CN103506147A - Acetylene hydrochlorination structured catalyst and preparation method thereof - Google Patents
Acetylene hydrochlorination structured catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of structured catalytic materials, in particular to an acetylene hydrochlorination structured catalyst and a preparation method thereof. The structured catalyst adopts a porous foam structure, and comprises a porous foam primary carrier, a coating secondary carrier and an active component, wherein the secondary carrier coating is evenly distributed on the surface of the primary carrier, and is 0.1-500 microns in thickness; the active component is evenly distributed in the secondary carrier coating. The structured catalyst adopts the porous foam as the primary carrier and the powder coating with large specific surface area as the secondary carrier to be loaded with the noble metal active component for the reaction of preparing chloroethylene through acetylene hydrochlorination, so as to solve the problems such as severe pollution, concentrated heat emission and short service life in the existing mercuric chloride catalyst for static beds. The technology is simple, and needs no complex equipment; under the same reaction conditions, the dosage of the noble metal catalyst with the same volume is only 1/3-1/10 of that reported at present, and the same conversion rate and selectivity can be achieved; the service life is 2-8 times of the reported service life.
Description
Technical field
The present invention relates to structured catalysis Material Field, specifically a kind of acetylene hydrochlorination reaction structure Catalysts and its preparation method.
Background technology
Polyvinyl chloride (PVC), as one of the world's five large general-purpose plastics, is widely used in the every field of the national economy such as building materials, household electrical appliances, commodity.In recent years, the demand of worldwide PVC resin constantly increases, and especially the apparent consumption amount of China's polyvinyl chloride in 2011 surpasses 1/5th of world consumption total amount, is second-biggest-in-the-world production and consumption big country.
In current industrial applications, vinyl chloride production technology mainly contains two kinds of carbide acetylene method and ethene balancing methods.Along with the development of vinyl chloride production technology, the developed country of rich in petroleum resources eliminates acetylene method with ethylene process substantially.But China is because being subject to the endowment of resources restriction of rich coal, oil-poor, weak breath, and the production technology of VCM mainly be take carbide as main, by December, 2007, carbide accounts for the more than 70% of China PVC aggregated capacity.Yet along with the severe contamination that plaque is day by day weary and mercury catalyst brings, particularly China of China's mercury resource added " Minamata treaty " to make the sustainable development of acetylene method process route be subject to serious restriction.Therefore, the process route that cleans of exploitation catalyst without mercury catalyzing acetylene hydrochlorination preparing chloroethylene seems extremely urgent.
At present, it is active component that the catalyst without mercury of catalyzing acetylene hydrochlorination mainly be take the rare precious metals such as gold, ruthenium and platinum, can obtain good catalytic effect, but because rare precious metal consumption is large, inactivation is fast, cost is high, therefore always cannot industrialization.
Summary of the invention
The object of the present invention is to provide a kind of acetylene hydrochlorination reaction structure Catalysts and its preparation method, solve the existing fixed bed problems such as mercuric chleride catalyst is seriously polluted, and heat release is concentrated, and the life-span is short.
Technical scheme of the present invention is:
A kind of acetylene hydrochlorination reaction structure catalyst, this structure catalyst is porous foam structure, by carrier of porous foam, coating secondary carrier and active component three parts, formed, secondary carrier coating is evenly distributed in carrier surface one time, the thickness of secondary carrier coating is 0.1～500 μ m, active component is evenly distributed in the coating of secondary carrier, and in secondary carrier, the content of active component accounts for 0.001wt%～70wt%.
Described acetylene hydrochlorination reaction structure catalyst, carrier of porous foam is foam-like carrier: foam silicon carbon, foamy carbon and foamed alumina, carrier is three-dimensional UNICOM network structure, and porosity is 30%～90%.
Described acetylene hydrochlorination reaction structure catalyst, secondary carrier coating is one or more the combination in activated carbon coating, aluminum oxide coating layer, magnesium oxide coating, titania coating, silica coating and molecular sieve coating, secondary carrier coating layer thickness is preferably 10～200 μ m, and in secondary carrier, the preferred content of active component accounts for 0.5wt%～10wt%.
Described acetylene hydrochlorination reaction structure catalyst, active component is one or more the combination in gold, platinum, palladium, ruthenium and rhodium.
