CN111389423A - Modified copper-based catalyst for acetylene hydrochlorination and preparation method thereof - Google Patents
Modified copper-based catalyst for acetylene hydrochlorination and preparation method thereof Download PDFInfo
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- CN111389423A CN111389423A CN202010366037.1A CN202010366037A CN111389423A CN 111389423 A CN111389423 A CN 111389423A CN 202010366037 A CN202010366037 A CN 202010366037A CN 111389423 A CN111389423 A CN 111389423A
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- activated carbon
- acetylene
- hydrochlorination
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 52
- 238000007038 hydrochlorination reaction Methods 0.000 title claims abstract description 45
- 150000001879 copper Chemical class 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 118
- 239000011259 mixed solution Substances 0.000 claims abstract description 35
- 238000002791 soaking Methods 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910000153 copper(II) phosphate Inorganic materials 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000012824 chemical production Methods 0.000 abstract description 2
- 238000010923 batch production Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 12
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 238000011068 loading method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- VWYGTDAUKWEPCZ-UHFFFAOYSA-L dichlorocopper;hydrate Chemical compound O.Cl[Cu]Cl VWYGTDAUKWEPCZ-UHFFFAOYSA-L 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 238000005554 pickling Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- -1 Polyethylene Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical group Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/618—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
Abstract
The invention relates to the field of chemical production, in particular to a modified copper-based catalyst for acetylene hydrochlorination and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) soaking the activated carbon in an acid solution for acid washing; (2) dissolving copper salt and a binder in deionized water to prepare a mixed solution; (3) adding acid-washed activated carbon into the mixed solution; (4) and fully soaking and drying the activated carbon to obtain the catalyst. The catalyst of the invention has the advantages of simple preparation method, easy industrial batch production, low cost and the like. The catalyst is applied to acetylene hydrochlorination, has high catalytic activity and stability, and has good industrial application prospect and economic benefit.
Description
Technical Field
The invention relates to the field of chemical production, in particular to a modified copper-based catalyst for acetylene hydrochlorination and a preparation method and application thereof.
Background
Polyvinyl chloride is widely applied to a plurality of fields such as building materials, agriculture, national defense and the like, and the yield of the polyvinyl chloride is the second place of the world polyester yield. Polyethylene is a monomer for the synthesis of polyvinyl chloride. As China is an energy structure with rich coal, poor oil and less gas, the production of chloroethylene is mainly prepared by acetylene hydrochlorination, and the catalyst is mercuric chloride. In the using process of the mercury catalyst, mercury is easy to lose and volatilize, and serious pollution damage is caused to the environment and people. Therefore, the development of a mercury-free catalyst for acetylene hydrochlorination is urgently expected.
In recent years, there has been a great deal of progress in the research of mercury-free catalysts. The mercury-free catalyst mainly comprises a metal catalyst and a nonmetal catalyst. The metal catalyst can be divided into a noble metal catalyst and a non-noble metal catalyst according to active components. Patent application CN103007972A discloses that a catalyst prepared by using copper salt as an active component and using a cocatalyst metal element as alkali metal and transition metal chloride is used for acetylene hydrochlorination, and the acetylene conversion rate of the catalyst is found to be low and cannot meet the requirements of industrial production. Noble metal catalysts generally have high catalytic activity and stability, but noble metal catalysts are expensive, which limits their industrial applications. Patent application CN103962131A discloses a preparation method of a mercury-free catalyst for acetylene hydrochlorination, which uses activated carbon as a carrier and any chloride of noble metal elements such as palladium, rhodium, gold and the like as an active component, and the prepared catalyst has good acetylene conversion rate and vinyl chloride selectivity, but the industrial application thereof is obviously high in cost. Non-metallic catalysts are also one of the hot spots in the research of acetylene hydrochlorination catalysts. The cost of the non-metal catalyst is lower than that of the noble metal catalyst, but the catalytic activity and the stability of the non-metal catalyst cannot meet the industrial requirements. Therefore, the research and development of an economic, green and high-performance modified copper-based catalyst for acetylene hydrochlorination become a key problem to be solved in the polyvinyl chloride industry, and have very important research significance.
