CN112156809A - Ionic liquid modified activated carbon loaded gold catalyst and application thereof in catalyzing acetylene hydrochlorination - Google Patents
Ionic liquid modified activated carbon loaded gold catalyst and application thereof in catalyzing acetylene hydrochlorination Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 108
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000010931 gold Substances 0.000 title claims abstract description 41
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 41
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 37
- 238000007038 hydrochlorination reaction Methods 0.000 title claims abstract description 18
- 238000001291 vacuum drying Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000005507 spraying Methods 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 239000000428 dust Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 22
- 244000060011 Cocos nucifera Species 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000011068 loading method Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 6
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 claims description 5
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 5
- -1 1-ethyl-3-methylimidazole phosphorus fluoride salt Chemical compound 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- RPZNPEMXYNMTKB-UHFFFAOYSA-N Br.CCN1CC=CC=C1 Chemical compound Br.CCN1CC=CC=C1 RPZNPEMXYNMTKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 claims description 4
- XOTZDSWJKMKAMT-UHFFFAOYSA-M tributyl(ethyl)phosphanium;bromide Chemical compound [Br-].CCCC[P+](CC)(CCCC)CCCC XOTZDSWJKMKAMT-UHFFFAOYSA-M 0.000 claims description 4
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 238000007605 air drying Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 239000008399 tap water Substances 0.000 description 7
- 235000020679 tap water Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 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
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses an ionic liquid modified activated carbon supported gold catalyst and application thereof in catalyzing acetylene hydrochlorination. The preparation method of the ionic liquid modified activated carbon comprises the following steps: firstly, performing alkali washing on the activated carbon to remove floating dust and impurities on the surface, then dissolving the ionic liquid in a corresponding solvent and spraying the solvent on an activated carbon carrier after alkali washing, and finally performing vacuum drying to obtain the ionic liquid modified activated carbon. The preparation process is simple and pollution-free, and is suitable for industrial mass production. The gold-based mercury-free catalyst prepared by taking the ionic liquid modified activated carbon as the carrier can show excellent catalytic performance in acetylene hydrochlorination, can greatly reduce the attenuation speed of the catalyst in long-term use and prolong the service life of the catalyst.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to an ionic liquid modified activated carbon supported gold catalyst and application of the catalyst in acetylene hydrochlorination.
Background
Based on the energy distribution condition, most of China adopts a calcium carbide method to produce polyvinyl chloride monomers, and the used catalyst is mainly a poisonous and volatile mercuric chloride loaded active carbon catalyst. The pollution problem caused by the mercury catalyst is urgently needed to be solved, and the research and development of the non-mercury catalyst which has high catalytic activity, high selectivity, long service life and no toxicity and is environment-friendly has attracted the wide attention of domestic and foreign scholars. The selection of proper carriers or the modification of the carriers to improve the properties of dispersion degree, active sites, adsorption capacity and the like is an important direction for improving the performance of the mercury-free catalyst.
An ionic liquid is a salt generally composed of an organic cation and an organic or inorganic anion, which has been widely used in various reactions such as Suzuki-Miyaura coupling reaction, hydrogenation reaction, hydroformylation reaction, and the like. At present, the catalyst prepared by the ionic liquid has excellent catalytic performance. The reports of patents related to acetylene hydrochlorination and ionic liquid mainly take the ionic liquid as a medium, and acetylene and hydrogen chloride are introduced into the ionic liquid to carry out reaction in a liquid phase. The ionic liquid is used as a medium to modify the carrier, so that the method has the potential of becoming a solution for preparing an efficient, economic and stable industrial-grade mercury-free catalyst, and is used for realizing large-scale acetylene hydrochlorination.
Disclosure of Invention
The invention aims to provide a gold-based mercury-free catalyst prepared by taking ionic liquid modified activated carbon as a carrier, which has excellent catalytic performance in acetylene hydrochlorination, can greatly reduce the attenuation speed of the catalyst in long-term use and can replace the existing mercury chloride catalyst, thereby providing a new application for the catalyst.
