CN101716508A - Catalyst used for synthesizing chloroethylene by acetylene and preparation method thereof - Google Patents
Catalyst used for synthesizing chloroethylene by acetylene and preparation method thereof Download PDFInfo
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- CN101716508A CN101716508A CN200910228149A CN200910228149A CN101716508A CN 101716508 A CN101716508 A CN 101716508A CN 200910228149 A CN200910228149 A CN 200910228149A CN 200910228149 A CN200910228149 A CN 200910228149A CN 101716508 A CN101716508 A CN 101716508A
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Abstract
The invention relates to a catalyst used for synthesizing chloroethylene by acetylene and a preparation method thereof. The catalyst is a granular catalyst prepared by taking active carbon as a carrier, and loading 2-15 percent of chloride of palladium or gold used as an active component, and 1-5 percent of rare earth chloride used as an auxiliary catalyst component on the active carbon through an immersion method. The catalyst is applied to the process of producing the chloroethylene through a direct catalytic conversion of the acetylene by taking the acetylene and hydrogen chloride as raw materials, has higher stability in comparison with a traditional mercuric chloride catalyst, and has no pollution to environment.
Description
Affiliated technical field
The present invention relates to a kind of catalyst and preparation method who is used for by the carbide synthesizing chloroethylene by acetylene.
Background technology
Industrial, vinyl chloride is mainly used in synthesizing polyvinyl chloride resin (PVC) and vinylidene chloride, refrigerant or the like.At present industrially transform acetylene by hydrogen chloride and make vinyl chloride on a large scale and normally adopt the heterogeneous catalyst that contains mercury chloride to finish, this catalyst tolerates temperature difference, easily distillation loss has severe toxicity, in process of production environment is caused serious pollution and infringement.China has classified useless mercuric chloride catalyst as mercurous hazardous waste, and the alternative work of mercury catalyst is imperative.Based on the consideration of environmental protection, research finds that can to replace mercury chloride to carry out the non-mercury catalyst system and catalyzing of suitability for industrialized production significant.This catalyst should environmentally friendly, difficultly lose, and stably catalyzed preferably performance is arranged again.
Purpose of the present invention just is to develop a kind of novel non-mercury catalyst and substitutes the mercury catalyst that has used many decades in industry, with the harm of thorough removal mercury to environment.
The present invention has effectively solved the mercury pollution that produces in the present carbide synthesizing chloroethylene by acetylene production process, and this catalyst has better stability of existing catalyst, long service life, the characteristics of environmentally safe.
Summary of the invention
For achieving the above object, the technical solution used in the present invention is:
A kind of catalyst that is used for synthesizing chloroethylene by acetylene, its chemical constituent mainly by active component, help catalyst component and carrier to form, it is characterized in that: used catalyst contains 2～15% palladium or the chloride of gold and 1～5% rare earth-iron-boron, and carrier is an activated carbon.
Above-described catalyst, the chloride of palladium or gold is selected from one or more in palladium bichloride and the gold chloride.
Above-described catalyst, rare earth-iron-boron wherein is selected from lanthanum chloride.
The performing step of this product is:
1, the surface treatment of activity carbon carrier
Activated carbon is put into hydrochloric acid solution reflow treatment 4-10 hour of 2 mol, removes foreign ions such as de-iron, zinc, spend deionised water then and remove wherein chlorion, 110 ℃ down after dry 12～20 hours as carrier.
2, Preparation of Catalyst
With active component and help catalyst component to be dissolved in deionized water to be made into certain density mixed solution, divide the activated carbon of secondary after dipping activation processing under the vacuum state at least with this solution, making quantitative maceration extract is active carbon adsorption, filters the back and promptly gets catalyst prod in dry 4～8 hours.Its product consists of:
MCl 2～15％；
Lanthanum chloride 1～5%;
The activity carbon carrier surplus
Wherein, MCl represents metal chloride, comprises one of chlorauride, two kinds of compositions of palladium bichloride or its mixture.The chloride of palladium or gold is selected from palladium bichloride and gold chloride.
The specific embodiment
The following examples will the present invention is further illustrated.