Patent CN 106944151B relates to a mercury-free catalyst for hydrochlorination of acetylene to synthesize vinyl chloride, and its preparation method and application, the preparation method is as follows: 1) dissolving base metal salt and amide in water to prepare a mixed solution; 2) adding activated carbon into the mixed solution obtained in the step 1) for impregnation; 3) filtering, draining and then heating and drying the activated carbon obtained in the step 2) to obtain the catalyst. The invention increases the concentration of the raw material gas on the surface of the catalyst by the synergistic effect of the base metal salt and the amides, and simultaneously plays a role in polarizing the reactants as a high-polarity aprotic polar solvent, thereby further improving the reaction efficiency and realizing high low-temperature activity, good selectivity and good stability of the catalyst; in addition, the preparation process is complex, which is not beneficial to industrial production.
Patent application CN 110368936A discloses a nano-material modified copper-based supported catalyst and a preparation method thereof. The nano material modified copper-based supported catalyst takes activated carbon as a carrier, a hydrophilic nano material as a modifier and copper salt as an active component. The invention utilizes the small-size, electronic and structural effects of various inorganic nano materials to effectively relieve the problems of easy agglomeration and easy carbon deposition of active component crystal grains of acetylene under high reaction load, thereby improving the activity and service life of the catalyst, making it possible to replace a highly toxic mercury catalyst in industry, having great environmental protection and social benefits, but further improving the activity and stability of the catalyst.
The application discloses a modified copper-based catalyst prepared by using activated carbon as a carrier and non-noble metal as an active component and adding a binder, and the modified copper-based catalyst has the advantages of low cost, simple preparation process, high catalyst activity and stability and the like, and has a good industrial application prospect.
Disclosure of Invention
Aiming at the technical defects in the prior art, the invention provides a modified copper-based catalyst for acetylene hydrochlorination and a preparation method and application thereof.
At present, a non-noble metal catalyst has certain reaction performance on acetylene hydrochlorination, but the stability and the activity can not completely meet the industrial requirements. According to the invention, the active component and the binder are simultaneously added into a plurality of components according to a certain proportion, the preparation method of the catalyst is simple, green and environment-friendly, and the catalyst has high catalytic activity and stability and meets the requirements of industrial production.
The invention is realized by the following technical scheme:
the invention provides a modified copper-based catalyst for acetylene hydrochlorination and a preparation method thereof, and the modified copper-based catalyst comprises the following steps:
(1) soaking activated carbon and pickling in an acid solution;
(2) dissolving copper salt and a binder in water to prepare a mixed solution;
(3) adding acid-washing activated carbon into the mixed solution for dipping;
(4) and fully drying the impregnated activated carbon to obtain the catalyst.
Preferably, in the step (1), the activated carbon is one or more of wood charcoal, coal charcoal and coconut shell charcoal.
Preferably, in the step (1), the specific surface area of the activated carbon is 300-2000m2G, ash value less than 10%.
Preferably, in the step (1), the specific surface area of the activated carbon is 700-1500m2/g。
Preferably, in step (1), the ash value of the activated carbon is less than 10%, preferably less than 6%.
Preferably, in step (2), the copper salt is CuSO4、CuCl2、Cu(NO3)2、Cu3(PO4)2And Cu2P2O7One or more of (a).
Preferably, in the step (2), the content of the copper salt in the mixed solution is 5 to 50 wt%.
Preferably, in the step (2), the content of the copper salt in the mixed solution is 10 to 30 wt%.
Preferably, in the step (2), the content of the binder in the mixed solution is 0.5 to 30 wt%.
Preferably, in the step (2), the content of the binder in the mixed solution is 1 to 20 wt%.
Preferably, in the step (2), the binder is one or more of an aluminum sol, a silica sol and a titanium sol.
Preferably, in the step (3), the acid washing solution used for acid washing of the activated carbon is one or more of hydrochloric acid, nitric acid and sulfuric acid.
