CN101087743B - Process for manufacture of 1,2-dichloroethane - Google Patents

Process for manufacture of 1,2-dichloroethane Download PDF

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CN101087743B
CN101087743B CN200580044789XA CN200580044789A CN101087743B CN 101087743 B CN101087743 B CN 101087743B CN 200580044789X A CN200580044789X A CN 200580044789XA CN 200580044789 A CN200580044789 A CN 200580044789A CN 101087743 B CN101087743 B CN 101087743B
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fraction
ethene
ethylene dichloride
reactor
reservoir
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CN101087743A (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

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

The method of preparation 1,2-ethylene dichloride
The present invention relates to a kind of method of 1,2-ethylene dichloride (DCE), a kind of method and a kind of method for preparing polyvinyl chloride (PVC) for preparing vinylchlorid (VC) of preparing.
Up to now, purity is usually used in preparing DCE above 99.8% ethene, and the latter is basically for the preparation of VCM.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 makes cost.
For example, patent application WO 00/26164 has put down in writing a kind of method for preparing DCE by simplifying ethane cracking and ethylene chlorination.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, then makes cut chlorination and/or oxychlorination.
Although prepare in the standard element 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 basically controlled by the operation of the stove in cracking hydrocarbon source 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 impact that operates.Quality and the fluctuation quantity for the treatment of the cracking load also are ethene amount causes of changes.For this reason, be difficult to carry out cracking therefrom to obtain stable ethylene production rate, therefore need regulate in real time its production.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 purity of using less than the method for 99.8% ethene, its advantage is, by the complex separations that makes ethene and other cracking product separation of abandoning preparation DCE is no advantage, thereby make cost, 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 of method that begins to prepare 1,2-ethylene dichloride from the hydrocarbon source, comprising:
A) make the source cracking of described hydrocarbon, make the product mixtures that contains ethene and other compositions;
The product mixtures that b) 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 1,2-ethylene dichloride;
D) make obtain 1, the 2-ethylene dichloride separates with the product stream that comes from chlorination and oxychlorination reactor.
The hydrocarbon source of considering can be any known hydrocarbon source.Preferably, (step hydrocarbon source 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 commercially available product, namely by main straight product (ethane, propane, butane or propane/butane are as mixture) and other less important 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 the institute that refers to cause forming the product mixtures that contains ethene and other compositions for the treatment of the hydrocarbon source 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 step, compression and the dry gas of the step of the heat of recovery of heat splitting gas, separating heavy product (for example quenching by organic quenching and water-based), 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 remove portion hydrogen and/or methane randomly, for example by PSA (pressure-variable adsorption) method or pass through embrane method.
Advantageously, in the method for the invention, come from compound, carbon monoxide, nitrogen and oxygen that the step product mixtures that contains ethene and other compositions a) comprises hydrogen, methane, contains 2～7 carbon atoms.With respect to the cumulative volume of described product mixtures, hydrogen, methane and except 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, step a) afterwards and steps d) before:
The product mixtures that b1) 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 1,2-ethylene dichloride.
The method according to this invention, the below's sign fraction B and the defined amount of fraction A are the amounts before they enter respectively chlorination/oxychlorination and chlorination.
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.
Be under the preferable case of ethane in the hydrocarbon source, advantageously, with respect to the cumulative volume of fraction B, fraction B comprises by volume and is 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.
Be under the preferable case of propane/butane mix in the hydrocarbon source, advantageously, with respect to the cumulative volume of fraction B, fraction B comprises by volume and is 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, fraction B is further characterized in that 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%, preferably at least 80%, in particularly preferred mode at least 85% through step b) the contained light compound of ratio ethene in the product mixtures processed.Advantageously, fraction A contains at the most 99.99%, preferably at the most 99.97%, in particularly preferred mode at the most 99.95% through step b) the contained light compound of ratio ethene in the product mixtures processed.
That fraction A contains at least 90% under the preferable case of ethane in the hydrocarbon source, preferably at least 95%, in particularly preferred mode at least 98% through step b) the contained light compound of ratio ethene in the product mixtures processed.Advantageously, fraction A contains at the most 99.99%, preferably at the most 99.98%, in particularly preferred mode at the most 99.97% through step b) the contained light compound of ratio ethene in the product mixtures processed.
That fraction A contains at least 70% under the preferable case of propane/butane mix in the hydrocarbon source, preferably at least 80%, in particularly preferred mode at least 85% through step b) the contained light compound of ratio ethene in the product mixtures processed.Advantageously, fraction A contains at the most 99.99%, preferably at the most 99.95%, in particularly preferred mode at the most 99.9% through step b) the contained light compound of ratio ethene in the product mixtures processed.
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 so that its account for fraction B ethylene content by volume 10%～90%.Advantageously, fraction A contains ethylene content by volume so that 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 so that its account for fraction B ethylene content by volume at least 10%, preferably at least 15%, in particularly preferred mode at least 20%.
Under the preferable case of ethane in the hydrocarbon source, advantageously, fraction A contains ethylene content by volume so that 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 so that its account for fraction B ethylene content by volume at least 15%, preferably at least 20%, in particularly preferred mode at least 22%.
Under the preferable case of propane/butane mix in the hydrocarbon source, advantageously, fraction A contains ethylene content by volume so that 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 so that 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, fraction A is further characterized in that 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 balance (namely by chlorination and oxychlorination of ethylene and pyrolysis make 1, the method of 2-ethylene dichloride (DCE) can produce the HCl of the 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 (namely 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.
