CN103191760A - Acetylene-hydrochlorinated low-content gold compound catalyst - Google Patents
Acetylene-hydrochlorinated low-content gold compound catalyst Download PDFInfo
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Abstract
The invention discloses an acetylene-hydrochlorinated low-content gold compound catalyst, particularly a nonmerculic catalyst which is suitable for synthesis of chloroethylene through an acetylene hydrochlorination reaction. The catalyst comprises carrier active carbon, a main catalysis element and auxiliary elements A and B, wherein the content of the carrier active carbon is 10,000 parts, the main catalysis element is thiosulfate of gold with the content of 1-120 parts, the auxiliary element A is thiosulfate of silver with the content of 50-1,000 parts, the auxiliary element B is alkali metal compound and a mixture of the alkali metal compounds with the content of 50-1,000 parts. According to the acetylene-hydrochlorinated low-content gold compound catalyst disclosed by the invention, the content of gold in the prepared gold compound catalyst is low; the cost of noble metal catalyst is remarkably reduced; the prepared gold compound catalyst is a good-activity, strong-stability and high-selectivity novel nonmerculic catalyst; and the acetylene-hydrochlorinated low-content gold compound catalyst has the advantages of simple production process, short production period and environment-friendliness.
Description
Technical field
The present invention relates to a kind of catalyst, particularly a kind of catalyst that is applicable to the acetylene hydrochlorination synthesizing chloroethylene.
Background technology
VCM is the important synthesis material of polyvinyl chloride, and polyvinyl chloride is one of synthetic resin of China's consumption and output maximum, and the fundamental realities of the country of the few oil of the many coals of China has determined acetylene hydrochlorination method production vinyl chloride still to occupy leading status in China.The environmental pollution that the use that the present subject matter that faces of acetylene hydrochlorination method synthesizing chloroethylene is mercury catalyst brings and a large amount of consumption of mercury resource.Along with strengthening day by day and the international growing tension of limitting the negotiation of mercury treaty of people's environmental consciousness, for keeping the living space of calcium carbide process PVC, the exploitation of no mercury catalyst is imperative.
The research and development of catalyst without mercury at present are divided into the gentle liquid-phase reaction system of gas-solid phase reaction.The gas-liquid phase reaction refers to the catalyst activity component is dissolved in the certain amount of solvent, feeds the reaction that reacting gas prepares vinyl chloride.The typical case of gas-liquid phase reaction is represented as CN200910236255.7 and CN201010185916.The conversion ratio of the acetylene of gas-liquid phase reaction at present is not very high, the catalyst system and catalyzing inactivation is very fast, in addition because the existence of hydrogen chloride, may cause certain corrosion to equipment, because the serial side reaction that has taken place in the system may cause the problem of practical operation such as solidifying of under normal temperature state liquid phase and enforcement, these catalyst system and catalyzings all do not obtain practical application at present in addition.
The gas-solid phase reaction system then is different from gas-liquid phase reaction system fully.Gas-solid phase reaction be with a certain amount of active constituent loading on specific solid phase carrier, feed the reaction that reaction gas prepares vinyl chloride then.The research of gas-solid phase catalyst without mercury is because it is simple to operate, can utilize existing reaction unit directly to react etc. and make it become present research focus.Acetylene hydrochlorination gas-solid phase catalyst without mercury mainly is divided into base metal and noble metal is main active component both direction.Base metal is owing to the cheap common concern that is subjected to the researcher, and wherein CN101497046, CN101671293, CN102151581A are the catalyst system and catalyzing of main active component with base metals such as Cu, Bi, MoP respectively, have obtained certain achievement.Some base metal catalysts activity is higher, but inactivation is very fast, and life of catalyst is undesirable.
