CN103551168A - Mercury-free catalyst applied to stationery bed for preparing chloroethylene and preparation method thereof - Google Patents
Mercury-free catalyst applied to stationery bed for preparing chloroethylene and preparation method thereof Download PDFInfo
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- CN103551168A CN103551168A CN201310549110.9A CN201310549110A CN103551168A CN 103551168 A CN103551168 A CN 103551168A CN 201310549110 A CN201310549110 A CN 201310549110A CN 103551168 A CN103551168 A CN 103551168A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 47
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 35
- 229910003803 Gold(III) chloride Inorganic materials 0.000 claims abstract description 19
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 claims abstract description 19
- 229940076131 gold trichloride Drugs 0.000 claims abstract description 19
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 17
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000007038 hydrochlorination reaction Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 61
- 239000003610 charcoal Substances 0.000 claims description 32
- 239000002250 absorbent Substances 0.000 claims description 27
- 230000002745 absorbent Effects 0.000 claims description 27
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 24
- 229910052753 mercury Inorganic materials 0.000 claims description 24
- 239000012065 filter cake Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 21
- 238000000967 suction filtration Methods 0.000 claims description 21
- 238000000151 deposition Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012752 auxiliary agent Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 5
- 239000010903 husk Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 229910001510 metal chloride Inorganic materials 0.000 abstract description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000010931 gold Substances 0.000 description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 244000060011 Cocos nucifera Species 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 3
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 3
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 101150116295 CAT2 gene Proteins 0.000 description 2
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 2
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 2
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 2
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- -1 gold ion Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical class SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Abstract
The invention provides a mercury-free catalyst applied to stationery bed for preparing chloroethylene and a preparation method thereof. The catalyst takes activated carbon, pretreated by hydrochloric acid or sodium hydroxide water solution, as a carrier, and gold trichloride and ferric chloride as active components, and compared with the ordinary mercury-free catalyst, according to the preparation method of the catalyst, the gold trichloride is guaranteed not to be reduced and can be uniformly and firmly loaded on the surface of the activated carbon carrier by replacing nitrohydrochloric acid in the preparation of the catalyst with hydrogen peroxide and taking other metal chloride, capable of promoting the decomposition of the hydrogen peroxide, as auxiliaries. The catalyst has high activity and selectivity in the reaction of preparing chloroethylene in the stationery bed through acetylene hydrochlorination, and the preparation method is simple and efficient, and green and environment-friendly, and has important practical significance in the industrial application.
Description
Technical field
The present invention proposes a kind of catalyst without mercury for fixed bed acetylene hydrochlorination synthesizing chloroethylene and preparation method thereof.It is carrier that this catalyst be take the pretreated active carbon of the aqueous solution of hydrochloric acid or NaOH, using gold trichloride and ferric trichloride jointly as active component, compare common catalyst without mercury, the preparation method of this catalyst replaces the chloroazotic acid in catalyst preparation with hydrogen peroxide, and using and can promote other metal chlorides of decomposing hydrogen dioxide solution as auxiliary agent, guarantee that gold trichloride is not reduced as far as possible, and can evenly load on securely carried by active carbon surface.This catalyst has very high activity and selective in the reaction of fixed bed preparing chloroethylene by acetylene hydrochlorination, and simple efficient, the environmental protection of preparation method, makes it in commercial Application, have important practical significance.
Background technology
Polyvinyl chloride is one of the world's five large-engineering plastics, is widely used in building, agricultural, the every field such as medical, and vinyl chloride is as the monomer of polyvinyl chloride, and its demand also constantly increases.Due to the energy resource structure of the oil-poor many coals of China, the main technique of the vinyl chloride of China's production is at present the hydrochlorinate of acetylene, is mainly to generate vinyl chloride by mercurous catalyst acetylene and hcl reaction.Along with the sharply decline of mercury storage level in recent years, and the pressure of Environmental security aspect, acetylene hydrochlorination used catalyst go mercuration imperative.
The security and the feature of environmental protection problem that due to mercury catalyst, in preparation and use procedure, exist are long-standing, have had a large amount of research for vinyl chloride catalyst without mercury at present.Nankai University Deng state just waits people to study to using the chloride of the common metals such as stannic chloride as the catalyst without mercury of active component, although that catalyst has is higher active and selective, the losing issue of active component is difficult to solve, and commercial Application difficulty is larger; The people such as the professor Hutchings of Britain Cardiff University have studied take the catalyst that the noble metals such as gold, palladium, platinum are active component, research shows to be still faced with severe loss of active component problem in the noble metal catalyst reactions such as palladium, platinum, and Au catalyst has shown excellent Activity and stabill.The research of current domestic acetylene hydrochlorination catalyst without mercury is mainly also to carry out for Au catalyst.
