CN102001930B - Method for purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production and application thereof - Google Patents
Method for purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production and application thereof Download PDFInfo
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- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 238000000034 method Methods 0.000 title claims abstract description 84
- 229940106681 chloroacetic acid Drugs 0.000 title claims abstract description 71
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 53
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 41
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 claims abstract description 95
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000007788 liquid Substances 0.000 claims abstract description 75
- 229960005215 dichloroacetic acid Drugs 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- 239000007789 gas Substances 0.000 claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 230000000694 effects Effects 0.000 claims abstract description 33
- 239000007791 liquid phase Substances 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000012071 phase Substances 0.000 claims abstract description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 36
- 235000011054 acetic acid Nutrition 0.000 claims description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- 238000005660 chlorination reaction Methods 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000010970 precious metal Substances 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 229910000510 noble metal Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000035484 reaction time Effects 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000009849 deactivation Effects 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 abstract 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 28
- 229960000583 acetic acid Drugs 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 14
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 230000009467 reduction Effects 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- HKMLRUAPIDAGIE-UHFFFAOYSA-N methyl 2,2-dichloroacetate Chemical compound COC(=O)C(Cl)Cl HKMLRUAPIDAGIE-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- FBCCMZVIWNDFMO-UHFFFAOYSA-N dichloroacetyl chloride Chemical compound ClC(Cl)C(Cl)=O FBCCMZVIWNDFMO-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005837 enolization reaction Methods 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- VHFUHRXYRYWELT-UHFFFAOYSA-N methyl 2,2,2-trichloroacetate Chemical compound COC(=O)C(Cl)(Cl)Cl VHFUHRXYRYWELT-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Abstract
The invention discloses a method for purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production and application thereof. The method comprises the following steps of: arranging a VIII-group metal serving as a hydrogenolysis catalyst bed layer in a catalytic reactor with a lining made from polytetrafluoroethylene or a zirconium material; making the solution of chloride flow through a fixed bed layer and making a hydrogen-nitrogen mixed gas and a liquid phase flow in parallel to enter the bed layer at the gage pressure of 100 to 800 kPa and the temperature of 100 and 200 DEG C; performing hydrogenolysis on all or most of polychlorinated acid in the solution of the chloride; taking a material out of the reactor; performing gas-liquid separation; crystallizing the liquid phase of the solution of the chloride; washing to obtain a chloroacetic acid product; and condensing, absorbing and separating a gas phase for recovering hydrogen, chlorine hydride and acetic acid. The method can improve the removal effect and the treatment efficiency of dichloroacetic acid and trichloroacetic acid and product purity, reduce the deactivation trend and the activity descent speed of a catalyst, shorten reaction time, reduce hydrogen consumption, improve raw material utilization rate and product yield, and further improve economic benefits.
Description
Technical field
The invention belongs to Monochloro Acetic Acid technical field of producing, more particularly relate to the improvement and bring new ideas of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production and uses thereof.
Background technology
Mono Chloro Acetic Acid is a kind of important organic fine industrial chemicals, is widely used in the fields such as agricultural chemicals, medicine, dyestuff, oil field chemical, papermaking chemical product, textile auxiliary agent, tensio-active agent, plating, spices, essence.Its maximum purposes is to produce carboxymethyl cellulose, is secondly to produce Thiovanic acid.Along with technical progress and development, the Application Areas that Mono Chloro Acetic Acid is new is developed gradually, and prospect is very wide.World's aggregate consumption is more than 800,000 t/a in recent years for Mono Chloro Acetic Acid, and the consumption of China is also more than 400,000 t/a.Chloroacetic synthetic method is the emphasis that people research and develop always, vinylchlorid, chloroethanol oxidation style are there is, chloroacetyl chloride, trieline hydrolysis method, ketene chlorination process, the novel synthesis such as Catalytic Chlorination of acetic acid method, but industrial process only has two kinds: trieline hydrolysis method and Catalytic Chlorination of acetic acid method.
Trieline hydrolysis method is taking the vitriol oil as catalyzer, carries out addition and the hydrolysis reaction of water simultaneously.Trieline hydrolysis method because of technological process compared with simple, product purity compared with high and developed, Europe once adopted this technique to build industrial production device, but due to raw material costliness, superseded in recent years.Catalytic Chlorination of acetic acid method is under the effect of catalyzer (as halogenide and the aceticanhydride etc. of iodine, phosphorus, sulphur or sulphur and phosphorus), in the time of 95-140 DEG C, Glacial acetic acid and chlorine carry out chlorination reaction and generate Monochloro Acetic Acid, the even trichoroacetic acid(TCA) of dichloro acetic acid that by-product is a small amount of in one or several tandem reactor.Due to the existence of by product, reaction product must just can obtain highly purified Mono Chloro Acetic Acid product after the purification process such as crystallization.