The research of noble metal catalyst aspect has also obtained certain progress.Mentioning with 0.5 ~ 3 part of (namely 0.24 ~ 1.43%) palladium, platinum, gold, rhodium chloride among the patent CN200810044560.1 is main active component, and one or more are co-catalyst in 1 ~ 10 part of stannous chloride, cerium chloride and bismuth chloride, at air speed 250 ~ 500h
-1, under the reaction condition that reaction temperature is 110 ~ 160 ℃, obtaining conversion of alkyne 95% ~ 98%, vinyl chloride is selectively greater than 99%.Halide, the complex compound of the gold of patent CN 200910196849.X employing 0.1 ~ 10% are main active component, and the halide of the potassium of employing 0.1 ~ 10%, barium, lanthanum, copper, acetate, phosphate, complex compound are for helping active component, at air speed 50 ~ 200h
-1Down, under 120 ~ 180 ℃ of conditions of reaction temperature, obtain conversion of alkyne 90% ~ 99%, vinyl chloride selectively be 97 ~ 99.9%.The main active component of patent CN200910228149.4 is the chloride of 2～15% palladiums or gold, and helping active component is 1～5% rare earth compound, and its main feature has prepared the noble metal catalyst without mercury for the method that adopts the secondary vacuum dipping, with it at 30 ~ 90h
-1Air speed under, under the reaction condition of 150 ℃ of reactions, react, obtain conversion of alkyne 98 ~ 99%, selective 98 ~ 99.9% of vinyl chloride.
Adopting gold, platinum, rhodium, ruthenium, palladium, iridium metals chloride, phosphate, sulfate and the oxide of 0.05 ~ 0.5% low precious metal content among the patent CN 201010272612.8 is main active component, 0.1 the phosphate of～5% copper, zinc, potassium, barium, nickel, bismuth, calcium, lithium and rare-earth metal chloride, sulfate and oxide are for helping active component, with active carbon, molecular sieve, silica gel, CNT, TiO
2Or aluminium oxide is carrier, at 20 ~ 2000h
-1Under the air speed, under 100 ~ 250 ℃ of reaction temperatures, obtain conversion of alkyne 40 ~ 85%, selective 98 ~ 99% of vinyl chloride.
It is main active component that patent CN201110150287.2 has also adopted chlorauride or the ruthenic chloride of 0.05 ~ 0.5% low precious metal content, the chloride of the bismuth of employing 0.05 ~ 0.5%, barium, manganese, iron etc. is for helping active component, be carrier with the active carbon, but its characteristics are washed to pH=4-5 for active carbon wherein through the persalt stir process, re-use modifier ultrasonic processing under the condition of 25 ~ 60KHz after the drying, modifier is: the ethanol solution of ethamine, ethylenediamine, triethylamine, hexamethylenetetramine, KH-550, KH-560, KH-570 silane coupler.This kind noble metal catalyst without mercury can obtain 65 ~ 99% conversion of alkyne.Adopting the halide of 0.1 ~ 5% palladium or the noble metal of complex compound and 0.1 ~ 3% among patent CN201110257696.2 and the patent CN 201110257697.7 respectively is active component, carrier is for being respectively molecular sieve HZSM-5, NaZSM-5, H β type and HY type modenite and active carbon, same its main feature also is the vehicle treated method: carrier is added pretreating reagent through stirring, dipping, backflow or ultrasonic, clean to faintly acid then.Pretreating reagent is: hydrochloric acid, nitric acid, phosphoric acid, potassium permanganate, hydrogen peroxide, NaOH, potassium hydroxide, ammoniacal liquor, organic acid etc.Under certain air speed and reaction condition, all can obtain higher conversion ratio.
It is active component that patent CN201110199651.4 adopts chloride or the nitrate of gold element, cobalt element, lanthanum element, auxiliary agent is the chloride of potassium, sodium, bismuth, iron etc., be that maceration extract prepares the noble metal catalyst without mercury with the chloroazotic acid, wherein the content of Precious Metals-Gold is 0.3 ~ 2%.Be 0.3% content at gold wherein, the employing molecular sieve is carrier, at 12h
-1Air speed under keep conversion of alkyne and reaching 970h more than 99%.
All adopted the main active component of precious metal element gold as catalyst in these several the patents.In the last few years, because the catalytic activity height of Precious Metals-Gold, the catalysis scope extensively becomes the research focus of industry, also obtained certain progress, obtain the better conversion rate, but in the acetylene hydrochlorination reaction system, because acetylene has higher reproducibility, easily make the Au in the main active component in the catalyst
3+And Au
+Be transformed into Au
0Thereby the inactivation that has caused catalyst, though so catalytic activity height of Precious Metals-Gold catalyst, but its less stable, life-span is shorter, and adding the scope that gold content covers in the noble metal catalyst without mercury is 0.05 ~ 15%, all than higher, make that the cost of Precious Metals-Gold catalyst without mercury is high, be difficult in and obtain commercial Application in the acetylene hydrochlorination.