Preferably, in the step (3), the volume of the mixed solution is 1 to 3 times of the volume of the activated carbon.
Preferably, in the step (3), the volume of the mixed solution is 1.05 to 2 times of the volume of the activated carbon.
Preferably, in step (3), the temperature of the impregnation is 25 to 100 ℃.
Preferably, in step (3), the temperature of the impregnation is 30-60 ℃.
Preferably, in the step (3), the time for soaking is 6-48 h.
Preferably, in the step (3), the time for soaking is 8-30 h.
Preferably, in the step (4), the temperature of the drying is 80-200 ℃.
Preferably, in the step (4), the temperature for drying is 100-180 ℃.
Preferably, in the step (4), the drying time is 6-48 h.
Preferably, in the step (4), the drying time is 8-30 h.
Another object of the present invention is to provide a modified copper-based catalyst for hydrochlorination of acetylene, prepared by the preparation method described in any of the above.
The invention also aims to provide the application of the catalyst in acetylene hydrochlorination.
The specific process of the catalyst used for the hydrochlorination reaction of acetylene is as follows: c is to be2H2And introducing the mixed gas and HCl into a fixed bed reactor filled with a catalyst for preparation, and carrying out hydrochlorination.
Preferably, HCl/C2H2In a molar ratio of 1:1-1.5:1；
Preferably, HCl/C2H2In a molar ratio of 1.05:1 to 1.2: 1;
preferably, the space velocity of the acetylene is 10-300h-1；
Preferably, the space velocity of the acetylene is 20-260h-1；
Preferably, the reaction temperature is 80-240 ℃;
preferably, the reaction temperature is 140 ℃ to 220 ℃;
preferably, the reaction pressure is 0.05 to 2 MPa;
preferably, the reaction pressure is from 0.1 to 1 MPa.
Compared with the existing catalyst for acetylene hydrochlorination and the preparation method, the catalyst and the preparation method have the following characteristics:
(1) the catalyst does not contain noble metal, and the cost of the catalyst is lower; the active components of the catalyst are cheap and easy to obtain, the binder in the catalyst can delay the loss of the active components of the catalyst in the use process of the catalyst in the hydrochlorination reaction of acetylene, and the catalyst has good stability;
(2) the catalyst prepared by the invention has simple preparation process and is easy for industrial mass production;
(3) the catalyst does not contain toxic and harmful metals and has no pollution to the environment.
Detailed Description
To better illustrate the patent, the following examples and comparative examples are now set forth. The following examples and comparative examples are intended to provide those skilled in the art with a more detailed understanding of the present invention or to make certain insubstantial modifications or adaptations of the invention in light of the above teachings. However, the scope of the present invention is not limited by these examples. The scope of protection of the invention is set forth in the appended claims.
Example 1
The preparation method of the modified copper-based catalyst and the application of the modified copper-based catalyst in acetylene hydrochlorination reaction comprise the following steps:
(1) soaking the activated carbon in hydrochloric acid for pickling;
(2) weighing 17g of hydrated copper chloride, dissolving the hydrated copper chloride in 50m L of deionized water, adding silica sol containing 2g of silicon dioxide, stirring to fully dissolve the silica sol, and preparing a mixed solution;
(3) soaking the pickled granular activated carbon in the prepared solution, wherein the volume of the activated carbon and the mixed solution is 1:1.05, and soaking for 24 hours at the temperature of 40 ℃;
(4) taking out the impregnated activated carbon, and drying at 140 ℃ for 12h to obtain the required catalyst A1;
(5) loading the catalyst into a fixed bed reactor, and introducing HCl/C2H2Carrying out hydrochlorination on the mixed gas with the molar ratio of 1.08, wherein the reaction temperature is 180 ℃, and the acetylene space velocity is 30h-1。
Example 2
The preparation method of the modified copper-based catalyst and the application of the modified copper-based catalyst in acetylene hydrochlorination reaction comprise the following steps:
(1) soaking the activated carbon in sulfuric acid for acid washing;