Domesticly generally adopt the chlorination of sulfur method catalysis acetic acid.Under sulphur exists, acetic acid and chlorine direct reaction generate Mono Chloro Acetic Acid.And generally adopt the chlorination of acetic anhydride catalysis acetic acid abroad, no matter be sulfur method or acetic anhydride method, except unloading phase, catalyzer actual in reaction process is Acetyl Chloride 98Min., sulphur and aceticanhydride are the propellant of Acetyl Chloride 98Min..Aceticanhydride is made catalyzer also difference compared with sulphur, and aceticanhydride is made catalyzer, and to produce the amount of Acetyl Chloride 98Min. be certain, is disposable, and it can be used as again reaction raw materials, the moisture of bringing in can also neutralization reaction system, therefore large usage quantity.And sulphur is done catalyzer constantly circulation in reaction process, consumption is less, but chlorine consumption is larger, generates SOx waste gas simultaneously.Although the price of sulphur and amount ratio aceticanhydride are low, the acetic acid of sulfur method and chlorine consumption rate acetic anhydride method are high, and the quality of acetic anhydride method by-product hydrochloric acid can reach the level of synthetic hydrochloric acid, and the by-product hydrochloric acid of sulfur method is because sulfur-bearing can not use in many industries.Acetic anhydride method is compared with sulfur method, and production consumes low, and " three wastes " pollute few.In intermediates chlorated liquid, Mono Chloro Acetic Acid massfraction reaches 93%-95%, and the growing amount of by-product dichloroacetic acid greatly reduces (for 3%-5%), and quality product is high and stable.Therefore, from comprehensive output, the advantage of acetic anhydride method is clearly, and this does not also consider the weak tendency of product aspect quality and the fund input aspect environment protection that sulfur method is produced.Along with the increase of Mono Chloro Acetic Acid demand, the raising that derived product requires Mono Chloro Acetic Acid quality product, extensive (ten thousand tons more than scale), continuous processing Mono Chloro Acetic Acid have had development space at home.
No matter adopt which kind of production method, inevitably produce the by product such as dichloro acetic acid, trichoroacetic acid(TCA) in production processes of chloroacetic acid, this is determined by reaction mechanism.The chlorination initial stage, reaction is carried out fast, and the chloroacetyl chloride therefore generating can be converted into rapidly Mono Chloro Acetic Acid; In the reaction later stage, acetic acid content reduces, and Mono Chloro Acetic Acid content raises, and causes chloroacetyl chloride surplus.Superfluous chloroacetyl chloride, after enolization reaction, continues chlorination and generates dichloroacetyl chloride, and then generates dichloro acetic acid.But because the generation source of chloroacetyl chloride can not be single, cannot determine that the generation of dichloro acetic acid carries out by parallel reactor mechanism or by consecutive reaction mechanism, or two kinds of reaction mechanisms are also deposited, so also do not control the effective ways that polychloride generates at present.Therefore, how simple as far as possible, from reaction mixture, extract Monochloro Acetic Acid that purity is higher to high yield and become further reducing costs, improve quality, reducing the emphasis of pollution of each manufacturer.