Summary of the invention
The object of the invention is to solve uses highly toxic mercury catalyst in the carbide acetylene method Production of PVC, the mercury consumption is big in the production, environmental pollution is serious, existing noble metal catalyst less stable, the problem that cost is high, and then provide a kind of catalytic activity good, selective high, bullion content low (being low to moderate below 0.5%), low a kind of catalyst compounded for acetylene hydrochlorination low content gold of catalyst cost.
A kind of acetylene hydrochlorination low content gold is catalyst compounded, the component that comprises following content: 10000 parts of carrier active carbons, 1 ~ 120 part of main catalytic composition composite metal salt, each 50～1000 parts of auxiliary element A and B, the main catalytic composition is the compound of gold, auxiliary element A is the compound of silver, and auxiliary element B is alkali metal compound or its mixture.
Described a kind of acetylene hydrochlorination low content gold is catalyst compounded, and its main catalytic composition is the thiosulfate of gold.It mainly acts on is the sodium byposulfite stable complex ion that forms gold, makes gold ion be not easy to be reduced.
Described a kind of acetylene hydrochlorination low content gold is catalyst compounded, and its auxiliary element A is the thiosulfate of silver.It mainly acts on is to select for use the same main group compound silver with similar electronic structure as composite component, and the thiosulfuric acid salt complex of silver, makes the more even of activity component impregnation, and simultaneously gold and silver composite has certain synergy.
Described a kind of acetylene hydrochlorination low content gold is catalyst compounded, and its auxiliary element B is potassium chloride.It mainly acts on is to select alkali metal compound for use, alkali metal compound has the effect of certain anti-carbon deposit, the more tiny homogeneous that active component is disperseed, increase dispersion degree of active components, and can also prevent gathering and inactivation of active component in course of reaction, so the adding of auxiliary element potassium chloride can further improve the stability of catalyst.
Described a kind of acetylene hydrochlorination low content gold is catalyst compounded, and its auxiliary element B is cesium chloride.
Described a kind of acetylene hydrochlorination low content gold is catalyst compounded, and it at first prepares certain density chlorauric acid solution, and it is standby to prepare certain density hypo solution again; Take by weighing a certain amount of chlorauric acid solution, add a certain amount of deionized water dilution; Take by weighing a certain amount of silver salt and stirring again; Adding a certain amount of hypo solution then stirs; Take by weighing a certain amount of auxiliary element B at last again and add in the above-mentioned solution and stir, in this solution, add active carbon, impregnation drying.
Described a kind of acetylene hydrochlorination low content gold is catalyst compounded, and the mass percent concentration of its thiosulfate solution is 3 ~ 35.6%, forms the stable complex ion of the thiosulfate of gold.
Described a kind of acetylene hydrochlorination low content gold is catalyst compounded, and its dip time is 4-24h, and baking temperature is 60-180 ℃.
Described a kind of acetylene hydrochlorination low content gold is catalyst compounded, and its described carrier active carbon specific area is 800 ~ 3500m
2/ g, micropore ratio 〉=50% of carrier.Adopt the active carbon of bigger serface, it is more even to make active component disperse, and increases dispersion degree of active components, under the situation that has guaranteed the activity of such catalysts site, greatly reduces gold content.
Described a kind of acetylene hydrochlorination low content gold is catalyst compounded, and its thiosulfate solution can be ammonia thiosulfate or potassium thiosulfate.
Described a kind of acetylene hydrochlorination low content gold is catalyst compounded, and its auxiliary element B can be alkaline earth metal compound, rare earth compound and composition thereof.