(2) weighing 25g of hydrated copper sulfate, dissolving the hydrated copper sulfate in 50m L of deionized water, adding titanium sol containing 2g of titanium dioxide, stirring to fully dissolve the titanium sol, and preparing a mixed solution;
(3) soaking the pickled granular activated carbon in the prepared solution, wherein the volume of the activated carbon and the mixed solution is 1:3, and soaking for 30 hours at the temperature of 30 ℃;
(4) taking out the impregnated activated carbon, and drying at the temperature of 80 ℃ for 48 hours to obtain the required catalyst A2;
(5) loading the catalyst into a fixed bed reactor, and introducing HCl/C2H2Carrying out hydrochlorination on the mixed gas with the molar ratio of 1.08, wherein the reaction temperature is 180 ℃, and the acetylene space velocity is 30h-1。
Example 3
The preparation method of the modified copper-based catalyst and the application of the modified copper-based catalyst in acetylene hydrochlorination reaction comprise the following steps:
(1) soaking the activated carbon in nitric acid for pickling;
(2) weighing 18.7g of copper nitrate, dissolving the copper nitrate in 50m L of deionized water, adding aluminum sol containing 2g of aluminum oxide, stirring to fully dissolve the copper nitrate, and preparing a mixed solution;
(3) soaking the pickled granular activated carbon in the prepared solution, wherein the volume of the activated carbon and the mixed solution is 1:1.05, and soaking for 6 hours at the temperature of 60 ℃;
(4) taking out the impregnated activated carbon, and drying at the temperature of 200 ℃ for 6 hours to obtain the required catalyst A3;
(5) loading the catalyst into a fixed bed reactor, and introducing HCl/C2H2Carrying out hydrochlorination on the mixed gas with the molar ratio of 1.08, wherein the reaction temperature is 180 ℃, and the acetylene space velocity is 30h-1。
Example 4
The preparation method of the modified copper-based catalyst and the application of the modified copper-based catalyst in acetylene hydrochlorination reaction comprise the following steps:
(1) soaking the activated carbon in hydrochloric acid for pickling;
(2) weighing 17g of copper chloride hydrate, dissolving the copper chloride hydrate in 50m L deionized water, adding aluminum sol containing 0.5g of alumina, stirring to fully dissolve the copper chloride hydrate and the aluminum sol, and preparing a mixed solution;
(3) soaking the pickled granular activated carbon in the prepared solution, wherein the volume of the activated carbon and the mixed solution is 1:2, and soaking for 48 hours at the temperature of 25 ℃;
(4) taking out the impregnated activated carbon, and drying at 100 ℃ for 30h to obtain the required catalyst A4;
(5) loading the catalyst into a fixed bed reactor, and introducing HCl/C2H2Carrying out hydrochlorination on the mixed gas with the molar ratio of 1.08, wherein the reaction temperature is 180 ℃, and the acetylene space velocity is 30h-1。
Example 5
The preparation method of the modified copper-based catalyst and the application of the modified copper-based catalyst in acetylene hydrochlorination reaction comprise the following steps:
(1) soaking the activated carbon in sulfuric acid for acid washing;
(2) weighing 17g of copper chloride hydrate, dissolving the copper chloride hydrate in 50m L deionized water, adding aluminum sol containing 3.5g of alumina, stirring to fully dissolve the copper chloride hydrate and the aluminum sol, and preparing a mixed solution;
(3) soaking the pickled granular activated carbon in the prepared solution, wherein the volume of the activated carbon and the mixed solution is 1:1.05, and soaking for 8 hours at the temperature of 100 ℃;
(4) taking out the impregnated activated carbon, and drying at 180 ℃ for 8 hours to obtain the required catalyst A5;
(5) loading the catalyst into a fixed bed reactor, and introducing HCl/C2H2Carrying out hydrochlorination on the mixed gas with the molar ratio of 1.08, wherein the reaction temperature is 180 ℃, and the acetylene space velocity is 30h-1。
Example 6
To further investigate the stability of the catalysts of the present invention, the catalysts prepared in example 1 above were selected and loaded into a fixed bed reactor and HCl/C was passed through2H2The mixed gas with the molar ratio of 1.08 is subjected to hydrochlorination reaction at the reaction temperature of 150 ℃ and the acetylene space velocity of 30h-1The catalyst is subjected to long-period performance evaluation, and after long-time stability evaluation, the catalyst can meet the requirements of industrial production.