The people's such as professor Hutchings research (Journal ofcatalysis, 1991,128:366-377) show, what in Au catalyst, play catalytic action is mainly trivalent gold ion.In the patent CN101735005A of Johnson Matty Public Limited Co, also mention that " prior art shows metallic gold (Au
0) as catalyst, be inactive ".Therefore gold is with Au
3+state evenly effectively to load on carrier surface be the assurance that catalyst has greater activity and stability.According to the people's such as professor Hutchings research (Journal of catalysis, 2012,297:128-136) show, in catalyst preparation process, the membership that adds of chloroazotic acid hinders Au in dipping process
3+in the reduction of catalyst surface, obviously improve catalyst surface Au
3+with Au
0ratio in Au
3+proportion, and can activate Au
3+with the avtive spot of carrier junction, thereby obviously improve the activity of catalyst.
Chloroazotic acid has important effect to improving the Activity and stabill of catalyst, but the introducing of chloroazotic acid is higher to the equipment requirement in catalyst preparation process, and chloroazotic acid danger is larger, has increased the difficulty of catalyst in industrial production.
Current domestic existence is in a large number for take the research of the catalyst that gold is main active component.Patent CN201110134609.4 and patent CN201110134607.5 have all announced catalyst without mercury of a kind of acetylene hydrochlorination preparing chloroethylene and preparation method thereof, but there iing bigger difference with this patent aspect catalyst formulation and preparation method, especially in preparation method, it still adopts chloroazotic acid as primary solvent.Patent CN201210100688.1 has announced a kind of catalyst without mercury, and four thiocyanic acids of mainly take close potassium aurate as main active component, and catalyst formulation and this patent have bigger difference.Patent CN201110150287.2 has announced a kind of preparation method of catalyst, and mainly with ultrasonic assistant soakage, preparation method and this patent have relatively big difference.In patent CN201110257697.7, announced catalyst without mercury and preparation method thereof, although mentioning employing hydrogen peroxide aspect carrier pretreatment, but this patent is to adopt in catalyst preparation, and utilize the interaction of active component and auxiliary agent and hydrogen peroxide to improve catalyst property, and it take palladium as main active component, from different described in this patent.
Summary of the invention
Based on above background, the present invention proposes a kind of catalyst without mercury for fixed bed acetylene hydrochlorination synthesizing chloroethylene and preparation method thereof.Main innovate point of the present invention is, with the aqueous solution of hydrochloric acid or NaOH, absorbent charcoal carrier is carried out to pretreatment; Adopt gold trichloride and ferric trichloride composite active center; The hydrogen peroxide of the employing environmental protection of novelty replaces the chloroazotic acid using in traditional catalyst preparation process simultaneously; Feature for this catalyst has adopted brand-new preparation technology; And this catalyst is had and the equal even higher catalytic activity of the catalyst without mercury that uses chloroazotic acid to prepare, thereby obtain a kind of catalyst without mercury of environment-friendly high-efficiency.
Concrete technical scheme of the present invention is as described below:
1. for a preparation method for the catalyst without mercury of fixed bed acetylene hydrochlorination synthesizing chloroethylene, it is characterized in that comprising following steps:
(1) pretreatment of absorbent charcoal carrier: it is in 1%～10% hydrochloric acid solution that auxiliary agent is joined to mass concentration, under room temperature condition, stir 1 hour, obtain the hydrochloric acid solution A containing auxiliary agent, add afterwards absorbent charcoal carrier, at 30～50 ℃ of temperature, standing airtight depositing more than 24 hours, then by the mixture suction filtration, the separation that obtain, afterwards gained filter cake is dried, obtain pretreated carrier B; Wherein adding quality containing the hydrochloric acid solution A of auxiliary agent is 2.5～5 times of absorbent charcoal carrier total suction;
(2) uploading of active component: under stirring at room condition, gold trichloride and ferric trichloride are dissolved in deionized water simultaneously, obtain solution C after fully dissolving; The hydrogen peroxide solution that is 5%～15% by mass concentration slowly joins in pretreated carrier B, slowly add afterwards solution C, liquid to be mixed stops after boiling, standing airtight depositing 24～48 hours, afterwards by sample suction filtration, separation, then gained filter cake is dried, obtain required catalyst without mercury; The quality that wherein adds hydrogen peroxide solution is 2 times of absorbent charcoal carrier total suction, and the quality of the solution C adding is 1～3 times of absorbent charcoal carrier total suction.
