CN102921473A - Novel nitrogen-modified carbon catalyst carrier and preparation method and use thereof - Google Patents
Novel nitrogen-modified carbon catalyst carrier and preparation method and use thereof Download PDFInfo
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- CN102921473A CN102921473A CN2012103666392A CN201210366639A CN102921473A CN 102921473 A CN102921473 A CN 102921473A CN 2012103666392 A CN2012103666392 A CN 2012103666392A CN 201210366639 A CN201210366639 A CN 201210366639A CN 102921473 A CN102921473 A CN 102921473A
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Abstract
The invention relates to a novel nitrogen-modified carbon catalyst carrier and a preparation method and use thereof. The nitrogen-modified carbon carrier is made by using commercial carbon materials (common active carbon, spherical active carbon, carbon nanotubes and the like) as raw materials and tripolycyanamide or urea as a modifier and by an impregnation method and a secondary activation method. The nitrogen-modified carbon material can be used in an acetylene hydrochlorination reaction as a catalyst carrier; when a catalyst is loaded onto the carrier under conditions of an air speed of acetylene of 30-180h<-1>, a temperature of 140 to 180 DEG C, and a ratio of n(HCL) to n(C2H2) equal to 1.05 to 1.15, the initial conversation rate is 20 to 300 percent higher than that of non-modified samples, the selectivity is near 100 percent and the catalytic performance is improved obviously.
Description
Technical field
The present invention relates to a kind of acetylene hydrochlorination catalytic reaction agent carrier and its preparation method and application, relate in particular to a kind of high selectivity nitrogen carbon modified material catalyst carrier and its preparation method and application that has.
Background technology
Along with the development of national economy and the day by day raising of living standards of the people, the demand of PVC (polyvinyl chloride) is increasing.PVC is obtained by VCM (VCM) polymerization, and the production method of VCM mainly contains ethylene process technique, ethane method technique and acetylene method technique.Because the resource distribution situation of China, all very shortage and price are very high always for unstripped gas ethene, and the petrochemical industry resource is day by day exhausted, and just coal provides raw material and price advantage for China has in a large number cheaply for this, so China is fit to take the acetylene method route as the main VCM of production.Therefore in the west area, such as the area of the rich coal resources such as Xinjiang, Inner Mongol, it is rapid that carbide newly-built or enlarging is produced the Corvic project development.It also is that fatal bottleneck problem is the mercuric chleride catalyst of synthesizing chloroethylene monomer (VCM) that present restriction acetylene method becomes the unique of Green Chemistry, the main active ingredient of this catalyst is mercury chloride, the mercury loss that easily distils is that carbide is produced the severe contamination source in the polyvinyl chloride.1 ton of PVC of the every production of carbide technique will consume about 1.4 kilograms of mercury, according to statistics, 2008 in the world the carbide total amount of producing PVC be 3,809 ten thousand tons, the amount of calculating according to this required mercury is about 5.333 ten thousand tons.Mercury is a heavy metal species in addition, severe toxicity is arranged, toxigenous concentration is 0.01～0.1mg/l, and can not be degraded by microorganisms, can only be with different valence states, Transport And Transformation between water, substrate and biology, occur to disperse and enrichment, enter and be difficult to again metabolism behind the human body and go out, be gathered in liver, kidney and the brain, the infringement nervous system has caused fearful " minamata disease ".It is predicted that the consumption mercury amount that acetylene method in 2014 is produced polyvinyl chloride resin can reach 17.5489 ten thousand tons, mercury is also because of its potential significant damage receive much concern [1].What therefore need to be resolved hurrily at present is to contain the pollution problem that mercury catalyst causes.Chinese scholars has been studied multiple low mercury, catalyst without mercury at present for this problem, and wherein the Au catalyst has obtained paying close attention to widely.
