerization that is expressed in the waterborne suspension should be understood as that any radical polymerization that finger carries out in aqueous medium in the presence of dispersion agent and oil soluble radical initiator.
The radical polymerization that is expressed in the water-based emulsion should be understood as that any radical polymerization that finger carries out in aqueous medium in the presence of emulsifying agent and water-soluble radical initiator.
Expression aqueous microsuspension polymerization, be also referred to as the polymerization in the aqueous dispersion that homogenizes, should be understood as that finger wherein uses oil-soluble initiator and by powerful mechanical stirring with there is any radical polymerization of the emulsion of the monomer droplet for preparing under the emulsifying agent condition.
Advantage of method of the present invention is, can regulate the flow velocity of ethene, can avoid chlorine to store, thereby avoids the safety issue of being correlated with.In fact, chlorine is stored this poisonous product that will require to liquefy, and can bring serious risk when leaking.Can also avoid the expensive and dangerous storage of HCl gas.
Another advantage of the inventive method is, by means of the storage of fraction B at least, for the operation of chlorination reactor and oxychlorination reactor very big handiness arranged.
Therefore, when chlorination stops, after the operation of suitably regulating tower, can store obsolete ethene.The lighter-than-air gas (fraction A) that does not contain ethene can find an exit in producer.Stop or during velocity variations, can also store the ethene that does not consume in oxychlorination, perhaps satisfy consumption peaks on the contrary.
Another advantage of the inventive method is, can have from the hydrocarbon source to the fully-integrated method that is begun to obtain polymkeric substance by the monomer of making at same location of manufacturing.
Below in conjunction with the description of drawings of specification sheets method of the present invention.Accompanying drawing is made of Fig. 1, schematically shows the present invention and prepares 1, an embodiment of 2-ethylene dichloride method.
To obtain and can therefrom extract the product mixtures that contains ethene and other compositions 1 introducing king-tower 2 of last running from the first separating step cracking hydrocarbon source, king-tower is the distillation tower that reboiler is installed in the bottom and condenser is installed at the top, thereby product mixtures is separated into two kinds of different fractions, i.e. the cut 4 of the cut 3 at tower 2 tops and tower 2 bottoms.
Cut 3 is rich in compound, particularly methane, hydrogen, nitrogen, oxygen and the carbon monoxide lighter than ethene, is transported to the unit 5 of ethylene chloride.The chlorine 6 that the supply flow velocity can be regulated hardly.With the DCE that forms, comprise any purifying type by part 7, be transported to pyrolysis unit 8.
The liquid distillate 4 that it is characterized in that utmost point low hydrogen content is transported to reservoir 9.This ethylene reservoir can be regulated the flow velocity of the ethene of the oxychlorination unit 10 that is transported to supply oxygen or air 11.Oxychlorination unit receives HCl 12 from the pyrolysis unit 8 of making VC 13, and the HCl flow velocity almost can not be regulated.Advantageously, the gas 14 that leaves from chlorination unit 5 can act as a fuel by upgrading.
Produced according to the present invention 1, the preferred embodiment of 2-ethylene dichloride method, reservoir 9 also partly is used to supply chlorination unit 5.

Claims (14)

