CN103170371A - Catalyst for preparing chloroethylene by acetylene hydrochlorination - Google Patents
Catalyst for preparing chloroethylene by acetylene hydrochlorination Download PDFInfo
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- CN103170371A CN103170371A CN2011104316480A CN201110431648A CN103170371A CN 103170371 A CN103170371 A CN 103170371A CN 2011104316480 A CN2011104316480 A CN 2011104316480A CN 201110431648 A CN201110431648 A CN 201110431648A CN 103170371 A CN103170371 A CN 103170371A
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Abstract
The invention provides a mercury-free and precious metal-free catalyst used for preparing chloroethylene by acetylene gas phase hydrochlorination, and catalyst takes active carbon, graphite, graphene or carbon nano tube as a carbon carrier, and a reactive metal is loaded on the carbon carrier to prepare the catalyst, wherein a nitrogen carrier is obtained through loading organic nitrogen atoms and modifying.
Description
Technical field
The invention provides a kind ofly without mercury non precious metal acetylene hydrochlorination catalyst, be used for acetylene and hydrogen chloride gas precursor reactant synthesizing chloroethylene.
Background technology
Polyvinyl chloride (PVC) is one of five large thermoplastic synthetic resins, and its output and consumption figure occupy first of five large synthetic resin at home.The demand of national PVC in 2010 reaches 1,200 ten thousand tons according to statistics, and output reaches 1,128 ten thousand tons.VCM almost all (more than 98%) all be used for producing Corvic, remaining for the production of chlorinated polyvinyl chloride thing and chlorinated solvent.The technology level of producing VCM directly affects quality, production cost and the market competitiveness of Corvic.
Present stage is used for industrial vinyl chloride production and mainly contains two kinds of preparation technologies, and the one, carbide acetylene method, main production raw material is calcium carbide, coal and crude salt; The 2nd, ethylene process, primary raw material are oil.On the international market production of PVC is mainly take ethylene process as main, and the domestic resource limitation that is subjected to rich coal, oil-poor, weak breath, and mainly take carbide acetylene method as main, by in December, 2010, carbide acetylene method accounts for more than 80% of VC in China aggregated capacity.
Namely acetylene method hydrochlorinate method production of carbide acetylene method vinyl chloride has just been realized industrialization as far back as 1931.Its main flow process is that calcium carbide and water reaction generate acetylene, and acetylene and hcl reaction generate vinyl chloride, use catalyst to be generally the mercuric chleride catalyst that loads on active carbon.The conversion ratio of acetylene reaches more than 98%, vinyl chloride selectively can reach 96～99%.But mercuric chleride catalyst contains the mercury element of severe toxicity, and environmental requirement recent years is more and more stricter, and the mercury resource is also day by day deficient, and the exploitation of alternative catalysts has important economy and social value.
(Journal of Catalysis, 1968,11 (2): 113-130) make the catalyst activity component with metal chloride, SiO such as nineteen sixty-eight Smith
2Make carrier, prepared the catalyst of multiple acetylene gas solid phase hydrogen chlorination reaction with infusion process, at 181 ℃, normal pressure, C
2H
2: HCl=1: under 1.3 condition, find that the hydrochlorinate activity of metal chloride has following order:
Hg
2+＞Bi
3+＞Ni
2+＞Zn
2+＞Cd
2+＞Cu
2+＞Mn
2+＞Ca
2+
But, due to SiO
2Stronger surface acidity cause catalyst easily to produce polymerizate, and the carbon distribution of catalyst surface is serious.
The people such as Shinoda (Chemistry Letters, 1975,4 (3): 219-220.) at 200 ℃, C
2H
2: HCl=1: 1.03, air speed 150h
-1Under, the activity of 20 various metals chlorides/activated-carbon catalyst catalyzing acetylene hydrochlorination is studied, find that the metal ion with higher catalytic activity is: Pd
2+, Hg
2+, Cu
2+, Cu
+And Ag
+
The people such as Hutchings (Journal of catalysis, 1985,96 (1): 292-295) the hydrochlorination activity with catalyst is associated with the standard electrode potential of metal, draw an important conclusion: the standard electrode EMF of metal is higher, and the catalytic activity of reacting for acetylene hydrochlorination will be higher.
The people (CN102151580A) such as the Li Wei of University Of Tianjin on active carbon load Cu
3The P catalyst, its conversion of alkyne is up to 70%, and vinyl chloride selectively is up to 60%, catalytic activity and selectively having much room for improvement.And the phosphor-copper compound is bad at HCl atmosphere stability inferior.