The present invention at first adopts S
2O
3 2-And Au
3+Complexing forms the stable [Au (S with δ-Π feedback bonding
2O
3)
2]
3-Complex ion makes the Au in the main active component
+Difficulty is reduced; Secondly, employing is with the thiosulfuric acid salt complex [Ag (S of main group transistion metal compound silver
2O
3)
2]
3-Reaching alkali metal compound potassium chloride and cesium chloride is composite component, wherein silver not only has similar electronic structure with gold, and has similar complex structure, can make activity component impregnation more even, simultaneously gold and silver composite has certain synergy, can improve the conversion ratio of catalyst; Composite with alkali metal potassium chloride and cesium chloride again, can further make the more tiny of active component particle dispersion and homogeneous, the poly-effect also that prevents active component is also played in the adding of potassium chloride or cesium chloride in this external course of reaction, also can play simultaneously certain anti-carbon effect, thereby improve the stability of catalyst, prolong life of catalyst; Adopt the active carbon of bigger serface at last, it is more even to make active component disperse, and increases dispersion degree of active components, under the situation that has guaranteed the activity of such catalysts site, greatly reduces gold content.
The present invention greatly reduces the content of gold under the prerequisite that does not reduce catalyst activity and stability in sum, and the cost of noble metal catalyst without mercury is reduced greatly.
Provided by the invention a kind of catalyst compounded for acetylene hydrochlorination low content gold, at 12h
-1Air speed when reaction, initial conversion can reach 40 ~ 99%, conversion ratio still can be kept stablely behind reaction 4 ~ 15h, and selectively can the reaching more than 98% of vinyl chloride can solve and use highly toxic mercury catalyst in the carbide acetylene method Production of PVC, the mercury consumption is big in the production, environmental pollution is serious, existing noble metal catalyst less stable, the problem that cost is high, wherein the golden mass percent that accounts for carrier is in 5 ‰ ~ 0.05 ‰ scopes, greatly reduces the cost of Precious Metals-Gold 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.
At first prepare chlorauric acid solution: the 1g gold chloride is dissolved in the 100ml volumetric flask is mixed with chlorauric acid solution.For the subsequent sample preparation is prepared.
Embodiment 1
Weighing Na
2S
2O
3﹒ 5H
2O is 16.9485g, and it is dissolved in the 30ml deionized water, and is standby after stirring.Weighing chlorauric acid solution 1.5839g adds the dilution of 10ml deionized water in this beaker in beaker.Weighing AgNO again
3Add in the middle of the chlorauric acid solution that has diluted for 0.6000g, after stirring, add standby hypo solution, being stirred to does not have precipitation.The KCL of last weighing 0.4500g joins in the above-mentioned solution liquid and stirring.Add the 15g active carbon in above-mentioned maceration extract, stir normal temperature dipping 12h, dry 12h under 105 ℃ of conditions then.This catalyst is used in the middle of the acetylene hydrochlorination synthesizing chloroethylene, at 12h
-1Under the air speed, logical nitrogen drying 30min under 180 ℃ of conditions, logical hydrogen chloride activation 30min feeds acetylene at last and begins reaction then, obtains conversion of alkyne 99%, selective 98% of vinyl chloride.
Embodiment 2
Weighing Na
2S
2O
3﹒ 5H
2O is 155.85g, and it is dissolved in the 30ml deionized water, and is standby after stirring.Weighing chlorauric acid solution 15.8390g adds the dilution of 10ml deionized water in this beaker in beaker.Weighing AgNO again
3Add in the middle of the chlorauric acid solution that has diluted for 0.0750g, after stirring, add standby hypo solution, being stirred to does not have precipitation.The KCL of last weighing 1.5000g joins in the above-mentioned solution liquid and stirring.Add the 15g active carbon in above-mentioned maceration extract, stir normal temperature dipping 12h, dry 12h under 105 ℃ of conditions then.This catalyst is used in the middle of the acetylene hydrochlorination synthesizing chloroethylene, at 12h
-1Under the air speed, logical nitrogen drying 30min under 180 ℃ of conditions, logical hydrogen chloride activation 30min feeds acetylene at last and begins reaction then, obtains conversion of alkyne 99.8%, selective 99% of vinyl chloride.
Embodiment 3
Weighing Na
2S
2O
3﹒ 5H
2O is 5.0079g, and it is dissolved in the 30ml deionized water, and is standby after stirring.Weighing chlorauric acid solution 0.1584g adds the dilution of 10ml deionized water in this beaker in beaker.Weighing AgNO again
3Add in the middle of the chlorauric acid solution that has diluted for 1.5000g, after stirring, add standby hypo solution, being stirred to does not have precipitation.The KCL of last weighing 0.1500g joins in the above-mentioned solution liquid and stirring.Add the 15g active carbon in above-mentioned maceration extract, stir normal temperature dipping 12h, dry 12h under 105 ℃ of conditions then.This catalyst is used in the middle of the acetylene hydrochlorination synthesizing chloroethylene, at 12h
-1Under the air speed, logical nitrogen drying 30min under 180 ℃ of conditions, logical hydrogen chloride activation 30min feeds acetylene at last and begins reaction then, obtains conversion of alkyne 45%, selective 98% of vinyl chloride.