Aiming at the purposes, the ionic liquid modified activated carbon supported gold catalyst adopted by the invention takes ionic liquid modified activated carbon as a carrier, and adopts an impregnation method to support active component gold; the loading amount of the gold is 0.05-0.2% by taking the mass of the catalyst as 100%; the mass content of the ionic liquid in the ionic liquid modified activated carbon is 5.0-25.0%, and the balance is activated carbon.
In the ionic liquid modified activated carbon, the mass content of the ionic liquid is preferably 10.0-20.0%, and the balance is activated carbon.
The ionic liquid is any one of 1-ethyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole borofluoride, 1-ethyl-3-methylimidazole phosphorus fluoride, N-ethylpyridine bromide, tributylmethyl ammonium chloride, tributylethyl phosphonium bromide and tetraphenylphosphonium bromide, and preferably any one of 1-ethyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole borofluoride and 1-ethyl-3-methylimidazole phosphorus fluoride.
The active carbon is any one of wood active carbon, coconut shell active carbon and coal active carbon, and is in any one of a columnar shape and a sheet shape.
The preparation method of the ionic liquid modified activated carbon comprises the following steps: firstly, performing alkali washing on the activated carbon to remove floating dust and impurities on the surface, then dissolving the ionic liquid in a corresponding solvent and spraying the solvent on an activated carbon carrier after alkali washing, and finally performing vacuum drying to obtain the ionic liquid modified activated carbon.
In the method, the alkali is any one of sodium hydroxide aqueous solution, sodium carbonate aqueous solution and ammonia water, wherein the mass fraction of the sodium hydroxide, the sodium carbonate and the ammonia is 5-20%.
In the method, the corresponding solvent is any one of water, methanol and ethanol, and the mass fraction of the ionic liquid in the corresponding solvent is 10-50%.
In the method, the temperature of the vacuum drying is 40-80 ℃, the vacuum degree is below 20Pa, and the vacuum drying time is 6-12 h.
The application of the ionic liquid modified activated carbon-loaded gold catalyst in preparing vinyl chloride by catalyzing acetylene hydrochlorination comprises the following specific application methods: filling a catalyst into a fixed bed tubular reactor, introducing acetylene gas and hydrogen chloride gas, and controlling the volume airspeed of acetylene to be 20-100 h-1The flow rate ratio of the hydrogen chloride to the acetylene is 1.02-1.2: 1, and the reaction is carried out at the temperature of 140-220 ℃.
In the application of preparing vinyl chloride by catalyzing acetylene hydrochlorination, the preferred volume space velocity of acetylene is controlled to be 40-60 h-1The flow rate ratio of the hydrogen chloride to the acetylene is 1.05-1.1: 1, and the temperature is 180-200 ℃.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts the ionic liquid to modify the active carbon, the ionic liquid can effectively improve the dispersion degree of the active components of the catalyst, thereby improving the activity of the catalyst, and the gold-based mercury-free catalyst prepared by taking the modified active carbon as a carrier shows excellent catalytic performance in acetylene hydrochlorination reaction.
2. According to the invention, the active carbon is modified by the ionic liquid, and the reduction of the active component can be effectively inhibited, so that the attenuation speed of the catalyst in long-term use is greatly reduced, the stability of the catalyst is improved, and the service life of the catalyst is prolonged.
3. The preparation method of the ionic liquid modified activated carbon is completely green and pollution-free, has a very simple process route, is easy to realize industrial production, and has high added value of products. The gold-based mercury-free catalyst prepared by taking the modified activated carbon as the carrier can replace the existing mercury chloride catalyst, thereby avoiding the pollution of the mercury-containing catalyst to the environment.
4. The preparation process of the catalyst is simple and pollution-free, and is suitable for industrial scale production, and the noble metal active component is easy to regenerate and recover.
Drawings
FIG. 1 is a graph comparing the acetylene conversion rates for gold-supported catalysts prepared from the ionic liquid modified activated carbon of example 1 of the present invention and the unmodified activated carbon of comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
In the catalyst of the embodiment, the loading amount of gold is 0.1% and the balance is ionic liquid modified activated carbon, wherein the mass of the catalyst is 100%; the mass content of the ionic liquid in the ionic liquid modified activated carbon is 15.0%, the balance is activated carbon, the ionic liquid is 1-ethyl-3-methylimidazole chloride salt, and the activated carbon is flaky coconut shell activated carbon.