Absorbent charcoal material is prepared high-quality porous adsorbent after the PROCESS FOR TREATMENT such as the charing of carbonaceous material process, activation.Because the characteristics such as the huge specific area of absorbent charcoal material, enough chemical stability and mechanical strength, excellent acidproof, alkaline-resisting, heat resistance, the easy regeneration of user are so it is widely used in the fields such as food, medicine, industry, agricultural, health, military affairs.Different purposes for absorbent charcoal material are carried out the existing relevant report of special modification to it, Liu Xiaojun [Liu Xiaojun, Zhan Liang, Liang Xiao is pleased, Qiao Wenming, Ling Licheng. and the Chinese science and technology paper is online, 2009,4 (12): 893-899.] etc. when the preparation spherical activated charcoal, use melamine as modifier, introduced nitrogenous, oxygen-containing functional group, enriched the surface chemical property of spherical activated charcoal.The mass fraction of the nitrogen element that obtains can be up to 5.4%, and main existence form is pyrroles and pyridines nitrogen.Liu Zhichang [] etc. has added the pore-foaming agent ferrocene in the preparation of bitumen ball, and uses the spherical activated charcoal for preparing to VB
12Done the research of absorption property.Experiment shows that the metallic in the ferrocene can produce catalytic action to water and pitch, thereby plays the effect of expansion duct and development central hole structure when activation.And the increase that central hole structure distributes can the Effective Raise spherical activated charcoal absorption property.Find that by research prepared spherical activated charcoal has extraordinary adsorption capacity to VB12, adsorbance and adsorption rate all increase to some extent.
Reaction has extremely excellent catalytic activity to nitrogen carbon modified material for acetylene hydrochlorination as catalyst carrier in sum, but up to the present, does not also have the relevant report about nitrogen carbon modified material catalyst carrier.The present invention relates to a kind of novel nitrogen carbon modified material catalyst carrier.
Summary of the invention
The object of the present invention is to provide a kind of novel nitrogen carbon modified material catalyst carrier and its preparation method and application, and this catalyst carrier is for the conversion ratio of acetylene hydrochlorination reaction and selectively all very high.
Technical scheme of the present invention may further comprise the steps:
1. the preparation of catalyst carrier:
The material with carbon element (granular active carbon, spherical activated charcoal, CNT etc.) for preparing is mixed with modifier (melamine or urea) by a certain percentage; add a certain amount of deionized water; at 85 ℃ of lower dipping 24h; put into vacuum tube furnace after the drying; under nitrogen protection, be warming up to 700-900 ℃ with 5 ℃/min; be cooled to and put into deionized water after the room temperature and boil 1h, can use after the drying.
2. the application of catalyst carrier: carrier is joined in the catalyst solution that configures, constantly stir, at 80 ℃ of lower dipping 10h, water bath method, for subsequent use at 120 ℃ of lower dry 12h.
Acetylene hydrochlorination reaction is carried out in internal diameter is the stainless steel fixed bed reactors of 10mm, loaded catalyst is 4～8mL, acetylene and hydrogen chloride pressure all are 0.1MPa, acetylene: hydrogen chloride (mol ratio)=1～1.2, and acetylene gas at first removes moisture by the drier that silica gel is housed; The hydrogen chloride gas warp
The molecular sieve adsorption post is dry.Remove moisture and air in the system with nitrogen blowing before the reaction, after then passing into first hydrogen chloride gas and activating 0.5h, pass into again acetylene gas and react.Gas flow is controlled with mass flowmenter.Product is carried out chromatography after removing hydrogen chloride gas with the sodium hydroxide solution absorption.
The specific embodiment
Embodiment 1:
1. the preparation of catalyst carrier:
Use commercially available spherical activated charcoal to mix with melamine in 1: 0.8 ratio; add a certain amount of deionized water; at 85 ℃ of lower dipping 24h; put into vacuum tube furnace after the drying; under nitrogen protection, be warming up to 750 ℃ with 5 ℃/min; be cooled to and put into deionized water after the room temperature and boil 1h, can use after the drying.