The preparation method of described acetylene hydrochlorination reaction structure catalyst, comprises the steps:
(1), by after the secondary carrier ball milling of powdery, add adhesive and solvent through fully stirring and make slip, secondary carrier: adhesive: the proportioning of solvent is 50～500g:50～200g:1000mL; Again a carrier foam framework is immersed in slurry, after taking-up, by extruding, air-blowing or centrifugation, remove unnecessary slurry;
(2) the above-mentioned carrier soaking after hanging material is carried out to baking and curing in thermal environment;
(3) by the carrier after solidifying, carry out pyrolysis, remove and affect reactive material;
(4) carrier after pyrolysis is immersed in the salting liquid that contains active component, the concentration of active component is 0.001wt%～70wt%, after 30～200 ℃ of oil baths heating 0.5～10 hour are aging, take out and dries, and obtains the structure catalyst of acetylene hydrochlorination reaction.
The preparation method of described acetylene hydrochlorination reaction structure catalyst, in step (1), secondary carrier be activated carbon, aluminium oxide, magnesia, titanium oxide, silica and molecular sieve one or more; Adhesive be epoxy resin, phenolic resins, polyvinyl alcohol, polyurethane, methylcellulose, butyl titanate, ethyl orthosilicate, aluminum hydroxide sol and Ludox one or more; Solvent be water, ethanol, ethylene glycol, acetic acid, toluene, dimethylbenzene, oxolane, acetone, benzinum, isopropyl alcohol and normal butane one or more.
The preparation method of described acetylene hydrochlorination reaction structure catalyst, in step (3), pyrolysis temperature is 300～1000 ℃, 0.5～12 hour time.
The preparation method of described acetylene hydrochlorination reaction structure catalyst, in step (4), the combination of one or more in the villaumite that the salt of active component is metal, nitrate, phosphate, acetate and complex compound thereof.
The present invention has following beneficial effect:
1, the present invention be take porous foam as a carrier, bigger serface powder coating is that secondary carrier supports noble metal active component for structure catalyst of preparing chloroethylene by acetylene hydrochlorination reaction and preparation method thereof, prepared acetylene hydrochlorination reaction structure catalyst, preparation method is simple, active component is stable, environmental friendliness, nontoxic pollution-free.
2, the preparation technology of the prepared acetylene hydrochlorination reaction structure catalyst of the present invention is simple, without complex apparatus, under equivalent responses condition, same volume catalyst noble metal dosage is only to report at present 1/3～1/10 of consumption, can reach identical conversion ratio and selective, the life-span is 2～8 times of the report life-span.
The specific embodiment
The structure catalyst of acetylene hydrochlorination reaction of the present invention, this structure catalyst is porous foam structure, by carrier of porous foam, coating secondary carrier and active component three parts, formed, secondary carrier coating is evenly distributed in carrier surface one time, the thickness of secondary carrier coating is 0.1～500 μ m, active component is evenly distributed in the coating of secondary carrier, and in secondary carrier, the content of active component accounts for 0.001wt%～70wt%.
In the present invention, carrier of porous foam mainly comprises the foam-like carriers such as foam silicon carbon, foamy carbon or foamed alumina, and carrier is three-dimensional UNICOM network structure, and porosity is 30%～90%; Secondary carrier coating comprise activated carbon coating, aluminum oxide coating layer, magnesium oxide coating, titania coating, silica coating and molecular sieve coating etc. one or more, secondary carrier coating is evenly distributed in carrier surface one time, and coating layer thickness is 0.1～500 μ m; The main metal of active component be gold, platinum, palladium, ruthenium and rhodium one or more, the salt of active component be metal villaumite, nitrate, phosphate, acetate and complex compound one or more, the preparation method of the structure catalyst of acetylene hydrochlorination reaction of the present invention, comprises the steps:
(1) by the secondary carrier of powdery, (secondary carrier is activated carbon, aluminium oxide, magnesia, titanium oxide, silica and molecular sieve one or more) after ball milling, (adhesive is epoxy resin to add adhesive, phenolic resins, polyvinyl alcohol, polyurethane, methylcellulose, butyl titanate, ethyl orthosilicate, aluminum hydroxide sol and Ludox one or more) and solvent (solvent is water, ethanol, ethylene glycol, acetic acid, toluene, dimethylbenzene, oxolane, acetone, benzinum, isopropyl alcohol and normal butane one or more) through fully stirring and make slip, secondary carrier: adhesive: the proportioning of solvent is 50～500g:50～200g:1000mL, again carrier foam framework is immersed in slurry, after taking-up, by extruding, air-blowing or the mode such as centrifugal, remove unnecessary slurry,
(2) the above-mentioned carrier soaking after hanging material is carried out to baking and curing in thermal environment;
(3) by the carrier after solidifying, carry out pyrolysis, pyrolysis temperature is 300～1000 ℃, 0.5～12 hour time, removes and affects reactive material;
(4) carrier after pyrolysis is immersed in the salting liquid that contains active component, the concentration of active component is that 0.001wt%～70wt%(is preferably 0.01～10wt%), after 30～200 ℃ of oil baths heating 0.5～10 hour is aging, take out and dry, obtain the structure catalyst of acetylene hydrochlorination reaction.