Embodiment 4
Weighing Na
2S
2O
3﹒ 5H
2O is 16.9485g, and it is dissolved in the 30ml deionized water, and is standby after stirring.Weighing chlorauric acid solution 1.5839g adds the dilution of 10ml deionized water in this beaker in beaker.Weighing AgNO again
3Add in the middle of the chlorauric acid solution that has diluted for 0.6000g, after stirring, add standby hypo solution, being stirred to does not have precipitation.The CsCL of last weighing 0.4500g joins in the above-mentioned solution liquid and stirring.Add the 15g active carbon in above-mentioned maceration extract, stir normal temperature dipping 12h, dry 12h under 105 ℃ of conditions then.This catalyst is used in the middle of the acetylene hydrochlorination synthesizing chloroethylene, at 12h
-1Under the air speed, logical nitrogen drying 30min under 180 ℃ of conditions, logical hydrogen chloride activation 30min feeds acetylene at last and begins reaction then, obtains conversion of alkyne 95%, selective 98% of vinyl chloride.
Embodiment 5
Weighing Na
2S
2O
3﹒ 5H
2O is 155.85g, and it is dissolved in the 30ml deionized water, and is standby after stirring.Weighing chlorauric acid solution 15.8390g adds the dilution of 10ml deionized water in this beaker in beaker.Weighing AgNO again
3Add in the middle of the chlorauric acid solution that has diluted for 0.0750g, after stirring, add standby hypo solution, being stirred to does not have precipitation.The CsCL of last weighing 1.5000g joins in the above-mentioned solution liquid and stirring.Add the 15g active carbon in above-mentioned maceration extract, stir normal temperature dipping 12h, dry 12h under 105 ℃ of conditions then.This catalyst is used in the middle of the acetylene hydrochlorination synthesizing chloroethylene, at 12h
-1Under the air speed, logical nitrogen drying 30min under 180 ℃ of conditions, logical hydrogen chloride activation 30min feeds acetylene at last and begins reaction then, obtains conversion of alkyne 99%, selective 99% of vinyl chloride.
Embodiment 6
Weighing Na
2S
2O
3﹒ 5H
2O is 5.0079g, and it is dissolved in the 30ml deionized water, and is standby after stirring.Weighing chlorauric acid solution 0.1584g adds the dilution of 10ml deionized water in this beaker in beaker.Weighing AgNO again
3Add in the middle of the chlorauric acid solution that has diluted for 1.5000g, after stirring, add standby hypo solution, being stirred to does not have precipitation.The CsCL of last weighing 0.1500g joins in the above-mentioned solution liquid and stirring.Add the 15g active carbon in above-mentioned maceration extract, stir normal temperature dipping 12h, dry 12h under 105 ℃ of conditions then.This catalyst is used in the middle of the acetylene hydrochlorination synthesizing chloroethylene, at 12h
-1Under the air speed, logical nitrogen drying 30min under 180 ℃ of conditions, logical hydrogen chloride activation 30min feeds acetylene at last and begins reaction then, obtains conversion of alkyne 40%, selective 98% of vinyl chloride.
Claims (9)
1. an acetylene hydrochlorination low content gold is catalyst compounded, the component that comprises following content: 10000 parts of carrier active carbons, 1 ~ 120 part of main catalytic composition composite metal salt, each 50～1000 parts of auxiliary element A and B, it is characterized in that the main catalytic composition is the compound of gold, auxiliary element A is the compound of silver, and auxiliary element B is alkali metal compound or its mixture.
2. a kind of acetylene hydrochlorination low content gold according to claim 1 is catalyst compounded, it is characterized in that the main catalytic composition is the thiosulfate of gold.
3. a kind of acetylene hydrochlorination low content gold according to claim 1 is catalyst compounded, it is characterized in that auxiliary element A is the thiosulfate of silver.