The Deng Guocai of Nankai University etc. (polyvinyl chloride, 1994,6:5-9) a series of metal chloride catalyzing acetylene hydrochlorination activity are studied.Found that, reaction has very high activity to stannous chloride to acetylene hydrochlorination, and has prepared three component S nCl with better catalytic activity
2-BiCl
3-CuCl active carbon composite catalyst.At 140 ℃ of reaction temperatures, HCl: C
2H
2=1.05～1.1, acetylene air speed 30h
-1The time, catalyst life 120 hours; Acetylene air speed 12h
-1The time catalyst life reach 700 hours.But main active component stannous chloride is easy volatilization loss in course of reaction
The people such as the Wei Xiaobo of Tsing-Hua University (the process engineering journal, 2008,8 (6): 1218-1222) take secret salt as active component, SiO
2Be carrier, prepared the two component composite catalyst BiPO that are used for the catalyzing acetylene hydrochlorination
4-Cu
3(PO
4)
3/ SiO
2This catalyst reacts under 200 ℃, and its initial activity is 2/3 of industrial mercury catalyst, and in course of reaction, the catalyst surface area carbon ratio is more serious, and the losing issue of the salt in course of reaction and regenerative process waits to solve.
In addition, US Patent No. 1934324 reports are arranged, as reaction medium, acetylene and hydrochloric acid reaction can carry out at 20～65 ℃ with the copper chloride aqueous hydrochloric acid solution, and yield is near 70%.Although this yield is lower, it gives us a prompting, and hydrogen chloride form with hydrochloric acid in the aqueous solution exists and participates in reaction, and therefore, in reaction, proton hydrate or Cl-are more favourable.
Also have in addition a lot of researchs to concentrate on perhaps (Journal of Molcular CatalysisA:Chemisry above the center of the conduct such as the element that uses precious metals pt, Pd, Rh, Ru, Ag and Au, 2007,275:101-108. and Journal of Molcular CatalysisA:Chemistry, 2004,212:345-352.The Sichuan chemical industry, 2007,10:13-15 and CN101249451A, CN200910196849A).
The research of the modification aspect of a lot of active carbons has been arranged, main by nitric acid or hydrogen peroxide oxidation (Environmental Pollution and Control, 2010,18～22), nitric acid/sulfuric acid nitration, heat treatment, aniline surface aggregate (power technology Vol.32 (3):, 2007,614～616), alkali activation (coal conversion Vol.31 (8):, 2011,57～61), water activation, ammonia activation (ACTA Scientiae Circumstantiae Vol.34 (4):, 2001, Vol.21 (1): 74～78).Its research focuses mostly in surface functional group, specific area, pore structure etc. on (catalysis journal aspect the impact of specific catalytic reaction or absorption property, 2009, Vol.30 (6): 555～559. Coal dressings and comprehensive utilization, 2011, No.1:49～54).
In sum, the mercury chloride/activated-carbon catalyst of industrial extensive use due to severe toxicity and the shortage of resources of mercury, must be eliminated as early as possible.The research of non-mercury catalyst mainly concentrates on aspect, metal ion activity center, and the research aspect carrier also mainly concentrates on carrier specific area, pore structure and surface oxygen functional group to the aspect that affects of catalytic activity.Seldom have introducing the research that affects the aspect of organic nitrogen atom acetylene in gas phase hydrochlorination catalyst activity.
Summary of the invention
The object of the present invention is to provide a kind of without mercury non precious metal acetylene hydrochlorination preparing chloroethylene catalyst, by on the carrier carbon surface of catalyst by the mode of in-situ polymerization, at a large amount of nitrogen-atoms of carrier carbon surface introducing, and make this nitrogen-atoms contain lone pair electrons, with the activation of H-Cl covalent bond in assistance HCl gas, and then improve catalytic activity.
The present invention realizes by the following method:
The polymer with nitrogen monomers such as polymerization initiator and acrylonitrile, acrylamide, aniline are adsorbed onto respectively or simultaneously the carbon carrier surface, form the uncertain polymer of the degree of polymerization by initator polymerization or thermal polymerization.
Further, the carbon carrier that in-situ polymerization was processed is 100～850 ℃ of heat treatments more than 20 minutes, so that the further cyclisation of polymer, oxidation, the dehydrogenation on carbon carrier surface, take off part nitrogen or further polymerization.
Then one or more in load Ti, Zr, Fe, Co, Ni, Cu, Zn, Bi, Sn, Sb and Pb and complex compound thereof again on carbon carrier surface that load has a polymer with nitrogen.
Compared with the prior art, the present invention has following features:
1) introduced organic compounds containing nitrogen in the mode of in-situ polymerization on the carbon carrier surface of acetylene hydrochlorination preparing chloroethylene catalyst first.
2) compare with original acetylene hydrochlorination preparing chloroethylene catalyst carrier method of modifying, in-situ polymerization is processed carbon carrier, can introduce than the relatively large n of group that contains on the carbon carrier surface, and pollute few.Do not resemble with nitric acid or sulfuric acid treatment, can produce a large amount of acid waste water.