Due to the difference of production technique and national conditions, in chlorated liquid, the conversion of dichloro acetic acid or removal technique have bigger difference both at home and abroad.At home, chlorated liquid is after crystallization goes out most of Mono Chloro Acetic Acid, and the processing of crystallizing chloroacetic acid mother liquor mainly contains following methods: generate methyl chloroacetate, methyl dichloroacetate and mixed ester with methanol esterification, this may be that the most general mother liquor of chloroacetic acid of China is processed approach.After mother liquor esterification, through neutralization, washing, drying and dehydrating, mixed ester can be used as intermediates and sells, or separates and can obtain methyl chloroacetate and methyl dichloroacetate product through rectification under vacuum.This method main drawback is that a. trichlorine impurity is not divisible, makes in methyl dichloroacetate product containing methyl trichloroacetate too highly, has had a strong impact on quality product.B. adopt total reflux esterification reaction tech, temperature of reaction is low, long reaction time, and capacity of equipment is low, and methanol consumption is large, ester products overstand and decomposing in still, esterification is operating as intermittent type.C. moisture too high in mixed ester product, easily acidolysis is rotten, and shortened storage period.Other mother liquor processing method has: produce sodium oxalate and oxyacetic acid, production carboxymethyl cellulose, the also method such as original production Mono Chloro Acetic Acid and acetic acid, degree of depth chlorination production dichloro acetic acid, trichoroacetic acid(TCA) and chloroform, generation Thiovanic acid and dichloro acetic acid, synthesizing glyoxalic acid of hydrodechlorination.Make a general survey of aforesaid method, mostly belong to small-scale production, complex procedures, various, has much brought again secondary pollution, can not eradicate pollution.The much more external also technique of original production Mono Chloro Acetic Acid and acetic acid of hydrodechlorinations that adopts, will generate Monochloro Acetic Acid and hydrogenchloride after dichloro acetic acid, trichoroacetic acid(TCA) hydrogenation.In chlorated liquid except Monochloro Acetic Acid, acetic acid without other impurity, the mother liquor after Monochloro Acetic Acid crystallization can be recycled in chloride process, has eradicated pollution, and has increased substantially quality product.Because of but the first-selected technique of extensive acetic anhydride method Monochloro Acetic Acid subsequent disposal.But the domestic research of this technology is less, need the research of carrying out this respect badly to meet the needs of Mono Chloro Acetic Acid development, and hydrogenation catalyst is appendix to precious metal palladium on gac or porous silica gel, because this catalyzer cost is higher, improper use meeting is sharply increased production cost, therefore the research of, carrying out chlorated liquid hydrogen addition technology is significant for the level that improves domestic Mono Chloro Acetic Acid development.
Chinese patent CN1382680A discloses a kind of method, in reaction system, add chlorine-resisting agent, can suppress the growing amount of dichloro acetic acid, available chlorine-resisting agent has manganese acetate, protochloride manganese, zinc chloride, zinc acetate or chromium acetate, and in product, the content of dichloro acetic acid can be down to below 3%.
Chinese patent CN101528657A discloses a kind of method, is the mixture of processing Monochloro Acetic Acid and dichloro acetic acid at pressure 1-10bar, 130～170 DEG C of temperature, under the use of catalyzer, makes the latter that hydrogenolysis occur.In reaction solution in Monochloro Acetic Acid production process, except these two kinds of materials, also contain the materials such as a certain amount of hydrochloric acid, water and acetic acid, this method does not mention whether being applicable to this system.
Chinese patent CN1197838C adopts palladium to make catalyzer, that dichloro acetic acid mol ratio is under 1.2～15: 1 condition in normal atmosphere 101.32kPa-100kPa (gauge pressure), 100～180 DEG C, hydrogen and pending mixture, make dichloro acetic acid generation hydrogenation, and repeat hydrogenated mixture, obtain the Monochloro Acetic Acid of low dichloroacetic acid content.Though this method can remove dichloro acetic acid or be down to lower content, under low pressure, repeat hydrogenation, required time is longer, and processing efficiency is lower.
German patent DE-A-1915037 discloses a kind of method, is hydrogenation one, two and trichoroacetic acid(TCA) mixture under the catalyzer existence being suspended in mixture, thereby reduces the concentration of dichloro acetic acid and trichoroacetic acid(TCA).The shortcoming of this method is in crude mixture, to add the particular active agent that dissolves in this mixture, has increased subsequent purification step, and hydrogen usage is larger simultaneously.
In above-mentioned patent, the removal effect of dichloro acetic acid is all undesirable, or processing efficiency is lower, and hydrogen gas consumption is larger, inevitably affects the economic benefit of product.
US Patent No. 5756840 adopts Pd/C catalyzer, and under 1bar, 130 DEG C of conditions, hydrogenolysis chloroethene will arrive mixture, makes dichloroacetic acid content be down to 0.35% by 3.2%.
European patent EP 0537838 under 135 DEG C, 1bar pressure, hydrogenolysis chloroacetic acid mixture, dichloroacetic acid content is down to 0.13% by 4%, moves 200 hours, catalyst activity reduction, formaldehyde content obviously raises.
Although these patent reaction effects increase, also exist long reaction time, hydrogen consumption is large, catalyst activity reduction is fast shortcoming, and all do not mention the problem whether chlorated liquid of the materials such as hydrochloric, acetic acid is suitable for.