The first embodiment according to the inventive method preferred variants the second seed variant, consider that the method for preparing DCE is advantageously unbalanced by external source HCl, advantageously, the molar fraction of ethene output accounts for through step b in the fraction A) difference of the molar weight of the contained ethene integral molar quantity of the product mixtures processed and external source HCl 45～55%, preferred 50～54%, in particularly preferred mode, be about 52.5%.
The second embodiment according to the inventive method preferred variants the 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 accounts for through step b) difference of the DCE molar weight of the contained ethene integral molar quantity of the product mixtures processed and coproduction 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 come from the step product mixtures that contains ethene and other compositions a) and 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, come from step first separating step of the product mixtures that contains ethene through can therefrom extracting cut C a) and process, the mixture that obtains is processed through second step, be separated into fraction A and fraction B.
According to the second preferred clastotype, come from step first separating step of the product mixtures that contains ethene through can therefrom extracting fraction A a) and process, the mixture that obtains is processed through second step, be separated into fraction B and cut C.
The first clastotype is particularly preferred.Many variants can come from this first clastotype of the step product mixtures that contains ethene a).
The preferred variants of the first clastotype comprises makes the mixture that obtains from the first separating step that is used for extraction cut C be separated into fraction A and fraction B through the second step processing, this step is the distilation steps that carries out by means of distillation tower, wherein distillation tower is equipped with relevant utility appliance, such 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 larger storage capacity, it preferably consists of the ethylene reservoir that is used for the supply chlorination reactor of replenishing as fraction A so, also supplies simultaneously oxychlorination reactor.
Advantageously, the reservoir B that be used for to collect fraction B is arranged in after the outlet of distillation tower bottom.Advantageously, collect therein liquid cut.
According to particularly preferred variant, therefore, method of the present invention is characterized in that, step a) afterwards and steps d) before:
The product mixtures that b1) 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 1,2-ethylene dichloride.
The special characteristic that in the above preferred variants of the inventive method is described in detail, particularly for fraction A, B and C, its sub-variant and the product mixtures that will contain ethene are separated into the separation method of these three kinds of cuts, 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, at the catalyzer that contains dissolving 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: advantageously more than or equal to 50 ℃ with preferably greater than or equal to 60 ℃, but advantageously be less than or equal to 80 ℃ and preferably be less than or equal to 70 ℃ temperature; Pressure in the gas phase is advantageously more than or equal to 1.5 with preferably greater than or equal to 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, reaction is being carried out under the following conditions: advantageously more than or equal to 60 ℃, preferably greater than or equal to 90 ℃, in particularly preferred mode, more than or equal to 95 ℃, but advantageously be less than or equal to 150 ℃ and preferably be less than or equal to 135 ℃ temperature; Pressure in the gas phase advantageously, more than or equal to 0.2, preferably greater than or equal to 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 the mixed chlorinated method of the overcooled boiling of circulation.The mixed chlorinated method of the statement overcooled boiling of circulation should be understood as that finger wherein for example by means of the interchanger or the cooling that loops reaction medium by circulating that are immersed in the reaction medium in interchanger, produce simultaneously the method for a certain amount of at least DCE 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 organic liquid medium of chlorination, carry out chlorination method.Preferably, the organic liquid medium of described chlorination is also referred to as liquid starting material, mainly is comprised 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 device.Be the dividing potential drop that increases fraction A and the dissolving of accelerating often to consist of the 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 product of the chlorination that obtains mainly contains the chlorizate of DCE and a small amount of by product such as vinyl trichloride or a small amount of ethane or methane.According to known pattern the DCE that obtains is separated with the product stream that comes from chlorination reactor, and usually can utilize the heat of chlorination reaction.
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 consists of 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 putting 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.It is preferred that the second is selected.Under the condition and range of usually recommending for this reaction, 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.Rear a kind of scheme allows easily to make unconverted reagent recirculation, thereby is preferred.
Can each reagent be introduced in the bed by any known device.For security reasons, usually advantageously oxygen and other reagent are separated separately introducing.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 consist of 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 a small amount of by product such as vinyl trichloride.According to known pattern the DCE that obtains is separated with the product stream that comes from oxychlorination reactor.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.
The important document that can carry out pyrolysis is well known by persons skilled in the art.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 device to collect 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 the radical polymerization in water-based emulsion and the polymerization in aqueous microsuspension that refers 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 danger when leaking.Can also avoid the expensive and dangerous storage of HCl gas.
Another advantage of the inventive method is, by means of at least storage of fraction B, for the operation of chlorination reactor and oxychlorination reactor very large handiness arranged.
Therefore, when chlorination stops, after the operation of suitable adjusting 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 on the contrary consumption peaks.
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 embodiment that the present invention prepares 1,2-ethylene dichloride method.
To obtain from the first separating step cracking hydrocarbon source and can therefrom extract the product mixtures that contains ethene and other compositions 1 introducing king-tower 2 of last running, 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 for supply chlorination unit 5.