3) carbon carrier of processing with in-situ polymerization is as the acetylene hydrochlorination catalyst carrier, and after the load base-metal salt, catalytic activity significantly improves than the catalyst of processing without in-situ polymerization.
Catalyst of the present invention is answered on device at fixed bed and is estimated, and fixed bed reactors are the steel pipe of a long 1000mm of diameter 20mm, acetylene air speed 36h
-1, charging acetylene: HCl is 1: 1.1,180 ℃ of reaction temperatures, reaction pressure are normal pressure, loaded catalyst 40ml.Discharging gas is analyzed with gas-chromatography, and conversion of alkyne and chloro ethylene yield are all pressed the mol ratio of charging acetylene and calculated.
The specific embodiment
Concrete technical solution of the present invention now is described in conjunction with the embodiments.Following examples illustrate that just technical scheme of the present invention can reliable and effectively realize, but technical solution of the present invention is not limited in following examples.
Comparative Examples 1
Carbon carrier: active carbon, bulk density 0.38g/ml, BET specific area 1091m
2/ g, particle diameter 2.5mm, particle length 2～6mm.Measure this active carbon 40ml.
Active constituent: take CuCl
22H2O (chemical pure, molecular weight 170.48, content 99%) 2.70g is dissolved in approximately and obtains solution A in 30ml distilled water.
Catalyst: the aforementioned active carbon that will dry is poured in solution A, room temperature dipping 1h.Dry in baking oven.Then estimate with aforesaid evaluating apparatus.
Activity rating result: conversion of alkyne 42.2%, chloro ethylene yield 40.1%
Embodiment 1
Carbon carrier: active carbon, bulk density 0.38g/ml, BET specific area 1091m
2/ g, particle diameter 2.5mm, particle length 2～5mm.Measure this active carbon 40ml, with the 5g acrylonitrile, the 0.01g dibenzoyl peroxide is dissolved in the solution impregnation that 50ml ethanol obtains, and normal-temperature vacuum is removed ethanol, after placing 24h, dries 1h in 250 ℃ of air atmospheres.
Catalyst: the copper chloride solution 50ml of preparation 0.016mol, flood above-mentioned active carbon, oven dry.Then estimate with aforesaid evaluating apparatus.
Activity rating result: conversion of alkyne 67.7%, chloro ethylene yield 67.2%.
Embodiment 2
Carbon carrier: active carbon, bulk density 0.38g/ml, BET specific area 1091m
2/ g, particle diameter 2.5mm, particle length 2～5mm.Measure this active carbon 40ml, 50ml contains aniline salt acid solution dipping and the ammonium persulfate hydrochloric acid solution dipping of 0.02mol, static 5h in nitrogen atmosphere under room temperature, 50 ℃ of drying under reduced pressure.
Catalyst: the copper chloride solution 50ml of preparation 0.016mol, flood above-mentioned active carbon, oven dry.Then estimate with aforesaid evaluating apparatus.
Activity rating result: conversion of alkyne 60.5%, chloro ethylene yield 58.2%.
Embodiment 3.
Claims (4)
1. catalyst that is used for acetylene in gas phase hydrochlorinate preparing chloroethylene, it is comprised of as carbon carrier, the metallic element activated centre that is in the carbon carrier surface active carbon, graphite, Graphene or CNT, it is characterized in that: described carbon carrier carries out in-situ polymerization and obtains by one or more in acrylonitrile, acrylamide, aniline are loaded on active carbon, graphite, Graphene or CNT;
Described metallic element activated centre is one or more in Ti, Zr, Fe, Co, Ni, Cu, Zn, Bi, Sn, Sb and Pb and complex compound thereof.
2. the catalyst for acetylene in gas phase hydrochlorinate preparing chloroethylene according to claim 1 is characterized in that: described in-situ polymerization, adopt one or several in ammonium persulfate, potassium peroxydisulfate and dibenzoyl peroxide as initator.
3. the catalyst for acetylene in gas phase hydrochlorinate preparing chloroethylene according to claim 1, it is characterized in that: described carbon carrier heats by one or more in acrylonitrile, acrylamide, aniline are loaded on active carbon, graphite, Graphene or CNT, carries out the original position thermal polymerization and obtains.
