CN103203241A - Low-mercury catalyst for hydrochlorination of acetylene - Google Patents
Low-mercury catalyst for hydrochlorination of acetylene Download PDFInfo
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- CN103203241A CN103203241A CN2013101461000A CN201310146100A CN103203241A CN 103203241 A CN103203241 A CN 103203241A CN 2013101461000 A CN2013101461000 A CN 2013101461000A CN 201310146100 A CN201310146100 A CN 201310146100A CN 103203241 A CN103203241 A CN 103203241A
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Abstract
The invention discloses a low-mercury catalyst and particularly relates to the low-mercury catalyst which is suitable for synthesizing vinyl chloride by hydrochlorination reaction of acetylene. The catalyst comprises a main active component, namely mercury chloride, auxiliary active components, namely at least one of oxides of cobalt, manganese, silver and copper and a carrier, namely activated carbon, wherein the mercury chloride accounts for 2-4% of the weight of the carrier of the catalyst, and the auxiliary active components account for 5-30% of the weight of the carrier of the catalyst in total. According to the prepared low-mercury complex catalyst disclosed by the invention, the auxiliary components are added, so that the anti-poisoning performance of the low-mercury catalyst is enhanced, the reduction of the mercury chloride during the using process is reduced, the loss of mercury is retarded, the service life of the low-mercury catalyst is significantly prolonged, and the low-mercury catalyst is the novel low-mercury catalyst with good activity, strong stability and high selectivity. The low-mercury catalyst has the advantages of simple production process, short production period and low mercury consumption.
Description
Technical field
The present invention relates to a kind of catalyst, particularly a kind of low-mercury catalyst for the acetylene hydrochlorination synthesizing chloroethylene.
Background technology
Polyvinyl chloride is one of the world's five big synthetic resin, is widely used in national economy key areas such as industry, agricultural, building materials.VCM is important organic chemical industry's synthesis material, and main application is to produce Corvic and other vinyl chloride copolymers, along with its demand of The development in society and economy grows with each passing day.The 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 ", having determined carbide acetylene method to produce polyvinyl chloride becomes main flow.Though the carbide acetylene method polyvinyl chloride plays an important role for alleviation China's oil shortage of resources, the external interdependency of minimizing oil, raising energy security, the present problem that faces is seriously restricting its development in the industry.
The catalyst of industrial use has high mercury catalyst and low-mercury catalyst, the mercury chloride content 10-12% of high mercury catalyst, the mercury chloride content 4-6.5% of low-mercury catalyst.Because the mercury chloride content height of high mercury catalyst, mercury consumption is big, progressively is being eliminated now.The application scale of low mercury catalyst is progressively enlarging, and the typical case of low mercury catalyst is represented as CN200610012455.0 and 201010203376.4.CN200610012455.0 is the technology of Hebei Kechuang auxiliary agent Co., Ltd, and this catalyst activity charcoal is carrier, contains mercury chloride 4-6.5, and helper component is zinc chloride, immersion process for preparing, and the low-mercury catalyst of Shi Yonging mostly is this company's production in the market.201010203376.4 be the technology of Xinjiang Tianye (Group) Co., Ltd., be specially: 100 parts of absorbent charcoal carriers, 1～8 part in main catalytic composition mercury chloride, 1～10 part of auxiliary element, each 1～10 part of auxiliary element A and B, auxiliary element A is cobalt chloride or manganese chloride, and auxiliary element B is potassium chloride or ammonium chloride, and this catalyst is realized producing in batches and using in its intra-company.