4. a kind of acetylene hydrochlorination low content gold according to claim 1 is catalyst compounded, it is characterized in that auxiliary element B is potassium chloride.
5. a kind of acetylene hydrochlorination low content gold according to claim 1 is catalyst compounded, it is characterized in that auxiliary element B is cesium chloride.
6. the catalyst compounded preparation method of a kind of acetylene hydrochlorination low content gold according to claim 1 is characterized in that at first preparing certain density chlorauric acid solution, and it is standby to prepare certain density hypo solution again; Take by weighing a certain amount of chlorauric acid solution, add a certain amount of deionized water dilution; Take by weighing a certain amount of silver salt and stirring again; Adding a certain amount of hypo solution then stirs; Take by weighing a certain amount of auxiliary element B at last again and add in the above-mentioned solution and stir, in this solution, add active carbon, impregnation drying.
7. a kind of acetylene hydrochlorination low content gold according to claim 6 is catalyst compounded, and the mass percent concentration that it is characterized in that thiosulfate solution is 3 ~ 35.6%.
8. a kind of acetylene hydrochlorination low content gold according to claim 6 is catalyst compounded, it is characterized in that dip time is 4-24h, and baking temperature is 60-180 ℃.
9. a kind of acetylene hydrochlorination low content gold according to claim 1 is catalyst compounded, it is characterized in that described carrier active carbon specific area is 800 ~ 3500m
2/ g, micropore ratio 〉=50% of carrier.
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| CN104289233A (en) * | 2014-08-29 | 2015-01-21 | 冯良荣 | Sulfide catalyst for preparing vinyl chloride through hydrochlorination of acetylene |
| CN104707602A (en) * | 2013-12-13 | 2015-06-17 | 索尔维公司 | Method for manufacturing vinyl chloride from acetylene and hydrogen chloride |
| CN107185533A (en) * | 2017-05-19 | 2017-09-22 | 新疆中泰化学股份有限公司 | Induction period controllable VCM synthesis Au-based catalyst and preparation method thereof |
| CN107442118A (en) * | 2017-08-04 | 2017-12-08 | 内蒙古大学 | A kind of preparation method of acetylene hydrochlorination preparing chloroethylene tantalum base catalyst |
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| CN112570043A (en) * | 2020-12-08 | 2021-03-30 | 西安凯立新材料股份有限公司 | Catalyst for acetylene hydrochlorination and application thereof |
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| EA030122B1 (en) * | 2013-12-13 | 2018-06-29 | Солвей Са | Method for production of vinyl chloride from acetylene and hydrogen chloride |
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| CN107715919B (en) * | 2017-09-29 | 2020-10-09 | 浙江工业大学 | Load type [ PdSClx]x-Catalyst, preparation thereof and application of catalyst in vinyl chloride synthesis |
| CN107715915A (en) * | 2017-09-29 | 2018-02-23 | 浙江工业大学 | A kind of palladium catalyst for vulcanizing ionic liquid complexing and preparation method and application |
| CN108126721A (en) * | 2017-12-21 | 2018-06-08 | 厦门大学 | A kind of Au-based catalyst and its preparation method and application |
| CN109876864A (en) * | 2019-02-14 | 2019-06-14 | 西安凯立新材料股份有限公司 | A kind of super low loading noble metal composite catalyst and preparation method thereof for acetylene hydrochlorination reaction |
| CN113692316A (en) * | 2019-06-20 | 2021-11-23 | 庄信万丰股份有限公司 | Gold-containing catalyst, preparation method and application |
| CN112007695A (en) * | 2020-09-23 | 2020-12-01 | 中国科学院大连化学物理研究所 | Sulfur-containing silane coupling agent modified gold catalyst for acetylene hydrochlorination |
| CN112007695B (en) * | 2020-09-23 | 2021-10-08 | 中国科学院大连化学物理研究所 | Sulfur-containing silane coupling agent modified gold catalyst for acetylene hydrochlorination |
| CN112570043A (en) * | 2020-12-08 | 2021-03-30 | 西安凯立新材料股份有限公司 | Catalyst for acetylene hydrochlorination and application thereof |
| CN113663740A (en) * | 2021-07-28 | 2021-11-19 | 新疆至臻化工工程研究中心有限公司 | Passivation type ultralow-content gold catalyst |
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