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
Preparation and the activity rating of acetylene hydrochlorination reaction structure catalyst of the present invention, comprise the steps:
(1) preparation of activated carbon coating/foam silicon carbon
Concrete operation step refers to patent application " a kind of activated carbon coating/foam silicon carbon structure catalyst and preparation method thereof ", number of patent application: 201210306110.1.
(2) dipping
By 40mg AuCl
3hCl4H
2o, is dissolved in 40ml water, adds 9ml hydrochloric acid and 3ml nitric acid, activated carbon coating/the foam silicon carbon that is 23.5ml by volume adds in the solution preparing, 140 ℃ of oil bath heating, after 5 hours, are dried 24 hours by gained catalyst at 120 ℃, obtain the structure catalyst of acetylene hydrochlorination reaction.
In the present embodiment, this structure catalyst is porous foam structure, by carrier of porous foam, coating secondary carrier and active component three parts, formed, secondary carrier coating is evenly distributed in carrier surface one time, the thickness of secondary carrier coating is 50 μ m, active component is evenly distributed in the coating of secondary carrier, and in secondary carrier, the content of active component accounts for 1.0wt%.
(3) catalytically active assessment
By gained catalyst at 165 ℃, acetylene air speed 240h
-1, hydrogen chloride and acetylene molar ratio are under 1.1:1 condition, to carry out catalytically active assessment, gained initial conversion is 97.32%, is selectively 99.9%, after reaction 12h, its conversion ratio is still>95%.
Embodiment 2
(1) preparation of aluminium oxide/foam silicon carbon
Concrete operation step refers to patent application " method of preparing aluminium oxide active coating and three-way catalyst on foamed conducting ceramic ", number of patent application: CN00136037.X.
(2) dipping
By 40mg AuCl
3hCl4H
2o, 2mgPdCl
2, be dissolved in 40ml water, add 3ml hydrochloric acid and 1ml nitric acid, aluminium oxide/the foam silicon carbon that is 23.5ml by volume adds in the solution preparing, 120 ℃ of oil bath heating, after 5 hours, are dried 24 hours by gained catalyst at 100 ℃, obtain the structure catalyst of acetylene hydrochlorination reaction.
In the present embodiment, this structure catalyst is porous foam structure, by carrier of porous foam, coating secondary carrier and active component three parts, formed, secondary carrier coating is evenly distributed in carrier surface one time, the thickness of secondary carrier coating is 100 μ m, active component is evenly distributed in the coating of secondary carrier, and in secondary carrier, the content of active component accounts for 0.55wt%.
(3) catalytically active assessment
By gained catalyst at 185 ℃, acetylene air speed 60h
-1, hydrogen chloride and acetylene molar ratio are 1.2:1, carry out catalytically active assessment under condition, gained initial conversion is 86.21%, is selectively 90.5%, after reaction 6h, its reaction conversion ratio is still>50%.
Embodiment 3
(1) preparation of titanium oxide/foam silicon carbon
Concrete operation step refers to patent application " a kind of titania coating/ceramic structure catalyst carrier and preparation method ", number of patent application: CN200910013444.8.
(2) dipping
By 40mg AuCl
3hCl4H
2o, is dissolved in 40ml water, adds 6ml hydrochloric acid and 2ml nitric acid, titanium oxide/the foam silicon carbon that is 23.5ml by volume adds in the solution preparing, 160 ℃ of oil bath heating, after 5 hours, are dried 48 hours by gained catalyst at 80 ℃, obtain the structure catalyst of acetylene hydrochlorination reaction.
In the present embodiment, this structure catalyst is porous foam structure, by carrier of porous foam, coating secondary carrier and active component three parts, formed, secondary carrier coating is evenly distributed in carrier surface one time, the thickness of secondary carrier coating is 60 μ m, active component is evenly distributed in the coating of secondary carrier, and in secondary carrier, the content of active component accounts for 0.75wt%.