Other research and reports about low-mercury catalyst are also a lot.CN02154466.2 has introduced a kind of environment-friendly type mercury catalyst and production technology thereof, and this catalyst is carrier with zeolite or molecular sieve, makes mercury content 3-9% by mercury ion exchange sodium ion.CN201010246013.9 is carrier with 13X or MCM41 molecular sieve, and load mercury chloride 2-7%, auxiliary agent are the chloride of bismuth, zinc, cuprous, barium.CN201110023199.6 is carrier with the ature of coal charcoal, rotary dipping, and vacuum drying, mercury chloride content 3-7%, auxiliary agent are the chloride of nickel, chromium, ferrous, iron, cobalt, barium.CN201110246027.5 is carrier with the active carbon, and mercury chloride content 4-5%, necessary auxiliary agent are barium chloride, cerium chloride, bismuth chloride, copper chloride, and nonessential auxiliary agent is one or more in potassium chloride, phosphoric acid, zinc chloride and the stannous chloride.CN201110380068.3 mercury chloride content 2.5-3.5%, helper component bismuth chloride, zinc chloride, manganese chloride, copper chloride, aluminium chloride, vanadium chloride, rare earth chloride, barium chloride, zeolite is as carrier.All adopted the mercury chloride of lower content as the main active component of catalyst in these several the patents, other metal chlorides are carrier as helping active component with active carbon or molecular sieve, but owing to contain H in the unstripped gas in the use
2S, PH
3Impurity causes the poisoning and deactivation of catalyst, because acetylene has higher reproducibility, easily makes the main active component Hg in the catalysis simultaneously
2+Be transformed into Hg
0, cause the mistake of catalysqt deactivation and mercury stream.Thereby the inactivation that has caused catalyst, so though the catalysis work of above-mentioned low-mercury catalyst can be satisfied production requirement, its stability and anti-poisoning performance are relatively poor, the life-span is shorter, fails to obtain in acetylene hydrochlorination commercial Application.
Summary of the invention
The object of the invention is further to reduce the use amount of mercury in the carbide acetylene method Production of PVC, promotes the source to reduce discharging, for the sustainable and healthy development of carbide acetylene method polyvinyl chloride industry provides technical guarantee.
A kind of low-mercury catalyst for acetylene hydrochlorination, comprise main active component mercury chloride, help active component and carrier, the content of main active component mercury chloride accounts for 2 ~ 4% of catalyst carrier gross weight, help the metal element content in the active component to account for 5 ~ 30% of catalyst carrier gross weight, wherein helping active component is one or more of oxide of cobalt, manganese, copper, silver.
Described a kind of low-mercury catalyst for acetylene hydrochlorination, helping active component is cobalt oxide.
Described a kind of low-mercury catalyst for acetylene hydrochlorination, helping active component is manganese oxide.
Described a kind of low-mercury catalyst for acetylene hydrochlorination helps active component content to account for 15 ~ 25% of catalyst carrier gross weight.
The preparation method of described a kind of low-mercury catalyst for acetylene hydrochlorination is: earlier with one or more dip loadings of cobalt, manganese, copper, silver-colored soluble metal compound to carrier; 90-110 ℃ of oven dry; 150-1000 ℃ of following nitrogen protection atmosphere roasting 1-5 hour, cooling back loading mercury chloride.
Described a kind of low-mercury catalyst for acetylene hydrochlorination, the metallic compound that helps active component are a kind of in metal nitrate or the metal sulfate.
The preparation method of described a kind of low-mercury catalyst for acetylene hydrochlorination, cobalt, manganese, copper, silver-colored load can be by repeatedly dip loading, oven dry, roasting realize.
Described a kind of low-mercury catalyst for acetylene hydrochlorination, its carrier specific area is 800 ~ 3500m
2The active carbon of/g, molecular sieve, silica gel, zeolite, diatomite, micropore ratio 〉=50% of carrier.
Described a kind of low-mercury catalyst for acetylene hydrochlorination is used for the acetylene hydrochlorination gas-solid phase reaction.
A kind of low-mercury catalyst for acetylene hydrochlorination provided by the invention, the adding of helper component can make the H in the acetylene gas in this catalyst
2S, PH
3Impurity and helper component reaction, reduce the reaction of foreign gas and mercury chloride, strengthened the anti-poisoning performance of low-mercury catalyst, simultaneously in industrial processes, occur once in a while under the excessive situation of acetylene, excessive acetylene can react with auxiliary substance, has alleviated the mercury chloride reduction in using, slow down the mercury loss, significantly improved the low-mercury catalyst life-span.
The present invention compares with composite interpolation metal chloride catalyst, because auxiliary substance exists with the form of oxide, and step load, auxiliary substance not can with the mercury chloride absorption of competing, also can not dissolve loss in the process of load mercury chloride, be that a kind of activity is good, stability is strong, selective high novel low-mercury catalyst.