2. the application of catalyst carrier: the modified spherical active carbon is joined in the mercuric chloride solution that configures, constantly stir, at 80 ℃ of lower dipping 10h, water bath method, for subsequent use at 120 ℃ of lower dry 12h.
Acetylene hydrochlorination reaction is carried out in internal diameter is the stainless steel fixed bed reactors of 10mm, loaded catalyst is 4～8mL, acetylene and hydrogen chloride pressure all are 0.1MPa, acetylene: hydrogen chloride (mol ratio)=1～1.2, and acetylene gas at first removes moisture by the drier that silica gel is housed; The hydrogen chloride gas warp
The molecular sieve adsorption post is dry.Remove moisture and air in the system with nitrogen blowing before the reaction, after then passing into first hydrogen chloride gas and activating 0.5h, pass into again acetylene gas and react.Gas flow is controlled with mass flowmenter.Product is carried out chromatography after removing hydrogen chloride gas with the sodium hydroxide solution absorption.
Claims (3)
1. nitrogen carbon modified material catalyst carrier, it is mainly take commercially available various material with carbon elements (common active carbon, spherical activated charcoal, CNT etc.) as raw material, take melamine or urea as modifier, adopt the standby nitrogen carbon modified material that obtains of infusion process and re-activation legal system.The nitrogen content of nitrogen carbon modified material is 3%-8%.
2. nitrogen carbon modified material catalyst carrier according to claim 1 is characterized in that the preparation method of catalyst carrier may further comprise the steps:
3. the according to claim 1 application of described catalyst carrier, it is characterized in that this nitrogen carbon modified material is applied in the acetylene hydrochlorination reaction as catalyst carrier, when supported catalyst, acetylene air speed 30-180h-1, temperature 140-180 ℃, n (HCl): n (C2H2)=1.05～1.1 o'clock, its initial conversion improves 20%-300% than unmodified sample, selectively near 100%.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103157499A (en) * | 2013-03-29 | 2013-06-19 | 石河子大学 | Preparation of novel nitrogen modified Au/N-AC catalyst and catalytic activity of catalyst on acetylene hydrochlorination reaction |
| CN103381369A (en) * | 2013-07-10 | 2013-11-06 | 清华大学 | Nitrogen doped carbon material loaded catalyst |
| CN104174421A (en) * | 2014-08-08 | 2014-12-03 | 浙江大学 | Heterogeneous catalyst for selective hydrogenation reaction of aryl nitro-compound and application of heterogeneous catalyst |
| 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 |
| CN104549401A (en) * | 2013-10-28 | 2015-04-29 | 天津大学 | Nonmetallic catalyst for acetylene hydrochlorination, as well as preparation method and application |
| CN106140239A (en) * | 2015-04-23 | 2016-11-23 | 北京化工大学 | A kind of polyacid base supported catalyst for desulfurizing oil and preparation method thereof |
| CN106450358A (en) * | 2016-12-08 | 2017-02-22 | 湘潭大学 | N-doped carbon nano-tube/carbon compound oxygen reduction catalyst and preparation method thereof |
| CN107519872A (en) * | 2017-08-04 | 2017-12-29 | 内蒙古大学 | A kind of boron, nitrogen codope acetylene hydrochlorination catalyst preparation method |
| 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 |
| CN109037685A (en) * | 2018-07-05 | 2018-12-18 | 朱文杰 | A kind of preparation method of conductive agent |
| CN109174005A (en) * | 2018-11-07 | 2019-01-11 | 河北科技大学 | A kind of method of modifying of regenerated carbon |
| CN109876840A (en) * | 2018-12-25 | 2019-06-14 | 南开大学 | A kind of preparation method and its application method of the non-metal catalyst for preparing vinyl chloride by hydrochlorination of acetylene |