(3) catalytically active assessment
By gained catalyst at 165 ℃, acetylene air speed 120h
-1, hydrogen chloride and acetylene molar ratio are under 1.15:1 condition, to carry out catalytically active assessment, gained initial conversion is 96.21%, is selectively 99.5%, after reaction 15h, its reaction conversion ratio is still>90%.
Embodiment 4
(1) preparation of molecular sieve/foam silicon carbon
Concrete operation step refers to patent application " a kind of preparation method of molecular sieve coating material on porous silicon carbide ceramic surface ", number of patent application: CN200910011054.7.
(2) dipping
By 40mg AuCl
3hCl4H
2o, is dissolved in 40ml water, adds 8ml hydrochloric acid and 2ml nitric acid, molecular sieve/the foam silicon carbon that is 23.5ml by volume adds in the solution preparing, 140 ℃ of oil bath heating, after 8 hours, are dried 48 hours by gained catalyst at 80 ℃, obtain the structure catalyst of acetylene hydrochlorination reaction.
In the present embodiment, this structure catalyst is porous foam structure, by carrier of porous foam, coating secondary carrier and active component three parts, formed, secondary carrier coating is evenly distributed in carrier surface one time, the thickness of secondary carrier coating is 35 μ m, active component is evenly distributed in the coating of secondary carrier, and in secondary carrier, the content of active component accounts for 1.5wt%.
(3) catalytically active assessment
By gained catalyst at 185 ℃, acetylene air speed 120h
-1, hydrogen chloride and acetylene molar ratio are under 1.1:1 condition, to carry out catalytically active assessment, gained initial conversion is 95.21%, is selectively 98.5%, after reaction 12h, its reaction conversion ratio is still>80%.
Embodiment 5
Difference from Example 1 is, a carrier is porous foam carbon, acetylene air speed 300h
-1.
In the present embodiment, this structure catalyst is porous foam structure, by carrier of porous foam, coating secondary carrier and active component three parts, formed, secondary carrier coating is evenly distributed in carrier surface one time, the thickness of secondary carrier coating is 150 μ m, active component is evenly distributed in the coating of secondary carrier, and in secondary carrier, the content of active component accounts for 0.8wt%.
The activity index of the present embodiment catalyst is: initial conversion is 93.72%, is selectively 99%, and after reaction 12h, its conversion ratio is still > 80%.
Embodiment 6
Difference from Example 2 is, one time carrier is porous foam carbon, with 100mgRuCl
3replace 40mgAuCl
3hCl4H
2o.
In the present embodiment, this structure catalyst is porous foam structure, by carrier of porous foam, coating secondary carrier and active component three parts, formed, secondary carrier coating is evenly distributed in carrier surface one time, the thickness of secondary carrier coating is 50 μ m, active component is evenly distributed in the coating of secondary carrier, and in secondary carrier, the content of active component accounts for 4wt%.
The activity index of the present embodiment catalyst is: initial conversion is 95.11%, is selectively 95%.After reaction 8h, its conversion ratio is still > 70%.
Embodiment 7
Difference from Example 3 is, one time carrier is porous foam carbon, with 100mgPtCl
2replace 40mgAuCl
3hCl4H
2o.
In the present embodiment, this structure catalyst is porous foam structure, by carrier of porous foam, coating secondary carrier and active component three parts, formed, secondary carrier coating is evenly distributed in carrier surface one time, the thickness of secondary carrier coating is 40 μ m, active component is evenly distributed in the coating of secondary carrier, and in secondary carrier, the content of active component accounts for 4.5wt%.
The activity index of the present embodiment catalyst is: initial conversion is 97.56%, is selectively 95%.After reaction 8h, its conversion ratio is still > 80%.
Embodiment 8
Difference from Example 1 is, a carrier is porous foam aluminium oxide.
In the present embodiment, this structure catalyst is porous foam structure, by carrier of porous foam, coating secondary carrier and active component three parts, formed, secondary carrier coating is evenly distributed in carrier surface one time, the thickness of secondary carrier coating is 80 μ m, active component is evenly distributed in the coating of secondary carrier, and in secondary carrier, the content of active component accounts for 1.5wt%.
The activity index of the present embodiment catalyst is: initial conversion is 80.23%, is selectively 98.5%.After reaction 8h, its conversion ratio is still > 70%.
Embodiment 9
Difference from Example 2 is, a carrier is foamed alumina.
In the present embodiment, this structure catalyst is porous foam structure, by carrier of porous foam, coating secondary carrier and active component three parts, formed, secondary carrier coating is evenly distributed in carrier surface one time, the thickness of secondary carrier coating is 120 μ m, active component is evenly distributed in the coating of secondary carrier, and in secondary carrier, the content of active component accounts for 2.0wt%.