The preparation method of the catalyst of the embodiment is as follows:
1. firstly, washing flaky coconut shell activated carbon for several times by using tap water to remove surface impurities and ash, then slowly adding the activated carbon into a 10% sodium hydroxide aqueous solution by mass, and heating and keeping boiling for 1 h. And after cooling, repeatedly soaking and washing with deionized water until the pH value is below 10, and finally drying in a blast drying oven at 120 ℃ to obtain the pretreated flaky coconut shell activated carbon.
2. Dissolving 1.5g of 1-ethyl-3-methylimidazolium chloride in 2.5g of deionized water, spraying the obtained ionic liquid solution on 8.5g of pretreated flaky coconut shell activated carbon on a rotary drum by using a spray gun, placing the sprayed activated carbon in a vacuum drying box, heating to 60 ℃, vacuumizing to below 20Pa, and vacuum-drying for 12 hours to obtain the ionic liquid modified activated carbon.
3. Adding chloroauric acid aqueous solution into the ionic liquid modified activated carbon according to an isometric impregnation method, impregnating for 6 hours, and then placing in a forced air drying oven for drying at 120 ℃ to prepare the mercury-free catalyst with gold loading of 0.1%.
Example 2
In the catalyst of this example, the loading amount of gold is 0.05% and the balance is ionic liquid modified activated carbon, with the mass of the catalyst being 100%; the mass content of the ionic liquid in the ionic liquid modified activated carbon is 15.0%, the balance is activated carbon, the ionic liquid is 1-ethyl-3-methylimidazol borofluoride, and the activated carbon is columnar wood activated carbon.
The preparation method of the catalyst of the embodiment is as follows:
1. firstly, washing columnar wood activated carbon for a plurality of times by tap water to remove surface impurities and ash, then slowly adding the activated carbon into a sodium hydroxide aqueous solution with the mass fraction of 5%, and heating and keeping boiling for 1 h. And cooling, soaking and washing with deionized water to a pH value below 10, and drying in a blast drying oven at 120 ℃ to obtain the pretreated columnar wood activated carbon.
2. Dissolving 1.5g of 1-ethyl-3-methylimidazolium borofluoride in 2.5g of deionized water, spraying the obtained ionic liquid solution on 8.5g of pretreated columnar wood activated carbon on a rotary drum by using a spray gun, placing the sprayed activated carbon in a vacuum drying box, heating to 60 ℃, vacuumizing to below 20Pa, and vacuum-drying for 12 hours to obtain the ionic liquid modified activated carbon.
3. Adding chloroauric acid aqueous solution into the ionic liquid modified activated carbon according to an isometric impregnation method, impregnating for 6 hours, and then placing in a forced air drying oven for drying at 120 ℃ to prepare the mercury-free catalyst with gold loading of 0.05%.
Example 3
In the catalyst of the embodiment, the loading amount of gold is 0.2% and the balance is ionic liquid modified activated carbon, wherein the mass of the catalyst is 100%; the mass content of the ionic liquid in the ionic liquid modified activated carbon is 15.0%, the balance is activated carbon, the ionic liquid is 1-ethyl-3-methylimidazole phosphate fluoride salt, and the activated carbon is columnar coal activated carbon.
The preparation method of the catalyst of the embodiment is as follows:
1. firstly, washing columnar coal activated carbon for a plurality of times by tap water to remove surface impurities and ash, then slowly adding the activated carbon into a sodium hydroxide aqueous solution with the mass fraction of 20%, and heating and keeping boiling for 1 h. And cooling, soaking and washing with deionized water to a pH value below 10, and drying in a blast drying oven at 120 ℃ to obtain the pretreated columnar coal-based activated carbon.