The specific embodiment:
For better explanation the present invention, enumerate following example.But scope of the present invention also not only is confined to example, and its claimed scope is recorded in the claim of claim.
Embodiment 1:
Weighing four water manganese nitrate 8.65g are dissolved in the 40ml deionized water, take by weighing absorbent charcoal carrier 20g and put into manganese nitrate solution, 60 ℃ of dipping 4h; Filter out residual liquid, after 105 ℃ of oven dry, 180 ℃ of following nitrogen protection atmosphere roasting 3 hours is cooled to room temperature under the nitrogen protection; Take by weighing mercury chloride 0.92g, be dissolved in the 40ml deionized water, with load the carrier of manganese put into mercuric chloride solution, 70 ℃ are soaked 4h; Filter raffinate, 105 ℃ of dryings get the acetylene hydrochlorination low-mercury catalyst.
Embodiment 2:
Weighing cobalt sulfate 7.51g is dissolved in the 40ml deionized water, takes by weighing Zeolite support 20g and puts into cobalt sulfate solution, 60 ℃ of dipping 4h; Filter out residual liquid, after 105 ℃ of oven dry, 900 ℃ of following nitrogen protection atmosphere roasting 3 hours is cooled to room temperature under the nitrogen protection; Repeat above-mentioned steps preparation cobalt sulfate solution, with 60 ℃ of dippings of load carrier once 4h, filter out residual liquid, after 105 ℃ of oven dry, 900 ℃ of following nitrogen protection atmosphere roasting 3 hours is cooled to room temperature under the nitrogen protection; Take by weighing mercury chloride 0.77g, be dissolved in the 40ml deionized water, with load the carrier of cobalt put into mercuric chloride solution, 70 ℃ are soaked 4h; Filter raffinate, 105 ℃ of dryings get the acetylene hydrochlorination low-mercury catalyst.
Embodiment 3:
Weighing nitrate trihydrate copper 7.29g is dissolved in the 40ml deionized water, takes by weighing absorbent charcoal carrier 20g and puts into copper nitrate solution, 60 ℃ of dipping 4h; Filter out residual liquid, after 105 ℃ of oven dry, 200 ℃ of following nitrogen protection atmosphere roasting 3 hours is cooled to room temperature under the nitrogen protection; Take by weighing mercury chloride 0.67g, be dissolved in the 40ml deionized water, with load the carrier of copper put into mercuric chloride solution, 70 ℃ are soaked 4h; Filter raffinate, 108 ℃ of dryings get the acetylene hydrochlorination low-mercury catalyst.
Embodiment 4:
Weighing silver nitrate 1.17g is dissolved in the 40ml deionized water, takes by weighing molecular sieve carrier 20g and puts into liquor argenti nitratis ophthalmicus, 60 ℃ of dipping 4h; Filter out residual liquid, after 103 ℃ of oven dry, 500 ℃ of following nitrogen protection atmosphere roasting 3 hours is cooled to room temperature under the nitrogen protection; Take by weighing mercury chloride 0.54g, be dissolved in the 40ml deionized water, with load the carrier of copper put into mercuric chloride solution, 70 ℃ are soaked 4h; Filter raffinate, 110 ℃ of dryings get the acetylene hydrochlorination low-mercury catalyst.
Embodiment 5:
Weighing anhydrous cupric sulfate 11.30g is dissolved in the 40ml deionized water, takes by weighing diatomite support 20g and puts into copper-bath, 60 ℃ of dipping 4h; Filter out residual liquid, after 103 ℃ of oven dry, 700 ℃ of following nitrogen protection atmosphere roasting 3 hours is cooled to room temperature under the nitrogen protection; Take by weighing mercury chloride 0.78g, be dissolved in the 40ml deionized water, with load the carrier of copper put into mercuric chloride solution, 70 ℃ are soaked 4h; Filter raffinate, 110 ℃ of dryings get the acetylene hydrochlorination low-mercury catalyst.
Claims (8)
1. low-mercury catalyst that is used for acetylene hydrochlorination, comprise main active component mercury chloride, help active component and carrier, the content of main active component mercury chloride accounts for 2 ~ 4% of catalyst carrier gross weight, help the metal element content in the active component to account for 5 ~ 30% of catalyst carrier gross weight, it is characterized in that: helping active component is one or more of oxide of cobalt, manganese, copper, silver.