The activity index of the present embodiment catalyst is: initial conversion is 75.21%, is selectively 98%.After reaction 12h, its conversion ratio is still > 65%.
Embodiment 10
Difference from Example 1 is, acetylene air speed 60h
-1.
In the present embodiment, this structure catalyst is porous foam structure, by carrier of porous foam, coating secondary carrier and active component three parts, formed, secondary carrier coating is evenly distributed in carrier surface one time, the thickness of secondary carrier coating is 70 μ m, active component is evenly distributed in the coating of secondary carrier, and in secondary carrier, the content of active component accounts for 1.0wt%.
The activity index of the present embodiment catalyst is: initial conversion is 98.23%, is selectively 99.5%.After reaction 200h, its conversion ratio is still > 90%.
Embodiment 11
Difference from Example 1 is, acetylene air speed 40h
-1.
In the present embodiment, this structure catalyst is porous foam structure, by carrier of porous foam, coating secondary carrier and active component three parts, formed, secondary carrier coating is evenly distributed in carrier surface one time, the thickness of secondary carrier coating is 70 μ m, active component is evenly distributed in the coating of secondary carrier, and in secondary carrier, the content of active component accounts for 1.0wt%.
The activity index of the present embodiment catalyst is: initial conversion is 99.21%, is selectively 99.8%.After reaction 400h, its conversion ratio is still > 90%.
Embodiment 12
Difference from Example 1 is, acetylene air speed 30h
-1.
In the present embodiment, this structure catalyst is porous foam structure, by carrier of porous foam, coating secondary carrier and active component three parts, formed, secondary carrier coating is evenly distributed in carrier surface one time, the thickness of secondary carrier coating is 70 μ m, active component is evenly distributed in the coating of secondary carrier, and in secondary carrier, the content of active component accounts for 1.0wt%.
The activity index of the present embodiment catalyst is: initial conversion is 99.45%, is selectively 99.9%.After reaction 500h, its conversion ratio is still > 90%.
Embodiment result shows, the present invention proposes a kind of structure catalyst of Novel ethyne hydrochlorination, can effectively reduce noble metal dosage, in the extending catalyst life-span, urges the technology development into catalyst without mercury.
Claims (8)
1. an acetylene hydrochlorination reaction structure catalyst, it is characterized in that: this structure catalyst is porous foam structure, by carrier of porous foam, coating secondary carrier and active component three parts, formed, secondary carrier coating is evenly distributed in carrier surface one time, the thickness of secondary carrier coating is 0.1～500 μ m, active component is evenly distributed in the coating of secondary carrier, and in secondary carrier, the content of active component accounts for 0.001wt%～70wt%.
2. according to acetylene hydrochlorination reaction structure catalyst claimed in claim 1, it is characterized in that: carrier of porous foam is foam-like carrier: foam silicon carbon, foamy carbon and foamed alumina, carrier is three-dimensional UNICOM network structure, and porosity is 30%～90%.
3. according to acetylene hydrochlorination reaction structure catalyst claimed in claim 1, it is characterized in that: secondary carrier coating is one or more the combination in activated carbon coating, aluminum oxide coating layer, magnesium oxide coating, titania coating, silica coating and molecular sieve coating, secondary carrier coating layer thickness is preferably 10～200 μ m, and in secondary carrier, the preferred content of active component accounts for 0.5wt%～10wt%.
4. according to acetylene hydrochlorination reaction structure catalyst claimed in claim 1, it is characterized in that: active component is one or more the combination in gold, platinum, palladium, ruthenium and rhodium.
5. a preparation method for acetylene hydrochlorination reaction structure catalyst claimed in claim 1, is characterized in that, comprises the steps:
(1), by after the secondary carrier ball milling of powdery, add adhesive and solvent through fully stirring and make slip, secondary carrier: adhesive: the proportioning of solvent is 50～500g:50～200g:1000mL; Again a carrier foam framework is immersed in slurry, after taking-up, by extruding, air-blowing or centrifugation, remove unnecessary slurry;
(2) the above-mentioned carrier soaking after hanging material is carried out to baking and curing in thermal environment;
(3) by the carrier after solidifying, carry out pyrolysis, remove and affect reactive material;
(4) carrier after pyrolysis is immersed in the salting liquid that contains active component, the concentration of active component is 0.001wt%～70wt%, after 30～200 ℃ of oil baths heating 0.5～10 hour are aging, take out and dries, and obtains the structure catalyst of acetylene hydrochlorination reaction.