2. 1.5g of 1-ethyl-3-methylimidazolium phosphofluorite is dissolved in 2.5g of methanol, the obtained ionic liquid solution is sprayed on 8.5g of pretreated columnar coal activated carbon on a rotary drum by a spray gun, the sprayed activated carbon is placed in a vacuum drying box, the temperature is raised to 40 ℃, the vacuum is pumped to below 20Pa, and the vacuum drying is carried out for 12 hours, so as to obtain the ionic liquid modified activated carbon.
3. Adding chloroauric acid aqueous solution into the ionic liquid modified activated carbon according to an isometric impregnation method, impregnating for 6 hours, and then placing in a forced air drying oven for drying at 120 ℃ to prepare the mercury-free catalyst with gold loading of 0.2%.
Example 4
In the catalyst of the embodiment, the loading amount of gold is 0.1% and the balance is ionic liquid modified activated carbon, wherein the mass of the catalyst is 100%; the mass content of the ionic liquid in the ionic liquid modified activated carbon is 5.0%, the balance is activated carbon, the ionic liquid is N-ethylpyridine bromide salt, and the activated carbon is flaky coconut shell activated carbon.
The preparation method of the catalyst of the embodiment is as follows:
1. firstly, washing flaky coconut shell activated carbon for several times by using tap water to remove surface impurities and ash, then slowly adding the activated carbon into a 10% sodium hydroxide aqueous solution by mass, and heating and keeping boiling for 1 h. And after cooling, repeatedly soaking and washing with deionized water until the pH value is below 10, and finally drying in a blast drying oven at 120 ℃ to obtain the pretreated flaky coconut shell activated carbon.
2. Dissolving 0.5g N-ethylpyridine bromide in 4.5g of deionized water, spraying the obtained ionic liquid solution on 9.5g of pretreated flaky coconut shell activated carbon on a rotary drum by using a spray gun, putting the sprayed activated carbon in a vacuum drying oven, heating to 80 ℃, vacuumizing to below 20Pa, and drying in vacuum for 6 hours to obtain the ionic liquid modified activated carbon.
3. Adding chloroauric acid aqueous solution into the ionic liquid modified activated carbon according to an isometric impregnation method, impregnating for 6 hours, and then placing in a forced air drying oven for drying at 120 ℃ to prepare the mercury-free catalyst with gold loading of 0.1%.
Example 5
In the catalyst of the embodiment, the loading amount of gold is 0.1% and the balance is ionic liquid modified activated carbon, wherein the mass of the catalyst is 100%; the mass content of the ionic liquid in the ionic liquid modified activated carbon is 25.0%, the balance of the ionic liquid modified activated carbon is activated carbon, the ionic liquid is tributylmethylammonium chloride, and the activated carbon is flaky coconut shell activated carbon.
The preparation method of the catalyst of the embodiment is as follows:
1. firstly, washing flaky coconut shell activated carbon for several times by using tap water to remove surface impurities and ash, then slowly adding the activated carbon into a 10% sodium hydroxide aqueous solution by mass, and heating and keeping boiling for 1 h. And after cooling, repeatedly soaking and washing with deionized water until the pH value is below 10, and finally drying in a blast drying oven at 120 ℃ to obtain the pretreated flaky coconut shell activated carbon.
2. Dissolving 2.5g of tributylmethylammonium chloride in 2.5g of deionized water, spraying the obtained ionic liquid solution on 7.5g of pretreated flaky coconut shell activated carbon on a rotary drum by using a spray gun, placing the sprayed activated carbon in a vacuum drying oven, heating to 60 ℃, vacuumizing to below 20Pa, and vacuum-drying for 12 hours to obtain the ionic liquid modified activated carbon.
3. Adding chloroauric acid aqueous solution into the ionic liquid modified activated carbon according to an isometric impregnation method, impregnating for 6 hours, and then placing in a forced air drying oven for drying at 120 ℃ to prepare the mercury-free catalyst with gold loading of 0.1%.
Example 6
In the catalyst of the embodiment, the loading amount of gold is 0.1% and the balance is ionic liquid modified activated carbon, wherein the mass of the catalyst is 100%; the mass content of the ionic liquid in the ionic liquid modified activated carbon is 15.0%, the balance is activated carbon, the ionic liquid is tributyl ethyl phosphonium bromide, and the activated carbon is flaky coconut shell activated carbon.
