CN105251502A - Mercury-free catalyst for acetylene hydrochlorination - Google Patents
Mercury-free catalyst for acetylene hydrochlorination Download PDFInfo
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- CN105251502A CN105251502A CN201410713910.4A CN201410713910A CN105251502A CN 105251502 A CN105251502 A CN 105251502A CN 201410713910 A CN201410713910 A CN 201410713910A CN 105251502 A CN105251502 A CN 105251502A
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Abstract
The invention discloses a mercury-free catalyst and especially relates to a mercury-free catalyst for acetylene hydrochlorination synthesis of vinyl chloride. The mercury-free catalyst comprises a composite carrier composed of active carbon and a metal oxide, and at least one of cobalt, manganese, copper, zinc, bismuth, barium and potassium as active ingredients. The mercury-free catalyst utilizes the composite carrier composed of active carbon and metal oxide, has dual properties of active carbon carriers and metal oxide carriers and has high acetylene hydrochlorination catalytic activity. Through interaction of the composite carrier and the active ingredient, the catalyst can produce weak and fast chemisorption of hydrogen chloride (as acetylene hydrochlorination raw material gas) so that the mercury-free catalyst for acetylene hydrochlorination is obtained. Through special properties of the composite carrier and special action of the active ingredient and the composite carrier, the catalyst has high reaction activity and is a novel mercury-free catalyst with good activity, strong stability and high selectivity. The mercury-free catalyst has the advantages of simple production processes, short production period and low production cost.
Description
Technical field
The present invention relates to a kind of catalyst, particularly relate to a kind of non-mercury catalyst for acetylene hydrochlorination.
Background technology
Polyvinyl chloride is one of large synthetic resin in the world five, is widely used in the national economy key areas such as industry, agricultural, building materials.VCM is important organic chemical industry's synthesis material, and main application produces Corvic and other vinyl chloride copolymers, along with its demand of socioeconomic development grows with each passing day.Vinyl chloride source mainly contains carbide acetylene method, oil ethylene process and dichloroethanes cracking process.The energy resource structure of China's " oil starvation, lean gas, rich coal ", determining carbide acetylene method production polyvinyl chloride becomes main flow.
The catalyst of industrial use is mercury catalyst, Hg chloride content 4-12%.This catalyst mercury chloride easily runs off, and the mercury be lost in nature causes severe environmental pollution, and follow-up mercuric pollution treatment difficulty is large, serious to the destruction of ecological environment.Mercury pollution problem has caused the extensive concern of international community, on January 19th, 2013, and United Nations Environment Programme have passed the international convention " Minamata pact " being intended to control and reduce mercury emissions in global range, and the Chinese government also increases the improvement to mercury pollution.For avoiding causing passive situation in the minimizing, mercuryless process of mercury, the substitute products of mercury catalyst must be researched and developed.Therefore the research and development of catalyst without mercury are of great immediate significance.Some Domestic colleges and universities, scientific research institutions and enterprise are also carrying out the research in this, and have applied for corresponding patent.201110023357.8 describe a kind of catalyst without mercury producing vinyl chloride for carbide, and this catalyst take active carbon as carrier, and active component is bismuth with elementary, and auxiliary agent is one or more in frerrous chloride, iron chloride, nickel chloride, barium chloride, bismuth chloride.201110040369.1 describe a kind of phosphorized copper Catalysts and its preparation method for VCM synthesis, and the carrier of this catalyst is active carbon, and active component is Cu
3p, auxiliary agent is one or more in copper chloride, nickel chloride, barium chloride.201310226980.2 describe a kind of anion-modified catalyst without mercury for acetylene hydrochlorination reaction, and the carrier of this catalyst is active carbon, and active component is the chloride of copper or tin, phosphate, sulfate or nitrate.
Summary of the invention
The present invention is for providing a kind of non-mercury catalyst for acetylene hydrochlorination, solve and use highly toxic mercury catalyst in carbide acetylene method Production of PVC under comparatively economic condition, in production, mercury consumption is large, environmental pollution is serious, existing noble metal catalyst dispersiveness is bad, the problem of less stable, and then provide that a kind of catalyst activity component disperses is high, catalytic activity good, selective height, the non-mercury catalyst of good stability.