6. according to the preparation method of acetylene hydrochlorination reaction structure catalyst claimed in claim 5, it is characterized in that, in step (1), secondary carrier be activated carbon, aluminium oxide, magnesia, titanium oxide, silica and molecular sieve one or more; Adhesive be epoxy resin, phenolic resins, polyvinyl alcohol, polyurethane, methylcellulose, butyl titanate, ethyl orthosilicate, aluminum hydroxide sol and Ludox one or more; Solvent be water, ethanol, ethylene glycol, acetic acid, toluene, dimethylbenzene, oxolane, acetone, benzinum, isopropyl alcohol and normal butane one or more.
7. according to the preparation method of acetylene hydrochlorination reaction structure catalyst claimed in claim 5, it is characterized in that, in step (3), pyrolysis temperature is 300～1000 ℃, 0.5～12 hour time.
8. according to the preparation method of acetylene hydrochlorination reaction structure catalyst claimed in claim 5, it is characterized in that, in step (4), the combination of one or more in the villaumite that the salt of active component is metal, nitrate, phosphate, acetate and complex compound thereof.
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| CN107442149A (en) * | 2016-05-31 | 2017-12-08 | 中国科学院金属研究所 | The foaming structure catalyst reacted for benzaldehyde Hydrogenation for phenmethylol and preparation |
| CN107586570A (en) * | 2017-10-16 | 2018-01-16 | 北京三聚环保新材料股份有限公司 | A kind of preparation method of Si modification carrier and the deoxidier and the preparation method of the deoxidier prepared by the carrier |
| CN109174089A (en) * | 2018-11-06 | 2019-01-11 | 陕西瑞科新材料股份有限公司 | A kind of preparation method of tourmaline powder carried palladium catalyst |
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| CN109746012A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院金属研究所 | Acetylene hydrochlorination reaction structure catalyst and preparation and application based on fine and close pipe wall hollow foamed material |
| CN109746005A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院金属研究所 | Acetylene hydrochlorination catalysts and preparation method and application based on porous tube wall hollow foam material |
| CN112844433A (en) * | 2021-01-14 | 2021-05-28 | 石河子大学 | Nonmetal catalyst for acetylene hydrochlorination and preparation method thereof |
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| CN107586570B (en) * | 2017-10-16 | 2021-10-01 | 北京三聚环保新材料股份有限公司 | Preparation method of silicon modified carrier, deoxidizer prepared from carrier and preparation method of deoxidizer |
| CN107586570A (en) * | 2017-10-16 | 2018-01-16 | 北京三聚环保新材料股份有限公司 | A kind of preparation method of Si modification carrier and the deoxidier and the preparation method of the deoxidier prepared by the carrier |
| CN109746012B (en) * | 2017-11-08 | 2022-01-14 | 中国科学院金属研究所 | Acetylene hydrochlorination structured catalyst based on compact pipe wall hollow foam material, and preparation and application thereof |
| CN109746012A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院金属研究所 | Acetylene hydrochlorination reaction structure catalyst and preparation and application based on fine and close pipe wall hollow foamed material |
| CN109746005A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院金属研究所 | Acetylene hydrochlorination catalysts and preparation method and application based on porous tube wall hollow foam material |
| CN109745971A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院金属研究所 | A kind of structural catalyst and its application based on hollow foam material |
| CN109746005B (en) * | 2017-11-08 | 2022-01-14 | 中国科学院金属研究所 | Acetylene hydrochlorination catalyst based on porous pipe wall hollow foam material and preparation method and application thereof |
| CN109174089A (en) * | 2018-11-06 | 2019-01-11 | 陕西瑞科新材料股份有限公司 | A kind of preparation method of tourmaline powder carried palladium catalyst |
| CN112844433A (en) * | 2021-01-14 | 2021-05-28 | 石河子大学 | Nonmetal catalyst for acetylene hydrochlorination and preparation method thereof |
| CN112844433B (en) * | 2021-01-14 | 2023-04-14 | 石河子大学 | Nonmetal catalyst for acetylene hydrochlorination and preparation method thereof |
| CN115318312A (en) * | 2022-09-01 | 2022-11-11 | 浙江工业大学 | High-stability platinum-carbon catalyst and preparation method and application thereof |
| CN115318312B (en) * | 2022-09-01 | 2024-01-30 | 浙江工业大学 | High-stability platinum-carbon catalyst and preparation method and application thereof |
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Application publication date: 20140115 |