Claims (11)

1. method that begins to prepare 1,2-ethylene dichloride from the hydrocarbon source comprises:
A) make the source cracking of described hydrocarbon, make the product mixtures that contains ethene and other compositions;
The product mixtures that b1) will contain ethene is separated into the fraction A that contains being rich in of the part ethene compound lighter than ethene, the fraction B that is rich in ethene and last running C;
B2) fraction A and fraction B are transported to independent reservoir, are respectively reservoir A and reservoir B;
The fraction A that c) will be kept among the reservoir A is transported to chlorination reactor, and the fraction B that will preserve in reservoir B simultaneously is transported to chlorination reactor and/or oxychlorination reactor, and the most of ethene that exists in reactor is converted to 1,2-ethylene dichloride;
D) make obtain 1, the 2-ethylene dichloride separates with the product stream that comes from chlorination and oxychlorination reactor.
2. method that begins to prepare 1,2-ethylene dichloride from the hydrocarbon source comprises:
A) make the source cracking of described hydrocarbon, make the product mixtures that contains ethene and other compositions;
The product mixtures that b1) will contain ethene is separated into the fraction A that contains being rich in of the part ethene compound lighter than ethene, the fraction B that is rich in ethene and last running C;
B2) fraction B is transported to reservoir B;
C) fraction A is transported to chlorination reactor, the fraction B that will preserve in reservoir B simultaneously is transported to chlorination reactor and/or oxychlorination reactor, and the most of ethene that exists in reactor is converted to 1,2-ethylene dichloride;
D) make obtain 1, the 2-ethylene dichloride separates with the product stream that comes from chlorination and oxychlorination reactor.
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 petroleum naphtha, gas oil, natural gas liquids, ethane, propane, butane, Trimethylmethane and its mixture.
4. 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.
5. method as claimed in claim 1 or 2 is characterized in that, comes from compound, carbon monoxide, nitrogen and oxygen that the step product mixtures that contains ethene and other compositions a) comprises hydrogen, methane, contains 2～7 carbon atoms.
6. preparation 1 as claimed in claim 1 or 2, 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 processed, the mixture that then obtains is processed through second step and is separated into fraction A and fraction B.
7. preparation 1 as claimed in claim 6, the method for 2-ethylene dichloride is characterized in that, and the second step that is separated into fraction A and fraction B is the distilation steps that carries out by means of distillation tower, and described distillation tower is equipped with relevant utility appliance.
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 for the collection fraction B is arranged at after the outlet of described distillation tower bottom.
10. preparation 1 as claimed in claim 1 or 2, 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. preparation 1 as claimed in claim 1 or 2, the method for 2-ethylene dichloride is characterized in that, fraction A contains ethylene content by volume so that its account for fraction B ethylene content by volume 10%～90%.
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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FR0413873 2004-12-23
FR0413873A FR2880019B1 (en) 2004-12-23 2004-12-23 PROCESS FOR PRODUCING 1,2-DICHLOROETHANE
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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CN111848335B (en) * 2019-05-27 2023-05-30 万华化学(福建)有限公司 Method for purifying 1, 2-dichloroethane in vinyl chloride production process

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