For a non-mercury catalyst for acetylene hydrochlorination, comprise the complex carrier that active carbon and metal oxide form, at least one of active component cobalt, manganese, copper, zinc, bismuth, barium, potassium.
As above for a non-mercury catalyst for acetylene hydrochlorination, active carbon accounts for 10 ~ 90% of carrier gross mass.
As above for a non-mercury catalyst for acetylene hydrochlorination, the metal oxide of composition complex carrier is insoluble to concentrated hydrochloric acid.
As above for a non-mercury catalyst for acetylene hydrochlorination, be insoluble at least one that concentrated hydrochloric acid metal oxide is cerium oxide, tungsten oxide, titanium oxide, molybdenum oxide, zirconia, vanadium oxide, silver oxide.
As above for a non-mercury catalyst for acetylene hydrochlorination, complex carrier can mix obtained by active carbon with metal oxide, also obtains by soluble metallic salt being loaded to roasting after on active carbon.
As above for a non-mercury catalyst for acetylene hydrochlorination, active component is one or more in cobalt, manganese, copper, zinc, bismuth, barium, the chloride of potassium, nitrate, sulfate or phosphate, and content accounts for 3 ~ 50% of catalyst carrier gross weight.
As above for a low-mercury catalyst for acetylene hydrochlorination, for acetylene hydrochlorination gas-solid phase reaction.
A kind of non-mercury catalyst for acetylene hydrochlorination provided by the invention, adopt the complex carrier that active carbon and metal oxide form, complex carrier not only has the double properties of absorbent charcoal carrier and metal oxide carrier, also shows higher acetylene hydrochlorination catalytic reaction active simultaneously.By the interaction between complex carrier and active component, catalyst can be made to produce more weak and chemisorbed faster to hydrogen chloride (acetylene hydrochlorination unstripped gas), obtain a kind of non-mercury catalyst of suitable acetylene hydrochlorination.
The present invention with single with active carbon or the metal oxide catalyst that is carrier compared with, due to the special nature of complex carrier and the interaction of complex carrier and active component, having higher reactivity, is that a kind of activity is good, stability is strong, selective high non-mercury catalyst.
Detailed description of the invention
In order to better the present invention is described, enumerate following instance.But scope of the present invention is also not only confined to example, and its claimed scope is recorded in the claim of claim.
Embodiment 1:
Take ammonium vanadate 3.44g, be dissolved in 30ml hot water; Take active carbon 15.00g, pour in the Ammonium Vanadate Solution prepared.60 DEG C of water bath methods, 105 DEG C of oven dry.300 DEG C of nitrogen protection atmosphere roasting 3 hours, cools to obtain complex carrier.Take copper chloride dihydrate 2.00g, be dissolved in 30ml warm water.The complex carrier prepared is poured in the copper chloride solution prepared.60 DEG C of water bath methods, 105 DEG C of dryings, obtain acetylene hydrochlorination non-mercury catalyst.
Embodiment 2:
Take titania powder 5.00g, take active carbon powder 15.00g, add water and binding agent, after mixed-forming, drying, obtain complex carrier.Take zinc chloride 3.00g, potassium nitrate 2g, be dissolved in 30ml warm water, make mixed solution.The complex carrier prepared is poured in the copper chloride solution prepared.50 DEG C of water bath methods, 110 DEG C of dryings, obtain acetylene hydrochlorination non-mercury catalyst.
Embodiment 3:
Take ammonium molybdate 5.00g, be dissolved in 35ml hot water; Take active carbon 15.00g, pour in the Ammonium Vanadate Solution prepared.65 DEG C of water bath methods, 115 DEG C of oven dry.500 DEG C of nitrogen protection atmosphere roasting 5 hours, cools to obtain complex carrier.Take cupric sulfate pentahydrate 2.00g, tetrahydrate manganese chloride 1.5g, barium chloride 1.0g, be dissolved in 35ml warm water, obtain the mixed solution of three kinds of materials.The complex carrier prepared is poured in the mixed solution prepared.65 DEG C of water bath methods, 115 DEG C of dryings, obtain acetylene hydrochlorination non-mercury catalyst.