2. for a preparation method for the catalyst without mercury of fixed bed acetylene hydrochlorination synthesizing chloroethylene, it is characterized in that comprising following steps:
(1) pretreatment of absorbent charcoal carrier: it is in 1%～5% sodium hydrate aqueous solution that absorbent charcoal carrier is joined to mass concentration, be warming up to afterwards 60～80 ℃ of reactions 2 hours, then by mixture suction filtration, separation and be washed to neutrality, afterwards gained filter cake is dried, obtain pretreated carrier A; The quality that wherein adds sodium hydrate aqueous solution is 2.5～5 times of absorbent charcoal carrier total suction;
(2) uploading of auxiliary agent: under stirring at room condition, auxiliary agent is dissolved in deionized water, then dropwise add concentrated hydrochloric acid, make the pH value of compounding agent solution in 2～5 scopes, join afterwards in pretreated carrier A, standing airtight depositing 24～48 hours, then by mixture suction filtration, separation, afterwards gained filter cake is dried, obtain pretreated carrier B; Wherein the quality of compounding agent solution is 2.5～5 times of absorbent charcoal carrier total suction;
(3) uploading of active component: under stirring at room condition, gold trichloride and ferric trichloride are dissolved in deionized water, obtain solution C after fully dissolving; The hydrogen peroxide solution that is 5%～15% by mass concentration slowly joins in pretreated carrier B, slowly add afterwards solution C, liquid to be mixed stops after boiling, standing airtight depositing 24～48 hours, afterwards by sample suction filtration, separation, then gained filter cake is dried, obtain required catalyst without mercury; The quality that wherein adds hydrogen peroxide solution is 2 times of absorbent charcoal carrier total suction, and the quality of the solution C adding is 1～3 times of absorbent charcoal carrier total suction.
Compare with existing known Catalysts and its preparation method, the present invention has following significantly innovation:
(1) aqueous solution with hydrochloric acid or NaOH carries out pretreatment to absorbent charcoal carrier.By can reduce functional group and the foreign metal ion that is unfavorable for this reaction in carrier to the pretreatment of carrier, thereby can effectively improve activity and the stability of golden series catalysts.
(2) adopt gold trichloride and ferric trichloride composite active center.The present invention adopts gold trichloride and ferric trichloride jointly as the activated centre of catalyst, can improve to greatest extent the two synergy in this catalyst; Ferric trichloride add adsorption reaction thing molecule more effectively, thereby improve catalytic activity and stability.Its effect is much better than take the catalyst of gold trichloride as single-activity center.
(3) adopt hydrogen peroxide as the solvent of active component.Hydrogen peroxide is as a kind of strong oxidizer, and its oxidation susceptibility guarantees that chlorauride is not reduced by the reproducibility group of carrier surface in preparation process, to greatest extent with Au
3+state load on carrier surface.When the hydrogen peroxide solution of chlorauride mixes with pretreatment carrier, under pretreatment carrier and the promoter effect uploaded, hydrogen peroxide decomposes rapidly, and a large amount of heat releases, make solution in fluidized state, and carrier is acutely rolled in the mixture of solution and carrier.This process can make active component load on equably activated carbon surface, and high temperature is conducive to the interaction of active component and carrier surface more.
(4) feature for this catalyst has adopted brand-new preparation technology.The method that adopts step impregnation, making has the chloride of catalytic action to be first uploaded at carrier surface to the decomposition of hydrogen peroxide.When hydrogen peroxide solution mixes with pretreatment carrier, the carrier of having uploaded auxiliary agent can make hydrogen peroxide decompose rapidly, makes solution reach fluidized state, make active component evenly, firmly load on carrier table and.And iron chloride and chlorauride add jointly, not only two kinds of active components can play good synergy to catalytic reaction, and can make hydrogen peroxide decompose in the best opportunity, better guarantee Au
3+existence, greatly improve the catalytic effect of catalyst.Through lot of experimental data, show, given iron chloride and the ratio of chlorauride can be considered economy and the effectiveness of catalyst preferably.