2. according to the described a kind of low-mercury catalyst for acetylene hydrochlorination of claim 1, it is characterized in that the described active component that helps is cobalt oxide.
3. a kind of low-mercury catalyst for acetylene hydrochlorination according to claim 1 is characterized in that the described active component that helps is manganese oxide.
4. a kind of low-mercury catalyst for acetylene hydrochlorination according to claim 1 is characterized in that the described active component content that helps accounts for 15 ~ 25% of catalyst carrier gross weight.
5. according to the preparation method of the arbitrary described a kind of low-mercury catalyst for acetylene hydrochlorination of claim 1-4; it is characterized in that: earlier with one or more dip loadings of cobalt, manganese, copper, silver-colored soluble metal compound to carrier; 90-110 ℃ of oven dry; 150-1000 ℃ of following nitrogen protection atmosphere roasting 1-5 hour, cooling back loading mercury chloride.
6. according to the arbitrary described a kind of low-mercury catalyst for acetylene hydrochlorination of claim 1-4, the metallic compound that it is characterized in that helping active component is a kind of in metal nitrate or the metal sulfate.
7. a kind of low-mercury catalyst preparation method for acetylene hydrochlorination according to claim 5 is characterized in that cobalt, manganese, copper, silver-colored load can be by repeatedly dip loading, oven dry, roasting realize.
8. according to the arbitrary described a kind of low-mercury catalyst for acetylene hydrochlorination of claim 1-4, it is characterized in that the carrier specific area is 800 ~ 3500m
2The active carbon of/g, molecular sieve, silica gel, zeolite, diatomite, micropore ratio 〉=50% of carrier.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103521246A (en) * | 2013-10-16 | 2014-01-22 | 刘金朝 | High-activity environment-friendly low-mercury composite catalyst |
| CN104324738A (en) * | 2014-04-24 | 2015-02-04 | 云南契合投资有限公司 | Low-mercury catalyst supported to mesoporous carbon material and application thereof |
| CN105032455A (en) * | 2015-08-05 | 2015-11-11 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Ultralow-mercury catalyst used for acetylene hydrochlorination |
| CN105080581A (en) * | 2015-09-11 | 2015-11-25 | 浙江工业大学 | Composite low solid mercury catalyst used for acetylene hydrochlorination and preparation method thereof |
| CN105983428A (en) * | 2015-01-30 | 2016-10-05 | 天津大学 | Catalyst used in low-temperature removal of hydrogen chloride from dichloroethane for preparation of vinyl chloride, 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 |
| CN110833838A (en) * | 2019-11-18 | 2020-02-25 | 铜仁市万山区昊海化工有限公司 | Ultra-low mercury catalyst and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103521246A (en) * | 2013-10-16 | 2014-01-22 | 刘金朝 | High-activity environment-friendly low-mercury composite catalyst |
| CN104324738A (en) * | 2014-04-24 | 2015-02-04 | 云南契合投资有限公司 | Low-mercury catalyst supported to mesoporous carbon material and application thereof |
| CN105983428A (en) * | 2015-01-30 | 2016-10-05 | 天津大学 | Catalyst used in low-temperature removal of hydrogen chloride from dichloroethane for preparation of vinyl chloride, and preparation method and application thereof |
| CN105983428B (en) * | 2015-01-30 | 2018-12-21 | 天津大学 | A kind of catalyst and Preparation method and use preparing vinyl chloride for dichloroethanes low temperature antichloration hydrogen |
| CN105032455A (en) * | 2015-08-05 | 2015-11-11 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Ultralow-mercury catalyst used for acetylene hydrochlorination |
| CN105032455B (en) * | 2015-08-05 | 2017-08-01 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of ultralow mercury catalyst for acetylene hydrochlorination |
| CN105080581A (en) * | 2015-09-11 | 2015-11-25 | 浙江工业大学 | Composite low solid mercury catalyst used for acetylene hydrochlorination and preparation method 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 |
| CN110833838A (en) * | 2019-11-18 | 2020-02-25 | 铜仁市万山区昊海化工有限公司 | Ultra-low mercury catalyst and preparation method thereof |
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