Summary of the invention
Object of the present invention, is just to overcome above-mentioned shortcoming and defect, and a kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production and uses thereof is provided.It is a kind of actual new catalytic hydrogenolysis technique of industry that is applicable to, under the atmosphere of nitrogen, hydrogen gas mixture, can greatly improve the removal effect of dichloro acetic acid and trichoroacetic acid(TCA), the inactivation trend of the processing efficiency of raising hydrogenation speed, dichloro acetic acid and product purity, reduction catalyzer and active lowering speed, Reaction time shorten, reduction hydrogen consumption, improve the yield of raw material availability and product, further increase economic efficiency.
In order to achieve the above object, the method for purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production of the present invention is included under certain temperature and pressure, processes the mother liquor after acetic acid chlorination.Further comprising the steps of:
(1) in the catalyticreactor of inner liner polytetrafluoroethylene or zirconium material, device group VIII noble metals a kind of or its combine as hydrogenolysis catalyst bed, and the ratio that precious metal accounts for carrier is 0.1～3.5%;
(2) under the gauge pressure of 100～800kPa and under the temperature condition of 100～200 DEG C, make the chlorated liquid in Monochloro Acetic Acid production process flow through fixed bed, make hydrogen-nitrogen mixture gas and liquid phase simultaneously and flow to into bed;
(3) under the effect of beds, make whole in chlorated liquid or most many Mono Chloro Acetic Acids generation hydrogenolysis, produce Monochloro Acetic Acid;
(4) material is gone out to reactor, and through gas-liquid separation;
(5) by not containing or containing the how chloroacetic chlorated liquid liquid phase crystallization of minute quantity, washing, obtaining Monochloro Acetic Acid product after gas-liquid separation;
(6) by the gas phase after gas-liquid separation through condensation, absorption, separation, thereby recover hydrogen, hydrogenchloride and acetic acid.
The present invention uses a kind of of group VIII noble metals or its combine as catalyzer, makes many Mono Chloro Acetic Acids generation hydrogenation, and generation Monochloro Acetic Acid, is removing the how chloroacetic while, has improved the yield of Monochloro Acetic Acid product.
Support of the catalyst can be activated carbon, silicon-dioxide, aluminum oxide, float stone or diatomite.Taking specific surface area as 500～1350m
2when the activated carbon of/g is carrier, effect is best.During using palladium as catalyst activity component, better effects if.
Catalyzer is diameter while being 0.2～15mm, the height right cylinder that is 0.3～30mm or the diameter spheroid that is 0.3～10mm, and effect is fine.
When the ratio that precious metal of the present invention accounts for carrier is 0.5～1%, effect is fine.
When pressure is the gauge pressure of 250～500kPa, effect is fine.When temperature is 130～150 DEG C, effect is fine.
Hydrogenolysis is to occur under the mixture atmosphere of pure hydrogen or hydrogen and other rare gas element, and rare gas element can be one of nitrogen, helium, argon gas, carbonic acid gas or mixture.Hydrogen usage is 1.2～8.0 times of dichloro acetic acid molar weight, and the mol ratio of rare gas element and hydrogen is between 0～5 time, and effect is fine.Hydrogen usage is 1.5～5.0 times of dichloro acetic acid molar weight, and the mol ratio of rare gas element and hydrogen is between 2～3 time, and effect is best.
Liquid phase effect in the time that the residence time of beds is 1.5～5 hours is fine.Liquid phase is in the time that the residence time of beds is 2～4 hours, and effect is best.
In other words, in the present invention, the preferred hydrogenolysis processing condition of dichloro acetic acid are: 120～180 DEG C of temperature; Pressure 250～500kPa; Hydrogen usage is 1.5～5.0 times of dichloro acetic acid molar weight; The mol ratio of nitrogen and hydrogen is (0-0.1): 1; Liquid phase is 2～4 hours in the residence time of beds.Wherein first process condition is: 150 DEG C of temperature; Pressure 360kPa; Hydrogen usage is 3.5 times of dichloro acetic acid molar weight, and the liquid phase residence time is 2.5 hours.
Equipment and pipeline can adopt inner liner polytetrafluoroethylene, enamel or adopt corrosion resistant metallic substance zirconium, tantalum, Hastelloy material to make.
The purposes of the method for above-mentioned purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production is for the chlorated liquid containing Monochloro Acetic Acid 75-95%, dichloro acetic acid 0.5-6%, trichoroacetic acid(TCA) 0-3%, hydrochloric acid 1～3%, acetic acid 5～15%.After catalytic hydrogenolytic cleavage, the dichloroacetic acid content in mixed solution is less than 0.01% or lower.