(5), as described in concrete technical scheme 1, when carrier pretreatment, adopt the pickling of carrier and the step of uploading of active component to carry out.Through experimental data, prove, this method can not only reduce the operating process in preparation process, and can make auxiliary agent better load on carrier surface, contributes to the lifting of catalyst activity.
(6), as described in concrete technical scheme 2, adopt sodium hydroxide solution to remove Na, K and to the great Si of catalyst toxicity.After carrier pretreatment, by salt acid for adjusting pH value, through experiment showed, that too low pH value is unfavorable for the decomposition of hydrogen peroxide; And when pH value is too high, easily cause the violent decomposition of hydrogen peroxide, there is potential safety hazard; Decomposing hydrogen dioxide solution speed under this pH value be beneficial to most gold on carrier load evenly firmly.And in whole preparation process, avoided using chloroazotic acid and a large amount of hydrochloric acid solutions, make whole process environmental protection, and danger has reduced greatly.
The specific embodiment
For this patent is described better, now list following examples.Following examples are in order to make industry personnel understand in more detail the present invention; or content according to the present invention is made some nonessential improvement and adjustment; but illustrated embodiment is not as a limitation of the invention, is contained in but does not comprise all claim protection domains.
Embodiment 1:
(1) pretreatment of carrier: it is in 5% hydrochloric acid solution that 0.3g cobalt chloride is dissolved in to 50g mass concentration, stirs 1 hour under room temperature condition, obtains the hydrochloric acid solution (a) of chloride containing cobalt; Afterwards 9g coconut husk charcoal carrier is joined in solution (a); At 50 ℃ of temperature, standing airtight depositing 24 hours, then by mixture suction filtration, separation, afterwards by gained filter cake 130 ℃ of oven dry, obtain carrier A after pretreatment;
(2) uploading of active component: under stirring at room condition, 0.01g gold trichloride and 0.05g ferric trichloride are dissolved in 20g deionized water, obtain solution (b) after fully dissolving; The hydrogen peroxide solution that is 5% by 20g mass concentration slowly joins after pretreatment in carrier A, slowly add afterwards solution (b), solution to be mixed stops after boiling, standing airtight depositing 24 hours, afterwards by mixture suction filtration, separation, then by gained filter cake 130 ℃ of oven dry, obtain required catalyst, be numbered Cat-1.
Embodiment 2:
(1) pretreatment of carrier: it is in 5% sodium hydroxide solution that 9g absorbent charcoal carrier is joined to 50g mass concentration, obtains the mixture (a) of carrier and solution; 60 ℃ of reactions 2 hours, then by mixture suction filtration, separation and be washed to neutrality, afterwards by gained filter cake 130 ℃ of oven dry, obtain carrier A after pretreatment;
(2) uploading of auxiliary agent: under stirring at room condition, 1g copper chloride is dissolved in 30g deionized water, then dropwise adds concentrated hydrochloric acid, making compounding agent solution pH value is 2, obtains certain density solution (b); Afterwards solution (b) is joined after pretreatment in carrier A, standing airtight depositing 24 hours, afterwards by mixture suction filtration, separation, 130 ℃ of oven dry, obtains carrier B after pretreatment by gained filter cake;
(3) uploading of active component: under stirring at room condition, 0.01g gold trichloride and 0.05g ferric trichloride are dissolved in 20g deionized water, obtain solution (c) after fully dissolving; The hydrogen peroxide solution that is 15% by 20g mass concentration slowly joins after pretreatment in carrier B, slowly add afterwards solution (c), solution to be mixed stops after boiling, standing airtight depositing 24 hours, afterwards by mixture suction filtration, separation, then by gained filter cake 130 ℃ of oven dry, obtain required catalyst, be numbered Cat-2.
Embodiment 3:
(1) pretreatment of carrier: it is in 5% hydrochloric acid solution that 0.3g ruthenium trichloride is dissolved in to 50g mass concentration, stirs 1 hour under room temperature condition, obtains the hydrochloric acid solution (a) containing ruthenium trichloride; , afterwards 9g coconut husk charcoal carrier is joined in solution (a); At 50 ℃ of temperature, standing airtight depositing 24 hours, then by mixture suction filtration, separation, afterwards by gained filter cake 130 ℃ of oven dry, obtain carrier A after pretreatment;
(2) uploading of active component: under stirring at room condition, 0.002g gold trichloride and 0.005g ferric trichloride are dissolved in 20g deionized water, obtain solution (b); The hydrogen peroxide solution that is 10% by 20g mass concentration slowly joins after pretreatment in carrier A, slowly add afterwards solution (b), solution to be mixed stops after boiling, standing airtight depositing 48 hours, afterwards by mixture suction filtration, separation, then by gained filter cake 130 ℃ of oven dry, obtain required catalyst, be numbered Cat-3.