Embodiment one
The employing specific surface is 900M
2The activated carbon of/g at first refluxed 8 hours in the hydrochloric acid solution of 2 mol, removed impurity such as de-iron, zinc, spent deionised water removal chlorion wherein then, and drying is 20 hours under 110 ℃.The gold chloride and the lanthanum chloride of metering are mixed with mixed solution, this solution is joined in the container that activated carbon is housed, the amount that adds solution is as the criterion with submergence activated carbon just, and impregnated activated carbon secondary under vacuum 10Kpa filters the back and promptly got catalyst prod in dry 8 hours.The catalyst activity component chlorauride of gained, help catalyst component lanthanum chloride content for being respectively 10%, 1.5%.Adopt this catalyst under normal pressure, reaction temperature is 150 ℃, and the volume ratio of acetylene and hydrogen chloride is to carry out at 1.0: 1.05, and the acetylene volume space velocity is 90h
-1, conversion of alkyne is 99.5%, the vinyl chloride selectivity is 99%.
Embodiment two
The employing specific surface is 950M
2The activated carbon of/g at first refluxed 8 hours in the hydrochloric acid solution of 2 mol, removed impurity such as de-iron, zinc, spent deionised water removal chlorion wherein then, and drying is 20 hours under 110 ℃.The gold chloride and the lanthanum chloride of metering are mixed with mixed solution, this solution is joined in the container that activated carbon is housed, the amount that adds solution is as the criterion with submergence activated carbon just, and impregnated activated carbon secondary under vacuum 10Kpa filters the back and promptly got catalyst prod down in dry 8 hours at 120 ℃.The catalyst activity component chlorauride of gained, help catalyst component lanthanum chloride content for being respectively 5%, 1.5%.Adopt this catalyst under normal pressure, reaction temperature is 150 ℃, and the volume ratio of acetylene and hydrogen chloride is 1.0: 1.05, and the acetylene volume space velocity is 90h
-1, conversion of alkyne is 99%, the vinyl chloride selectivity is 99%.
Embodiment three
The employing specific surface is 950M
2The activated carbon of/g at first refluxed 8 hours in the hydrochloric acid solution of 2 mol, removed impurity such as de-iron, zinc, spent deionised water removal chlorion wherein then, and drying is 20 hours under 110 ℃.The palladium bichloride and the lanthanum chloride of metering are mixed with mixed solution, this solution is joined in the container that activated carbon is housed, the amount that adds solution is as the criterion with submergence activated carbon just, and impregnated activated carbon secondary under vacuum 10Kpa filters the back and promptly got catalyst prod down in dry 8 hours at 120 ℃.The catalyst activity component palladium bichloride of gained, help catalyst component lanthanum chloride content to be respectively 10%, 1.5%.Adopt this catalyst under normal pressure, reaction temperature is 150 ℃, and the volume ratio of acetylene and hydrogen chloride is 1.0: 1.05, and the acetylene volume space velocity is 30h
-1, conversion of alkyne is 98.2%, the vinyl chloride selectivity is 98%.
Claims (4)
1. catalyst that is used for synthesizing chloroethylene by acetylene, its chemical constituent mainly by active component, help catalyst component and carrier to form, it is characterized in that used catalyst contains 2～15% palladium or the chloride of gold and 1～5% rare earth-iron-boron, carrier is an activated carbon.
2. according to the described catalyst of claim 1, the chloride of palladium or gold is selected from one or more in palladium bichloride and the gold chloride.
3. according to the described catalyst of claim 1, rare earth-iron-boron wherein is selected from lanthanum chloride.
4. described Preparation of catalysts method of claim 1 is characterized in that:
(1) activated carbon is carried out surface treatment, comprising:
Activated carbon is put into hydrochloric acid solution reflow treatment 4-10 hour of 2 mol, removes foreign ion and wash removal chlorion wherein then, 110 ℃ down after dry 12～20 hours as carrier;
(2) adopt at least the secondary vacuum dipping to carry out load, comprising:
Active component is made into the certain density aqueous solution, and with the activated carbon of this solution branch at least twice after dipping activation processing under the vacuum state, making quantitative maceration extract is that activated carbon is adsorbed, gets catalyst prod of the present invention behind the filtration drying.