| CN109926081A (en) * | 2017-12-15 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of catalyst, preparation and regeneration method for 1,2- dichloroethanes cracking preparing chloroethylene |
| CN111420694A (en) * | 2020-04-02 | 2020-07-17 | 鄂尔多斯市瀚博科技有限公司 | Copper-based catalyst taking nitrogen modified activated carbon as carrier and preparation method and application thereof |
| CN112705186A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | 2, 5-dichlorotoluene isomerization catalyst, preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102631942A (en) * | 2012-04-17 | 2012-08-15 | 清华大学 | Composite metal salt catalyst for hydrochlorination reaction of acetylene |
-
2012
- 2012-09-28 CN CN2012103666392A patent/CN102921473A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102631942A (en) * | 2012-04-17 | 2012-08-15 | 清华大学 | Composite metal salt catalyst for hydrochlorination reaction of acetylene |
Non-Patent Citations (3)
| Title |
|---|
| 刘小军等: "三聚氰胺改性沥青基球形活性炭的实验研究", 《中国科技论文在线》, vol. 4, no. 12, 31 December 2009 (2009-12-31) * |
| 王志等: "沥青基球状活性炭担载尿素用于N02的低温选择性催化还原行为研究", 《燃料化学学报》, vol. 40, no. 4, 30 April 2012 (2012-04-30), pages 463 - 468 * |
| 谈俊等: "掺氮碳纳米管的结构、制备及其催化应用", 《工业催化》, vol. 1, 28 February 2011 (2011-02-28), pages 15 - 21 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103157499A (en) * | 2013-03-29 | 2013-06-19 | 石河子大学 | Preparation of novel nitrogen modified Au/N-AC catalyst and catalytic activity of catalyst on acetylene hydrochlorination reaction |
| CN103381369A (en) * | 2013-07-10 | 2013-11-06 | 清华大学 | Nitrogen doped carbon material loaded catalyst |
| CN104549401A (en) * | 2013-10-28 | 2015-04-29 | 天津大学 | Nonmetallic catalyst for acetylene hydrochlorination, as well as preparation method and application |
| CN104174421A (en) * | 2014-08-08 | 2014-12-03 | 浙江大学 | Heterogeneous catalyst for selective hydrogenation reaction of aryl nitro-compound and application of heterogeneous catalyst |
| 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 |
| CN106140239A (en) * | 2015-04-23 | 2016-11-23 | 北京化工大学 | A kind of polyacid base supported catalyst for desulfurizing oil and preparation method thereof |
| CN106450358A (en) * | 2016-12-08 | 2017-02-22 | 湘潭大学 | N-doped carbon nano-tube/carbon compound oxygen reduction catalyst and preparation method thereof |
| CN107519872A (en) * | 2017-08-04 | 2017-12-29 | 内蒙古大学 | A kind of boron, nitrogen codope acetylene hydrochlorination catalyst preparation method |
| CN109926081A (en) * | 2017-12-15 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of catalyst, preparation and regeneration method for 1,2- dichloroethanes cracking preparing chloroethylene |
| 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 |
| CN109037685A (en) * | 2018-07-05 | 2018-12-18 | 朱文杰 | A kind of preparation method of conductive agent |
| CN109174005A (en) * | 2018-11-07 | 2019-01-11 | 河北科技大学 | A kind of method of modifying of regenerated carbon |
| CN109876840A (en) * | 2018-12-25 | 2019-06-14 | 南开大学 | A kind of preparation method and its application method of the non-metal catalyst for preparing vinyl chloride by hydrochlorination of acetylene |
| CN112705186A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | 2, 5-dichlorotoluene isomerization catalyst, preparation method and application thereof |
| CN112705186B (en) * | 2019-10-24 | 2023-09-29 | 中国石油化工股份有限公司 | 2, 5-dichlorotoluene isomerization catalyst, preparation method and application thereof |
| CN111420694A (en) * | 2020-04-02 | 2020-07-17 | 鄂尔多斯市瀚博科技有限公司 | Copper-based catalyst taking nitrogen modified activated carbon as carrier and preparation method and application thereof |
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Application publication date: 20130213 |