Comparative example 1
The difference compared with example 1 is only the acid wash of the activated carbon.
The preparation method of the modified copper-based catalyst and the application of the modified copper-based catalyst in acetylene hydrochlorination reaction comprise the following steps:
(1) soaking the activated carbon in a mixed solution of dilute sulfuric acid and hydrogen peroxide for acid washing;
(2) weighing 17g of hydrated copper chloride, dissolving the hydrated copper chloride in 50m L of deionized water, adding silica sol containing 2g of silicon dioxide, stirring to fully dissolve the silica sol, and preparing a mixed solution;
(3) soaking the acid-washed active carbon in the prepared solution, wherein the volume of the active carbon and the mixed solution is 1:1.05, and soaking for 24 hours at the temperature of 40 ℃;
(4) taking out the impregnated activated carbon, and drying at 140 ℃ for 12h to obtain the required catalyst B1;
(5) loading the catalyst into a fixed bed reactor, and introducing HCl/C2H2Hydrogen chlorine is carried out on mixed gas with the molar ratio of 1.08The reaction temperature is 180 ℃, and the space velocity of acetylene is 30h-1。
Comparative example 2
The difference compared with example 1 is only the acid wash of the activated carbon.
The preparation method of the modified copper-based catalyst and the application of the modified copper-based catalyst in acetylene hydrochlorination reaction comprise the following steps:
(1) soaking activated carbon in a mixed solution of hydrogen peroxide and deionized water for cleaning;
(2) weighing 17g of hydrated copper chloride, dissolving the hydrated copper chloride in 50m L of deionized water, adding 2g of zirconia nano material, stirring to fully dissolve the zirconium oxide nano material, and preparing a mixed solution;
(3) soaking the acid-washed active carbon in the prepared solution, wherein the volume of the active carbon and the mixed solution is 1:1.05, and soaking for 24 hours at the temperature of 40 ℃;
(4) taking out the impregnated activated carbon, and drying at 140 ℃ for 12h to obtain the required catalyst B2;
(5) loading the catalyst into a fixed bed reactor, and introducing HCl/C2H2Carrying out hydrochlorination on the mixed gas with the molar ratio of 1.08, wherein the reaction temperature is 180 ℃, and the acetylene space velocity is 30h-1。
Comparative example 3
The difference compared to example 1 is only that no binder is added.
The preparation method of the modified copper-based catalyst and the application of the modified copper-based catalyst in acetylene hydrochlorination reaction comprise the following steps:
(1) soaking the activated carbon in hydrochloric acid for pickling;
(2) weighing 17g of hydrated copper chloride, dissolving in 50m L deionized water, stirring to fully dissolve the hydrated copper chloride, and preparing into a mixed solution;
(3) soaking the pickled granular activated carbon in the prepared solution, wherein the volume of the activated carbon and the mixed solution is 1:1.05, and soaking for 24 hours at the temperature of 40 ℃;
(4) taking out the impregnated activated carbon, and drying at 140 ℃ for 12h to obtain the required catalyst B3;
(5) loading the catalyst into a fixed bed reactor, and introducing HCl/C2H2Carrying out hydrochlorination on the mixed gas with the molar ratio of 1.08, wherein the reaction temperature is 180 ℃, and the acetylene space velocity is 30h-1。
The acetylene conversion and vinyl chloride selectivity of the catalysts A1-A5 obtained in examples 1-5 and the catalysts B1-B3 obtained in comparative examples 1-3 were shown in Table 1.