Comparative example 1:
Object is to compare with embodiment 2, by contrast, draws the active impact of NaOH pretreatment carrier on catalyst.
Preparation process is identical with embodiment 2, only changing in embodiment 2 carrier pretreatment " it is in 5% sodium hydroxide solution that 9g absorbent charcoal carrier is joined to 50g mass concentration " is " 9g absorbent charcoal carrier is joined in 50g deionized water ", and gained catalyst is numbered Cat-4.
Comparative example 2:
Object is to compare with embodiment 1, by contrast, draws with FeCl
3as auxiliary agent and with FeCl
3impact as common activated centre on catalyst activity.
(1) pretreatment of carrier: it is in 5% hydrochloric acid solution that 0.3g cobalt chloride and 0.05g ferric trichloride are dissolved in to 50g mass concentration simultaneously, stirs 1 hour under room temperature condition, obtains solution (a); Afterwards 9g coconut husk charcoal carrier is joined in solution (a); At 50 ℃ of temperature, standing airtight depositing 24 hours, then by mixture suction filtration, separation, afterwards by gained filter cake 130 ℃ of oven dry, obtain carrier A after pretreatment;
(2) uploading of active component: under stirring at room condition, 0.01g gold trichloride is dissolved in 20g deionized water, obtains solution (b) after fully dissolving; The hydrogen peroxide solution that is 5% by 20g mass concentration slowly joins after pretreatment in carrier A, slowly add afterwards solution (b), solution to be mixed stops after boiling, standing airtight depositing 24 hours, afterwards by mixture suction filtration, separation, then by gained filter cake 130 ℃ of oven dry, obtain required catalyst, be numbered Cat-5.
Comparative example 3:
Object is to contrast with embodiment 1, draws the whether impact on catalyst activity of use of hydrogen peroxide by contrast.
(1) pretreatment of carrier: it is in 5% hydrochloric acid solution that 0.3g cobalt chloride is dissolved in to 50g mass concentration, stirs 1 hour under room temperature condition, obtains the hydrochloric acid solution (a) of chloride containing cobalt; Afterwards 9g coconut husk charcoal carrier is joined in solution (a); At 50 ℃ of temperature, standing airtight depositing 24 hours, then by mixture suction filtration, separation, afterwards by gained filter cake 130 ℃ of oven dry, obtain carrier A after pretreatment;
(2) uploading of active component: under stirring at room condition, 0.01g gold trichloride and 0.05g ferric trichloride are dissolved in 20g deionized water, obtain solution (b) after fully dissolving; 20g deionized water is slowly joined after pretreatment in carrier A, slowly add afterwards solution (b), by standing airtight the depositing 24 hours of gained sample, afterwards by mixture suction filtration, separation, then by gained filter cake 130 ℃ of oven dry, obtain required catalyst, be numbered Cat-6.
The activity rating result of Cat-1 to Cat-6 catalyst.Evaluating catalyst condition: fixed bed reactors, acetylene air speed 120h
-1, hydrogen chloride and acetylene molar ratio are 1.05, and catalyst activates 2 hours before using under 180 ℃ of hydrogen chloride atmosphere, and catalyst reaction temperatures is 180 ℃.
| Catalyst numbering | Cat-1 | Cat-2 | Cat-3 | Cat-4 | Cat-5 | Cat-6 |
| Acetylene conversion ratio (%) | 99.2 | 98.5 | 93.0 | 97.2 | 98.5 | 95.1 |
| Vinyl chloride selective (%) | 99.7 | 99.6 | 98.2 | 99.5 | 99.6 | 99.3 |
Claims (4)
1. for a catalyst without mercury for fixed bed acetylene hydrochlorination synthesizing chloroethylene, it is characterized in that: the pretreated active carbon of the aqueous solution of hydrochloric acid or NaOH of take is carrier; Take gold trichloride and ferric trichloride as active component, and its content accounts for 0.05%～1% of catalyst gross mass; One or more of take in cobalt chloride, copper chloride, ruthenium trichloride are auxiliary agent, and its content accounts for 3%～10% of catalyst gross mass; Wherein the active carbon as carrier is that specific area is greater than 900m
2coconut husk charcoal or the spherical activated charcoal of/g; The mol ratio of gold trichloride and ferric trichloride is x:1-x, and wherein x is 0.05～0.5.