4. according to claim 1～3 described catalyst for acetylene in gas phase hydrochlorinate preparing chloroethylene, it is characterized in that: described carbon carrier carries out in-situ polymerization by one or more in acrylonitrile, acrylamide, aniline are loaded on active carbon, graphite, Graphene or CNT, then is heated to 100～850 ℃ of heat treatment certain more than 20 minutes and obtain after polymerization is completed.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289254A (en) * | 2014-10-11 | 2015-01-21 | 中国科学院上海高等研究院 | Nitrogen-modified catalyst applied to preparation of vinyl chloride and preparation method of nitrogen-modified catalyst |
| CN104437565A (en) * | 2014-11-03 | 2015-03-25 | 扬州大学 | Method for preparing chloroethylene by reaction of chloroform and acetylene, and catalyst used in method |
| CN104437564A (en) * | 2014-11-03 | 2015-03-25 | 扬州大学 | Catalyst for environment-friendly catalytic production of chloroethylene and method for producing chloroethylene by using catalyst |
| CN104525256A (en) * | 2014-12-26 | 2015-04-22 | 中国科学院上海高等研究院 | Polypyrrole activated carbon catalyst and application thereof |
| CN104525257A (en) * | 2015-01-07 | 2015-04-22 | 中国科学院上海高等研究院 | Polypyrrole activated carbon catalyst and application thereof in vinyl chloride synthesis |
| CN106492851A (en) * | 2016-08-18 | 2017-03-15 | 刘金朝 | A kind of environmental protection low mercury catalyst and its preparation method and application |
| CN108511766A (en) * | 2018-04-24 | 2018-09-07 | 深圳大学 | A kind of bifunctional electrocatalyst and preparation method thereof |
| CN110142053A (en) * | 2019-05-28 | 2019-08-20 | 沈阳化工大学 | A kind of acetylene hydrochlorination synthesis vinyl chloride thereof catalyst without mercury preparation method |
| CN111744510A (en) * | 2019-03-28 | 2020-10-09 | 新疆大学 | Carbon nano tube mercury-free catalyst for acetylene hydrochlorination |
| CN111760577A (en) * | 2020-03-12 | 2020-10-13 | 榆林碳氢研究院股份有限公司 | Preparation method of catalyst with large specific surface area for preparing vinyl chloride by hydrochlorinating acetylene |
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| US3925247A (en) * | 1972-12-28 | 1975-12-09 | Onoda Cement Co Ltd | Method for preparing catalyst for the production of vinyl fluoride |
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2011
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| US3925247A (en) * | 1972-12-28 | 1975-12-09 | Onoda Cement Co Ltd | Method for preparing catalyst for the production of vinyl fluoride |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289254A (en) * | 2014-10-11 | 2015-01-21 | 中国科学院上海高等研究院 | Nitrogen-modified catalyst applied to preparation of vinyl chloride and preparation method of nitrogen-modified catalyst |
| CN104437565A (en) * | 2014-11-03 | 2015-03-25 | 扬州大学 | Method for preparing chloroethylene by reaction of chloroform and acetylene, and catalyst used in method |
| CN104437564A (en) * | 2014-11-03 | 2015-03-25 | 扬州大学 | Catalyst for environment-friendly catalytic production of chloroethylene and method for producing chloroethylene by using catalyst |
| CN104525256A (en) * | 2014-12-26 | 2015-04-22 | 中国科学院上海高等研究院 | Polypyrrole activated carbon catalyst and application thereof |
| CN104525256B (en) * | 2014-12-26 | 2017-02-01 | 中国科学院上海高等研究院 | Polypyrrole activated carbon catalyst and application thereof |
| CN104525257A (en) * | 2015-01-07 | 2015-04-22 | 中国科学院上海高等研究院 | Polypyrrole activated carbon catalyst and application thereof in vinyl chloride synthesis |
| CN106492851A (en) * | 2016-08-18 | 2017-03-15 | 刘金朝 | A kind of environmental protection low mercury catalyst and its preparation method and application |
| CN106492851B (en) * | 2016-08-18 | 2019-10-29 | 刘金朝 | A kind of environmental protection low mercury catalyst and its preparation method and application |
| CN108511766A (en) * | 2018-04-24 | 2018-09-07 | 深圳大学 | A kind of bifunctional electrocatalyst and preparation method thereof |
| CN108511766B (en) * | 2018-04-24 | 2020-07-14 | 深圳大学 | Bifunctional electrocatalyst and preparation method thereof |
| CN111744510A (en) * | 2019-03-28 | 2020-10-09 | 新疆大学 | Carbon nano tube mercury-free catalyst for acetylene hydrochlorination |
| CN110142053A (en) * | 2019-05-28 | 2019-08-20 | 沈阳化工大学 | A kind of acetylene hydrochlorination synthesis vinyl chloride thereof catalyst without mercury preparation method |
| CN111760577A (en) * | 2020-03-12 | 2020-10-13 | 榆林碳氢研究院股份有限公司 | Preparation method of catalyst with large specific surface area for preparing vinyl chloride by hydrochlorinating acetylene |
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Application publication date: 20130626 |