1. one kind begins to prepare 1 from the hydrocarbon source, and the method for 2-ethylene dichloride comprises:
A) make the source cracking of described hydrocarbon, make the product mixtures that contains ethene and other compositions;
B) product mixtures that will contain ethene is transported at least one reservoir;
C) product mixtures that contains ethene with aforementioned storage is fed to chlorination reactor and/or oxychlorination reactor, and the most of ethene that exists in reactor is converted to 1, the 2-ethylene dichloride;
D) make obtain 1,2-ethylene dichloride and the product flow point that comes from chlorination and oxychlorination reactor from.
2. preparation 1 as claimed in claim 1, the method for 2-ethylene dichloride is characterized in that, described hydrocarbon source is selected from petroleum naphtha, gas oil, natural gas liquids, ethane, propane, butane, Trimethylmethane and its mixture.
3. preparation 1 as claimed in claim 1 or 2, the method for 2-ethylene dichloride is characterized in that, described hydrocarbon source is selected from ethane, propane, butane and propane/butane mix.
4. as each described method of claim 1～3, it is characterized in that the product mixtures that contains ethene and other compositions that comes from step a) comprises hydrogen, methane, contains compound, carbon monoxide, nitrogen and the oxygen of 2～7 carbon atoms.
5. as each described preparation 1 of claim 1～4, the method for 2-ethylene dichloride is characterized in that, after step a) and before the step d):
B1) product mixtures that will contain ethene is separated into the cut (fraction A) that contains being rich in of the part ethene compound lighter than ethene, the cut (fraction B) that is rich in ethene and last running (cut C);
B2) fraction A and fraction B are transported to independent reservoir (being respectively reservoir A and reservoir B); And
C) fraction A of preserving among the reservoir A is transported to chlorination reactor, simultaneously the fraction B of preserving among the reservoir B is transported to chlorination reactor and/or oxychlorination reactor, the most of conversion of ethylene that exists in reactor becomes 1, the 2-ethylene dichloride.
6. preparation 1 as claimed in claim 5, the method of 2-ethylene dichloride, it is characterized in that first separating step of product mixtures through can therefrom extracting cut C that contains ethene handled, the mixture that obtains then is separated into fraction A and fraction B through second step process.
7. preparation 1 as claimed in claim 6, the method of 2-ethylene dichloride, it is characterized in that, second step that is separated into fraction A and fraction B is the distilation steps that carries out by means of distillation tower, described distillation tower is equipped with relevant utility appliance, as at least one reboiler and at least one condenser that comprises the backflow reservoir.
8. preparation 1 as claimed in claim 7, the method for 2-ethylene dichloride is characterized in that, and fraction A is left from the top of described distillation tower, and fraction B is left from the bottom of described distillation tower.
9. preparation 1 as claimed in claim 8, the method for 2-ethylene dichloride is characterized in that, the reservoir B that is used to collect fraction B is arranged at after the outlet of described distillation tower bottom.
10. as each described preparation 1 of claim 5～9, the method for 2-ethylene dichloride is characterized in that, with respect to the cumulative volume of fraction B, it is 40%～99.5% ethene by volume that fraction B contains.
11. as each described preparation 1 of claim 5～10, the method for 2-ethylene dichloride is characterized in that, fraction A contains ethylene content by volume, make its account for fraction B ethylene content by volume 10%～90%.
12. as each described preparation 1 of claim 1～11, the method for 2-ethylene dichloride is characterized in that, after step a) and before the step d):
B1) product mixtures that contains ethene is separated into and contains the cut (fraction A) of being rich in of the part ethene compound lighter, the cut (fraction B) that is rich in ethene and last running (cut C) than ethene;
B2) fraction B is transported to reservoir (reservoir B or storage tank B); And
C) fraction A is transported to chlorination reactor, the fraction B of preserving among the reservoir B is transported to chlorination reactor and/or oxychlorination reactor, the most of conversion of ethylene that exists in reactor becomes 1, the 2-ethylene dichloride.
13. a method for preparing vinylchlorid is characterized in that, make by each described method of claim 1～12 obtain 1, the 2-ethylene dichloride carries out pyrolysis.
14. a vinylchlorid that obtains according to the described method of claim 13 by polymerization prepares the method for polyvinyl chloride.
CN200580044789XA 2004-12-23 2005-12-21 Process for manufacture of 1,2-dichloroethane Expired - Fee Related CN101087743B (en)

Applications Claiming Priority (7)

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FR0413873A FR2880019B1 (en) 2004-12-23 2004-12-23 PROCESS FOR PRODUCING 1,2-DICHLOROETHANE
FR0413873 2004-12-23
FR0503254A FR2883871B1 (en) 2005-04-01 2005-04-01 PROCESS FOR PRODUCING 1,2-DICHLOROETHANE
FR0503254 2005-04-01
FR0503252 2005-04-01
FR0503252 2005-04-01
PCT/EP2005/057045 WO2006067190A1 (en) 2004-12-23 2005-12-21 Process for the manufacture of 1,2-dichloroethane

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