TABLE 1 acetylene conversion and vinyl chloride Selectivity of the hydrochlorination reaction
| Catalyst and process for preparing same | Initial conversion of acetylene (%) | Vinyl chloride selectivity (%) |
| A1 | 97.1 | 99.2 |
| A2 | 93.7 | 99.0 |
| A3 | 95.6 | 98.8 |
| A4 | 94.2 | 99.0 |
| A5 | 92.6 | 99.1 |
| B1 | 90.4 | 94.1 |
| B2 | 86.4 | 95.3 |
| B3 | 83.6 | 84.5 |
Therefore, the catalyst provided by the invention has higher acetylene conversion rate and selectivity when being used for acetylene hydrochlorination reaction.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification or replacement by those skilled in the art within the technical scope of the present invention will fall within the scope of the present invention.
Claims (10)
1. A preparation method of a modified copper-based catalyst for acetylene hydrochlorination is characterized by comprising the following steps:
(1) soaking the activated carbon in an acid solution for acid washing;
(2) dissolving copper salt and a binder in deionized water to prepare a mixed solution;
(3) adding acid-washing activated carbon into the mixed solution for dipping;
(4) and drying the impregnated activated carbon to obtain the catalyst.
2. The preparation method according to claim 1, wherein in the step (1), the activated carbon is one or more of wood carbon, coal carbon and coconut shell carbon; the specific surface area of the activated carbon is 300-2000m2/g, preferably 700-1500m2(ii)/g; the ash value is less than 10%, preferably less than 6%.
3. The method according to claim 1, wherein in step (2), the copper salt is selected from CuSO4、CuCl2、Cu(NO3)2、Cu3(PO4)2And Cu2P2O7One or more of; the content of copper salt in the mixed solution is 5-50 wt%, preferably 10-30 wt%; the content of the binder in the mixed solution is 0.5 to 30 wt%, preferably 1 to 20 wt%.
4. The method according to claim 1, wherein in the step (2), the binder is one or more of an aluminum sol, a silica sol, and a titanium sol.
5. The method according to claim 1, wherein in the step (3), the acid-washing solution used for acid-washing the activated carbon is one or more of hydrochloric acid, nitric acid and sulfuric acid.
6. The method according to claim 1, wherein, in the step (3),
the volume of the mixed solution is 1 to 3 times, preferably 1.05 to 2 times of the volume of the activated carbon;
the dipping temperature is 25-100 ℃, and preferably 30-60 ℃;
the impregnation time is 6 to 48h, preferably 8 to 30 h.
7. The method according to claim 1, wherein, in the step (4),
the drying temperature is 80-200 ℃, preferably 100-180 ℃;
the drying time is 6-48h, preferably 8-30 h.
8. A modified copper-based catalyst for hydrochlorination of acetylene, obtainable by a process according to any one of claims 1 to 7.
9. Use of the modified copper-based catalyst of claim 8 in the hydrochlorination of acetylene.
10. The use of the modified copper-based catalyst in acetylene hydrochlorination according to claim 9, wherein the specific process of the catalyst in acetylene hydrochlorination is as follows:
c is to be2H2Introducing the mixed gas and HCl into a fixed bed reactor filled with a catalyst for preparation, and carrying out hydrochlorination; wherein the reactor is a fixed bed reactor;
HCl/C2H2in a molar ratio of 1:1 to 1.5:1, preferably 1.05:1 to 1.2: 1;
C2H2the space velocity of the catalyst is 10 to 300h-1Preferably 20-260h-1；
The reaction temperature is 80-240 ℃, preferably 140-220 ℃;
the pressure of the reaction is 0.05 to 2MPa, preferably 0.1 to 1 MPa.
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| CN112916049A (en) * | 2021-01-27 | 2021-06-08 | 南开大学 | Oxygen-containing polydentate ligand modified copper-based catalyst for acetylene hydrochlorination reaction and preparation method and application thereof |
| CN113634265A (en) * | 2021-07-26 | 2021-11-12 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Catalyst for synthesizing vinyl chloride by hydrochlorinating Cu-Ru acetylene and preparation method 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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