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| CN200910228149A CN101716508A (en) | 2009-11-10 | 2009-11-10 | Catalyst used for synthesizing chloroethylene by acetylene and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102259007A (en) * | 2011-06-07 | 2011-11-30 | 李伟 | Method for preparing mercury-free catalyst for synthesis of chloroethylene by acetylene process |
| CN102327777A (en) * | 2011-07-15 | 2012-01-25 | 天津大学 | Gold-containing catalyst for preparing vinyl chloride by using acetylene method as well as preparation method and application of catalyst |
| CN102755888A (en) * | 2012-07-04 | 2012-10-31 | 中昊(大连)化工研究设计院有限公司 | Preparation and application of synthesizing chloroethylene mercury free catalyst through acetylene method |
| CN102794174A (en) * | 2011-05-24 | 2012-11-28 | 代斌 | Au-La catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene and preparation method thereof |
| CN102806095A (en) * | 2012-08-29 | 2012-12-05 | 天津大沽化工股份有限公司 | Multi-component non-mercury accelerant for preparing vinyl chloride through acetylene hydrochlorination and application method of multi-component non-mercury accelerant |
| CN103191763A (en) * | 2013-04-23 | 2013-07-10 | 李永定 | Catalyst composition for producing vinyl chloride, as well as preparation method and application thereof |
| CN104368365A (en) * | 2013-10-21 | 2015-02-25 | 姚剑寒 | Mercury-free solid catalyst for PVC (polyvinyl chloride) conversion by acetylene method and preparation method thereof |
| CN105080470A (en) * | 2015-09-08 | 2015-11-25 | 成都中科能源环保有限公司 | Methane/carbon dioxide separating absorbent |
| CN105195229A (en) * | 2015-10-27 | 2015-12-30 | 宁夏新龙蓝天科技股份有限公司 | Method for preparing low-mercury catalyst by employing low-ash-content active carbon |
| CN110075927A (en) * | 2019-06-03 | 2019-08-02 | 浙江工业大学 | A kind of catalyst for vinyl chloride synthesis and preparation method thereof and a kind of synthetic method of vinyl chloride |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101249451A (en) * | 2008-04-10 | 2008-08-27 | 四川大学 | Non-mercury catalyst for acetylene hydrochlorination and method of preparing the same |
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2009
- 2009-11-10 CN CN200910228149A patent/CN101716508A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101249451A (en) * | 2008-04-10 | 2008-08-27 | 四川大学 | Non-mercury catalyst for acetylene hydrochlorination and method of preparing the same |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102794174A (en) * | 2011-05-24 | 2012-11-28 | 代斌 | Au-La catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene and preparation method thereof |
| CN102259007A (en) * | 2011-06-07 | 2011-11-30 | 李伟 | Method for preparing mercury-free catalyst for synthesis of chloroethylene by acetylene process |
| CN102327777A (en) * | 2011-07-15 | 2012-01-25 | 天津大学 | Gold-containing catalyst for preparing vinyl chloride by using acetylene method as well as preparation method and application of catalyst |
| CN102755888A (en) * | 2012-07-04 | 2012-10-31 | 中昊(大连)化工研究设计院有限公司 | Preparation and application of synthesizing chloroethylene mercury free catalyst through acetylene method |
| CN102806095A (en) * | 2012-08-29 | 2012-12-05 | 天津大沽化工股份有限公司 | Multi-component non-mercury accelerant for preparing vinyl chloride through acetylene hydrochlorination and application method of multi-component non-mercury accelerant |
| CN102806095B (en) * | 2012-08-29 | 2014-08-13 | 天津大沽化工股份有限公司 | Multi-component non-mercury accelerant for preparing vinyl chloride through acetylene hydrochlorination and application method of multi-component non-mercury accelerant |
| CN103191763A (en) * | 2013-04-23 | 2013-07-10 | 李永定 | Catalyst composition for producing vinyl chloride, as well as preparation method and application thereof |
| CN104368365A (en) * | 2013-10-21 | 2015-02-25 | 姚剑寒 | Mercury-free solid catalyst for PVC (polyvinyl chloride) conversion by acetylene method and preparation method thereof |
| CN105080470A (en) * | 2015-09-08 | 2015-11-25 | 成都中科能源环保有限公司 | Methane/carbon dioxide separating absorbent |
| CN105080470B (en) * | 2015-09-08 | 2018-01-16 | 成都中科能源环保有限公司 | A kind of methane/carbon dioxide separating adsorbent |
| CN105195229A (en) * | 2015-10-27 | 2015-12-30 | 宁夏新龙蓝天科技股份有限公司 | Method for preparing low-mercury catalyst by employing low-ash-content active carbon |
| CN110075927A (en) * | 2019-06-03 | 2019-08-02 | 浙江工业大学 | A kind of catalyst for vinyl chloride synthesis and preparation method thereof and a kind of synthetic method of vinyl chloride |
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Application publication date: 20100602 |