2. a preparation method for catalyst without mercury described in claim 1, is characterized in that comprising following steps:
(1) pretreatment of absorbent charcoal carrier: it is in 1%～10% hydrochloric acid solution that auxiliary agent is joined to mass concentration, under room temperature condition, stir 1 hour, obtain the hydrochloric acid solution A containing auxiliary agent, add afterwards absorbent charcoal carrier, at 30～50 ℃ of temperature, standing airtight depositing more than 24 hours, then by the mixture suction filtration, the separation that obtain, afterwards gained filter cake is dried, obtain pretreated carrier B; Wherein adding quality containing the hydrochloric acid solution A of auxiliary agent is 2.5～5 times of absorbent charcoal carrier total suction;
(2) uploading of active component: under stirring at room condition, gold trichloride and ferric trichloride are dissolved in deionized water simultaneously, obtain solution C after fully dissolving; The hydrogen peroxide solution that is 5%～15% by mass concentration slowly joins in pretreated carrier B, slowly add afterwards solution C, liquid to be mixed stops after boiling, standing airtight depositing 24～48 hours, afterwards by sample suction filtration, separation, then gained filter cake is dried, obtain required catalyst without mercury; The quality that wherein adds hydrogen peroxide solution is 2 times of absorbent charcoal carrier total suction, and the quality of the solution C adding is 1～3 times of absorbent charcoal carrier total suction.
3. a preparation method for catalyst without mercury described in claim 1, is characterized in that comprising following steps:
(1) pretreatment of absorbent charcoal carrier: it is in 1%～5% sodium hydrate aqueous solution that absorbent charcoal carrier is joined to mass concentration, be warming up to afterwards 60～80 ℃ of reactions 2 hours, then by mixture suction filtration, separation and be washed to neutrality, afterwards gained filter cake is dried, obtain pretreated carrier A; The quality that wherein adds sodium hydrate aqueous solution is 2.5～5 times of absorbent charcoal carrier total suction;
(2) uploading of auxiliary agent: under stirring at room condition, auxiliary agent is dissolved in deionized water, then dropwise add concentrated hydrochloric acid, make the pH value of compounding agent solution in 2～5 scopes, join afterwards in pretreated carrier A, standing airtight depositing 24～48 hours, then by mixture suction filtration, separation, afterwards gained filter cake is dried, obtain pretreated carrier B; Wherein the quality of compounding agent solution is 2.5～5 times of absorbent charcoal carrier total suction;
(3) uploading of active component: under stirring at room condition, gold trichloride and ferric trichloride are dissolved in deionized water, obtain solution C after fully dissolving; The hydrogen peroxide solution that is 5%～15% by mass concentration slowly joins in pretreated carrier B, slowly add afterwards solution C, liquid to be mixed stops after boiling, standing airtight depositing 24～48 hours, afterwards by sample suction filtration, separation, then gained filter cake is dried, obtain required catalyst without mercury; The quality that wherein adds hydrogen peroxide solution is 2 times of absorbent charcoal carrier total suction, and the quality of the solution C adding is 1～3 times of absorbent charcoal carrier total suction.
4. a using method for catalyst described in claim 1, is characterized in that this catalyst without mercury is applied in fixed bed reactors, before use, need under 150 ℃ of-180 ℃ of hydrogen chloride atmosphere, activate 2 hours; Catalyst serviceability temperature scope is 110～200 ℃.
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| CN104289247A (en) * | 2014-10-11 | 2015-01-21 | 中国科学院上海高等研究院 | Catalyst applied to preparation of vinyl chloride by catalytic cracking of 1,2-dichloroethane as well as preparation method and application of catalyst |
| CN105080574A (en) * | 2014-12-02 | 2015-11-25 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Highly acidic multi-component composite catalyst for acetylene hydrochlorination |
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| CN107185533A (en) * | 2017-05-19 | 2017-09-22 | 新疆中泰化学股份有限公司 | Induction period controllable VCM synthesis Au-based catalyst and preparation method thereof |
| CN108295876A (en) * | 2018-01-30 | 2018-07-20 | 浙江工业大学 | A kind of preparation method of low-mercury catalyst and application |
| CN111774094A (en) * | 2019-04-03 | 2020-10-16 | 南开大学 | A kind of copper-based mercury-free catalyst for producing vinyl chloride by calcium carbide method and preparation and use method thereof |
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