The present invention is a kind of chloroacetic catalytic hydrogenolysis technique of purifying, and is mainly used in the processing of mixed solution after chlorination in Monochloro Acetic Acid production process, makes dichloro acetic acid and trichoroacetic acid(TCA) be converted into the dichloro acetic acid that does not contain or contain minute quantity in Monochloro Acetic Acid, product.
Technical scheme of the present invention is: in inner liner polytetrafluoroethylene or the catalyticreactor for zirconium material, beds is housed, under certain temperature and pressure, the chlorated liquid in Monochloro Acetic Acid production process flows through fixed bed.Meanwhile, hydrogen-nitrogen mixture gas and liquid phase also flow to into bed, and under the effect of catalyzer, whole or most many Mono Chloro Acetic Acids generation hydrogenolysis in chlorated liquid, produces Monochloro Acetic Acid.Material goes out after reactor through gas-liquid separation, liquid phase for not containing or containing the how chloroacetic chlorated liquid of minute quantity, can obtain high-quality Monochloro Acetic Acid product through the technique such as crystallization, washing.Gas phase is through condensation, absorption, the materials such as separation, recover hydrogen, hydrogenchloride and acetic acid.
Task of the present invention is exactly to complete like this.
Adopt after above-mentioned technique, speed of response has been accelerated in the raising of hydrogen dividing potential drop, and the hydrogen chloride gas that raw material and reaction are generated that adds of nitrogen more enters gas phase, hydrogenolysis is carried out more complete; And the introducing of nitrogen makes hydrogenolysis carry out more steadily, reduce the hydrogenolysis of the local excess load of catalyzer, be conducive to the life-span of extending catalyst.Meanwhile, hydrogenation is more conducive to reduce the hydrogenation side reaction of Monochloro Acetic Acid stably.Therefore, under processing condition of the present invention, in mixed solution dichloro acetic acid concentration can be down to very low, in chlorated liquid, contain and hydrogenolysis generate hydrogenchloride on reaction impact reduce to very little, improved utilization ratio and the yield of raw material.
It is a kind of actual new catalytic hydrogenolysis technique of industry that is applicable to, under the atmosphere of nitrogen, hydrogen gas mixture, can greatly improve the removal effect of dichloro acetic acid and trichoroacetic acid(TCA), the inactivation trend of the processing efficiency of raising hydrogenation speed, dichloro acetic acid and product purity, reduction catalyzer and active lowering speed, Reaction time shorten, reduction hydrogen consumption, improve the yield of raw material availability and product, further increase economic efficiency.The present invention can be widely used in the purification of Monochloro Acetic Acid in Monochloro Acetic Acid production.
Embodiment
Embodiment 1.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.Be included under certain temperature and pressure, process the mother liquor after acetic acid chlorination.Further comprising the steps of: (1), in the catalyticreactor of inner liner polytetrafluoroethylene or zirconium material, device group VIII noble metals a kind of or its combine as hydrogenolysis catalyst bed, and the ratio that precious metal accounts for carrier is 3.5%; (2) under the gauge pressure of 500kPa and under the temperature condition of 150 DEG C, make the chlorated liquid in Monochloro Acetic Acid production process flow through fixed bed, make hydrogen-nitrogen mixture gas and liquid phase simultaneously and flow to into bed; (3) under the effect of beds, make whole in chlorated liquid or most many Mono Chloro Acetic Acids generation hydrogenolysis, produce Monochloro Acetic Acid; (4) material is gone out to reactor, and through gas-liquid separation; (5) by not containing or containing the how chloroacetic chlorated liquid liquid phase crystallization of minute quantity, washing, obtaining Monochloro Acetic Acid product after gas-liquid separation; (6) by the gas phase after gas-liquid separation through condensation, absorption, separation, thereby recover hydrogen, hydrogenchloride and acetic acid.Effect is fine.