Embodiment 4:
Take anhydrous nitric acid zirconium 6g, be dissolved in 40ml hot water; Take active carbon 15.00g, pour in the zirconium nitrate solution prepared.60 DEG C of water bath methods, 105 DEG C of oven dry.350 DEG C of nitrogen protection atmosphere roasting 6 hours, cools to obtain complex carrier.Take copper chloride dihydrate 3.00g, barium chloride 2g, be dissolved in 30ml warm water, obtain the mixed solution of two kinds of materials.The complex carrier prepared is poured in the mixed solution prepared.60 DEG C of water bath methods, 105 DEG C of dryings, obtain acetylene hydrochlorination non-mercury catalyst.
Embodiment 5:
Take tungsten trioxide powder 10.00g, take active carbon powder 15.00g, add water and binding agent, mixed-forming, drying, the roasting of 300 DEG C of nitrogen protection atmosphere obtained complex carrier after 3 hours.Take zinc chloride 2.00g, barium chloride 1g, be dissolved in 30ml warm water, make mixed solution.The complex carrier prepared is poured in the copper chloride solution prepared.50 DEG C of water bath methods, 110 DEG C of dryings, obtain acetylene hydrochlorination non-mercury catalyst.
Claims (6)
1. for a non-mercury catalyst for acetylene hydrochlorination, it is characterized in that: carrier is the complex carrier that active carbon and metal oxide form, and active component is at least one of cobalt, manganese, copper, zinc, bismuth, barium, potassium compound.
2. a kind of non-mercury catalyst for acetylene hydrochlorination according to claim 1, it is characterized in that the complex carrier that described active carbon and metal oxide form, active carbon accounts for 10 ~ 90% of carrier gross weight.
3., according to the arbitrary described a kind of non-mercury catalyst for acetylene hydrochlorination of claim 1-2, it is characterized in that the metal oxide of described composition complex carrier is insoluble to concentrated hydrochloric acid.
4., according to the arbitrary described a kind of non-mercury catalyst for acetylene hydrochlorination of claim 1-2, the metal oxide being insoluble to concentrated hydrochloric acid described in it is characterized in that is at least one of cerium oxide, tungsten oxide, titanium oxide, molybdenum oxide, zirconia, vanadium oxide, silver oxide.
5. according to the arbitrary described a kind of non-mercury catalyst for acetylene hydrochlorination of claim 1-2, it is characterized in that described complex carrier can mix with metal oxide obtained by active carbon, also obtaining by soluble metallic salt being loaded to roasting after on active carbon.
6. according to the arbitrary described a kind of non-mercury catalyst for acetylene hydrochlorination of claim 1-2, it is characterized in that described active component is cobalt, manganese, copper, zinc, bismuth, barium, the chloride of potassium, nitrate, sulfate or phosphate, content accounts for 3 ~ 50% of catalyst carrier gross weight.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106362741A (en) * | 2016-08-05 | 2017-02-01 | 厦门大学 | Compound gold-based catalyst, and preparation method and application thereof |
| CN106423287A (en) * | 2016-09-10 | 2017-02-22 | 新疆大学 | Supported mercury-free catalyst, preparation method thereof and application of supported mercury-free catalyst in preparation of vinyl chloride through ethyne hydrochlorination |
| 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 |
| CN107552061A (en) * | 2016-06-30 | 2018-01-09 | 中国石油化工股份有限公司 | Activated carbon base sulfur-resistant transformation catalyst and preparation method thereof |
| CN108373400A (en) * | 2018-02-05 | 2018-08-07 | 陕西北元化工集团股份有限公司 | A kind of acetylene method VCM synthesis technique |
| CN109806905A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of catalyst without mercury, preparation method and preparing the application in vinyl chloride |
| CN110368936A (en) * | 2019-08-09 | 2019-10-25 | 美澜催化材料科技(大连)有限公司 | Nano-material modified copper-based support type acetylene hydrochlorination catalyst of one kind and preparation method thereof |
| CN110465279A (en) * | 2019-08-21 | 2019-11-19 | 福建省鑫森炭业股份有限公司 | Catalyst without mercury carrier active carbon and preparation method thereof for PVC production |