Embodiment 2.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.Be included under certain temperature and pressure, process the mother liquor after acetic acid chlorination.Further comprising the steps of: (1), in the catalyticreactor of inner liner polytetrafluoroethylene or zirconium material, device group VIII noble metals a kind of or its combine as hydrogenolysis catalyst bed, and the ratio that precious metal accounts for carrier is 2%; (2) under the gauge pressure of 800kPa and under the temperature condition of 100 DEG C, make the chlorated liquid in Monochloro Acetic Acid production process flow through fixed bed, make hydrogen-nitrogen mixture gas and liquid phase simultaneously and flow to into bed; (3) under the effect of beds, make whole in chlorated liquid or most many Mono Chloro Acetic Acids generation hydrogenolysis, produce Monochloro Acetic Acid; (4) material is gone out to reactor, and through gas-liquid separation; (5) by not containing or containing the how chloroacetic chlorated liquid liquid phase crystallization of minute quantity, washing, obtaining Monochloro Acetic Acid product after gas-liquid separation; (6) by the gas phase after gas-liquid separation through condensation, absorption, separation, thereby recover hydrogen, hydrogenchloride and acetic acid.Effect is fine.
Embodiment 3.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.Be included under certain temperature and pressure, process the mother liquor after acetic acid chlorination.Further comprising the steps of: (1), in the catalyticreactor of inner liner polytetrafluoroethylene or zirconium material, device group VIII noble metals a kind of or its combine as hydrogenolysis catalyst bed, and the ratio that precious metal accounts for carrier is 0.1%; (2) under the gauge pressure of 100kPa and under the temperature condition of 200 DEG C, make the chlorated liquid in Monochloro Acetic Acid production process flow through fixed bed, make hydrogen-nitrogen mixture gas and liquid phase simultaneously and flow to into bed; (3) under the effect of beds, make whole in chlorated liquid or most many Mono Chloro Acetic Acids generation hydrogenolysis, produce Monochloro Acetic Acid; (4) material is gone out to reactor, and through gas-liquid separation; (5) by not containing or containing the how chloroacetic chlorated liquid liquid phase crystallization of minute quantity, washing, obtaining Monochloro Acetic Acid product after gas-liquid separation; (6) by the gas phase after gas-liquid separation through condensation, absorption, separation, thereby recover hydrogen, hydrogenchloride and acetic acid.Effect is fine.
Embodiment 4.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.Its support of the catalyst is one of activated carbon, silicon-dioxide, aluminum oxide, float stone or diatomite.All the other are with embodiment 1.
Embodiment 5.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.Its support of the catalyst is taking specific surface area as 500～1350m
2the activated carbon of/g, all the other are with embodiment 1.
Embodiment 6.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.It is using palladium as catalyst activity component, and all the other are with embodiment 1.
Embodiment 7.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.Its catalyzer is that diameter is the spheroid that 0.2～15mm, the height right cylinder that is 0.3～30mm or diameter are 0.3～10mm.All the other are with embodiment 1.
Embodiment 8.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.The ratio that its precious metal accounts for carrier is 0.5～1%, and all the other are with embodiment 1.
Embodiment 9.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.Its reaction conditions is: the gauge pressure that pressure is 300kPa, temperature is 150 DEG C.All the other are with embodiment 1.
Embodiment 10.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.Its hydrogenolysis is to occur under the mixture atmosphere of pure hydrogen or hydrogen and other rare gas element, and rare gas element is nitrogen, and all the other are with embodiment 1.
Embodiment 11.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.Its its hydrogenolysis is to occur under the mixture atmosphere of pure hydrogen or hydrogen and other rare gas element, helium, and all the other are with embodiment 1.
Embodiment 12.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.Its hydrogen usage is 1.2 times of dichloro acetic acid molar weight, and the mol ratio of rare gas element and hydrogen is between 1, and all the other are with embodiment 1.
Embodiment 13.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.Its hydrogen usage is 8.0 times of dichloro acetic acid molar weight, and the mol ratio of rare gas element and hydrogen is between 5., all the other are with embodiment 1.
Embodiment 14.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.Its hydrogen usage is 3 times of dichloro acetic acid molar weight, and the mol ratio of rare gas element and hydrogen is between 3., all the other are with embodiment 1.
Embodiment 15.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.Its liquid phase is 1.5 hours in the residence time of beds, and all the other are with embodiment 1.
Embodiment 16.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.Its liquid phase is 5 hours in the residence time of beds, and all the other are with embodiment 1.
Embodiment 17.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.Its liquid phase is 3 hours in the residence time of beds, and all the other are with embodiment 1.
Embodiment 18.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.Its equipment and pipeline adopt the metallic substance zirconium material of inner liner polytetrafluoroethylene to make.All the other are with embodiment 1.
Embodiment 19.A kind of purposes of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.It is for the chlorated liquid containing Monochloro Acetic Acid 75-95%, dichloro acetic acid 0.5-6%, trichoroacetic acid(TCA) 0-3%, hydrochloric acid 1～3%, acetic acid 5～15%.All the other are with embodiment 1.Effect is fine.