| CN110961112A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Catalyst for acetylene hydrochlorination reaction and preparation method and application thereof |
| CN110963883A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Method for hydrochlorinating acetylene |
| CN111569834A (en) * | 2020-06-01 | 2020-08-25 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Mercury removing adsorbent for crude chloroethylene gas |
| CN111672525A (en) * | 2020-06-11 | 2020-09-18 | 美澜催化材料科技(大连)有限公司 | In-situ synthesis layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst on activated carbon and preparation method thereof |
| CN113083319A (en) * | 2021-04-09 | 2021-07-09 | 贵州大学 | Method for preparing chloroethylene synthetic catalyst by extracting and separating manganese slag |
| CN113351215A (en) * | 2020-03-05 | 2021-09-07 | 石河子市中易连疆新能源有限责任公司 | Core-shell structure catalyst, preparation method and application thereof |
| CN113797942A (en) * | 2021-08-20 | 2021-12-17 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Phosphorus-modified copper-based catalyst for acetylene hydrochlorination reaction and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107552061A (en) * | 2016-06-30 | 2018-01-09 | 中国石油化工股份有限公司 | Activated carbon base sulfur-resistant transformation catalyst and preparation method thereof |
| CN106362741A (en) * | 2016-08-05 | 2017-02-01 | 厦门大学 | Compound gold-based catalyst, and preparation method and application thereof |
| 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 |
| CN106423287A (en) * | 2016-09-10 | 2017-02-22 | 新疆大学 | Supported mercury-free catalyst, preparation method thereof and application of supported mercury-free catalyst in preparation of vinyl chloride through ethyne hydrochlorination |
| CN109806905A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of catalyst without mercury, preparation method and preparing the application in vinyl chloride |
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| CN110963883A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Method for hydrochlorinating acetylene |
| CN110961112A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Catalyst for acetylene hydrochlorination reaction and preparation method and application thereof |
| CN110368936A (en) * | 2019-08-09 | 2019-10-25 | 美澜催化材料科技(大连)有限公司 | Nano-material modified copper-based support type acetylene hydrochlorination catalyst of one kind and preparation method thereof |
| CN110465279A (en) * | 2019-08-21 | 2019-11-19 | 福建省鑫森炭业股份有限公司 | Catalyst without mercury carrier active carbon and preparation method thereof for PVC production |
| CN110465279B (en) * | 2019-08-21 | 2022-10-18 | 福建省鑫森炭业股份有限公司 | Mercury-free catalyst carrier activated carbon for PVC production and preparation method thereof |
| CN113351215A (en) * | 2020-03-05 | 2021-09-07 | 石河子市中易连疆新能源有限责任公司 | Core-shell structure catalyst, preparation method and application thereof |
| CN113351215B (en) * | 2020-03-05 | 2022-12-20 | 石河子市中易连疆新能源有限责任公司 | Core-shell structure catalyst, preparation method and application thereof |
| CN111569834A (en) * | 2020-06-01 | 2020-08-25 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Mercury removing adsorbent for crude chloroethylene gas |
| CN111672525A (en) * | 2020-06-11 | 2020-09-18 | 美澜催化材料科技(大连)有限公司 | In-situ synthesis layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst on activated carbon and preparation method thereof |
| CN113083319A (en) * | 2021-04-09 | 2021-07-09 | 贵州大学 | Method for preparing chloroethylene synthetic catalyst by extracting and separating manganese slag |
| CN113797942A (en) * | 2021-08-20 | 2021-12-17 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Phosphorus-modified copper-based catalyst for acetylene hydrochlorination reaction and preparation method and application thereof |
| CN113797942B (en) * | 2021-08-20 | 2024-01-09 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Phosphorus-modified copper-based catalyst for hydrochlorination of acetylene as well as preparation method and application thereof |
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