Embodiment 20.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.In reactor, pack 0.8%Pd/C catalyzer into, it is the right cylinder of diameter 1mm, high 3mm, the high 16000mm of bed, and diameter 800mm, bed temperature is 171 DEG C, reactor pressure is 400kPa.Chlorated liquid and gas mixture are from reaction its top feed after preheating, and parallel flow is crossed bed, and the residence time of liquid phase is 2.5h, and hydrogen flowing quantity is that consumption is 8.91kg/h, and nitrogen flow is 9kg/h.Gas-liquid mixture goes out from reactor bottom, air inlet liquid/gas separator, and gas phase and liquid phase are carried out respectively subsequent disposal and recovery.Chlorated liquid composition sees attached list.When device operation 30h, dichloro acetic acid residue 0.03% in hydrogenolysis liquid, Monochloro Acetic Acid has reacted 1.7%.After operation 300h, dichloro acetic acid residue 0.06% in hydrogenolysis liquid, Monochloro Acetic Acid has reacted 1.3%, and in catalyzer, active principle content is 0.7%.
Embodiment 21.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.In reactor, pack 0.8%Pd/C catalyzer into, it is the right cylinder of diameter 1mm, high 3mm, the high 16000mm of bed, and diameter 800mm, bed temperature is 171 DEG C, reactor pressure is 400kPa.Chlorated liquid and gas mixture are from reaction its top feed after preheating, and parallel flow is crossed bed, and the residence time of liquid phase is 2.5h, and hydrogen flowing quantity is that consumption is 8.91kg/h, and nitrogen flow is 9kg/h.Gas-liquid mixture goes out from reactor bottom, air inlet liquid/gas separator, and gas phase and liquid phase are carried out respectively subsequent disposal and recovery.Chlorated liquid composition sees attached list.After device operation 300h, dichloro acetic acid residue 0.042% in hydrogenolysis liquid, Monochloro Acetic Acid has reacted 1.1%, and in catalyzer, active principle content is 0.7%.
Embodiment 22.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.In reactor, pack 0.8%Pd/C catalyzer into, it is the right cylinder of diameter 1mm, high 3mm, the high 16000mm of bed, and diameter 800mm, bed temperature is 171 DEG C, reactor pressure is 400kPa.Chlorated liquid and hydrogen are from reaction its top feed after preheating, and parallel flow is crossed bed, and the residence time of liquid phase is 2.5h, and hydrogen flowing quantity is that consumption is 17.91kg/h.Gas-liquid mixture goes out from reactor bottom, air inlet liquid/gas separator, and gas phase and liquid phase are carried out respectively subsequent disposal and recovery.Chlorated liquid composition sees attached list.When device operation 30h, dichloro acetic acid residue 0.4% in hydrogenolysis liquid, Monochloro Acetic Acid has reacted 3.1%.After operation 300h, dichloro acetic acid residue 1.0% in hydrogenolysis liquid, Monochloro Acetic Acid has reacted 2.7%, and in catalyzer, active principle content is 0.5%.
Embodiment 23.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.In reactor, pack 0.8%Pd/C catalyzer into, it is the right cylinder of diameter 1mm, high 3mm, the high 16000mm of bed, and diameter 800mm, bed temperature is 130 DEG C, reactor pressure is 800kPa.Chlorated liquid and gas mixture are from reaction its top feed after preheating, and parallel flow is crossed bed, and the residence time of liquid phase is 2.5h, and hydrogen flowing quantity is that consumption is 8.91kg/h, and nitrogen flow is 9kg/h.Gas-liquid mixture goes out from reactor bottom, air inlet liquid/gas separator, and gas phase and liquid phase are carried out respectively subsequent disposal and recovery.Chlorated liquid composition sees attached list.When device operation 30h, dichloro acetic acid residue 0.9% in hydrogenolysis liquid, Monochloro Acetic Acid has reacted 1.3%.After operation 300h, dichloro acetic acid residue 1.2% in hydrogenolysis liquid, Monochloro Acetic Acid has reacted 1.2%, and in catalyzer, active principle content is 0.7%.
Embodiment 24.A kind of method of purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production.In reactor, pack 0.8%Pd/C catalyzer into, it is the right cylinder of diameter 1mm, high 3mm, the high 16000mm of bed, and diameter 800mm, bed temperature is 171 DEG C, reactor pressure is 400kPa.Chlorated liquid and gas mixture are from reaction its top feed after preheating, and parallel flow is crossed bed, and the residence time of liquid phase is 2.5h, and hydrogen flowing quantity is that consumption is 16.3kg/h, and nitrogen flow is 17.9kg/h.Gas-liquid mixture goes out from reactor bottom, air inlet liquid/gas separator, and gas phase and liquid phase are carried out respectively subsequent disposal and recovery.Chlorated liquid composition sees attached list.When device operation 30h, dichloro acetic acid residue 0.01% in hydrogenolysis liquid, Monochloro Acetic Acid has reacted 6.2%.After operation 300h, dichloro acetic acid residue 0.02% in hydrogenolysis liquid, Monochloro Acetic Acid has reacted 5.1%, and in catalyzer, active principle content is 0.6%.
In embodiment 20-24, the proportion of composing of chlorated liquid is as following table:
Embodiment 1-24 is a kind of actual new catalytic hydrogenolysis technique of industry that is applicable to, under the atmosphere of nitrogen, hydrogen gas mixture, can greatly improve the removal effect of dichloro acetic acid and trichoroacetic acid(TCA), the inactivation trend of the processing efficiency of raising hydrogenation speed, dichloro acetic acid and product purity, reduction catalyzer and active lowering speed, Reaction time shorten, reduction hydrogen consumption, improve the yield of raw material availability and product, further increase economic efficiency.It can be widely used in the purification of Monochloro Acetic Acid in Monochloro Acetic Acid production.
Claims (1)
1. the method for a purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production, be included under certain temperature and pressure, process the mother liquor after acetic acid chlorination, described mother liquor is containing the chlorated liquid of Monochloro Acetic Acid 75-95%, dichloro acetic acid 0.5-6%, trichoroacetic acid(TCA) 0-3%, hydrochloric acid 1～3%, acetic acid 5～15%, characterized by further comprising following steps:
(1) in the catalyticreactor of inner liner polytetrafluoroethylene or zirconium material, device group VIII noble metals a kind of or its combine as hydrogenolysis catalyst bed, and the ratio that precious metal accounts for carrier is 0.5～1%;
(2) under the gauge pressure of 250～500kPa and under the temperature condition of 130～150 DEG C, make the chlorated liquid in Monochloro Acetic Acid production process flow through fixed bed, make hydrogen-nitrogen mixture gas and liquid phase simultaneously and flow to into bed;
(3) under the effect of beds, make whole in chlorated liquid or most many Mono Chloro Acetic Acids generation hydrogenolysis, produce Monochloro Acetic Acid;
(4) material is gone out to reactor, and through gas-liquid separation;
(5) by not containing or containing the how chloroacetic chlorated liquid liquid phase crystallization of minute quantity, washing, obtaining Monochloro Acetic Acid product after gas-liquid separation;
(6) by the gas phase after gas-liquid separation through condensation, absorption, separation, thereby recover hydrogen, hydrogenchloride and acetic acid;
Hydrogen usage is 1.5～5.0 times of dichloro acetic acid molar weight, and the mol ratio of rare gas element and hydrogen is between 2～3, and liquid phase is 2～4 hours in the residence time of beds; Catalyzer is that diameter is the spheroid that 0.2～15mm, the height right cylinder that is 0.3～30mm or diameter are 0.3～10mm; Support of the catalyst is that specific surface area is activated carbon, silicon-dioxide, aluminum oxide, float stone or the diatomite of 500～1350m2/g; Using palladium as catalyst activity component.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1124243A (en) * | 1994-12-05 | 1996-06-12 | 萨尔斯吉特建筑公司 | Preparation of monochloro acetic acid |
| CN1309115A (en) * | 2000-02-15 | 2001-08-22 | 大赛璐化学工业株式会社 | High purity monochloroacetic acid and preparing process thereof |
| CN101528657A (en) * | 2006-09-01 | 2009-09-09 | 布斯化工技术股份公司 | Manufacture of substantially pure monochloroacetic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1124243A (en) * | 1994-12-05 | 1996-06-12 | 萨尔斯吉特建筑公司 | Preparation of monochloro acetic acid |
| CN1309115A (en) * | 2000-02-15 | 2001-08-22 | 大赛璐化学工业株式会社 | High purity monochloroacetic acid and preparing process thereof |
| CN101528657A (en) * | 2006-09-01 | 2009-09-09 | 布斯化工技术股份公司 | Manufacture of substantially pure monochloroacetic acid |
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