The preparation method of the catalyst of the embodiment is as follows:
1. firstly, washing flaky coconut shell activated carbon for several times by using tap water to remove surface impurities and ash, then slowly adding the activated carbon into a 10% sodium hydroxide aqueous solution by mass, and heating and keeping boiling for 1 h. And after cooling, repeatedly soaking and washing with deionized water until the pH value is below 10, and finally drying in a blast drying oven at 120 ℃ to obtain the pretreated flaky coconut shell activated carbon.
2. Dissolving 1.5g of tributyl ethyl phosphonium bromide in 2.5g of deionized water, spraying the obtained ionic liquid solution on 8.5g of pretreated flaky coconut shell activated carbon on a rotary drum by using a spray gun, placing the sprayed activated carbon in a vacuum drying oven, heating to 60 ℃, vacuumizing to below 20Pa, and vacuum-drying for 12 hours to obtain the ionic liquid modified activated carbon.
3. Adding chloroauric acid aqueous solution into the ionic liquid modified activated carbon according to an isometric impregnation method, impregnating for 6 hours, and then placing in a forced air drying oven for drying at 120 ℃ to prepare the mercury-free catalyst with gold loading of 0.1%.
Example 7
In the catalyst of the embodiment, the loading amount of gold is 0.1% and the balance is ionic liquid modified activated carbon, wherein the mass of the catalyst is 100%; the mass content of the ionic liquid in the ionic liquid modified activated carbon is 15.0%, the balance is activated carbon, the ionic liquid is tetraphenylphosphonium bromide, and the activated carbon is flaky coconut shell activated carbon.
The preparation method of the catalyst of the embodiment is as follows:
1. firstly, washing flaky coconut shell activated carbon for several times by using tap water to remove surface impurities and ash, then slowly adding the activated carbon into a 10% sodium hydroxide aqueous solution by mass, and heating and keeping boiling for 1 h. And after cooling, repeatedly soaking and washing with deionized water until the pH value is below 10, and finally drying in a blast drying oven at 120 ℃ to obtain the pretreated flaky coconut shell activated carbon.
2. Dissolving 1.5g of tetraphenylphosphonium bromide in 2.5g of ethanol, spraying the obtained ionic liquid solution on 8.5g of pretreated flaky coconut shell activated carbon on a rotary drum by using a spray gun, putting the sprayed activated carbon in a vacuum drying oven, heating to 60 ℃, vacuumizing to below 20Pa, and vacuum-drying for 6 hours to obtain the ionic liquid modified activated carbon.
3. Adding chloroauric acid aqueous solution into the ionic liquid modified activated carbon according to an isometric impregnation method, impregnating for 6 hours, and then placing in a forced air drying oven for drying at 120 ℃ to prepare the mercury-free catalyst with gold loading of 0.1%.
Example 8
The ionic liquid modified activated carbon-supported gold catalyst prepared in the embodiment 1-7 is applied to the preparation of vinyl chloride by the catalytic hydrochlorination of acetylene.
The acetylene hydrochlorination was continuously evaluated using a fixed bed reactor. The catalyst is filled in a fixed bed tubular reactor, raw materials of acetylene gas and hydrogen chloride gas come from a high-pressure steel cylinder, the flow rate is adjusted by a mass flow meter and then mixed to enter the reactor, the temperature of the reactor is controlled by a temperature program controller, and reaction products are absorbed by alkali liquor and then are subjected to online monitoring and analysis by a gas chromatograph. The test is carried out at the acetylene volume space velocity of 250h-1(aiming at evaluating the catalyst effect more quickly and controlling the volume space velocity of acetylene to be 20-100 h in practical application-1Preferably controlling the volume space velocity of acetylene to be 40-60 h-1) The flow rate ratio of hydrogen chloride to acetylene was 1.1:1, and the temperature was 180 ℃ and the test results are shown in Table 1.
For comparison, the activated carbon used in examples 1 to 3 was directly prepared into a mercury-free catalyst with the same gold loading without modification by an ionic liquid, and the catalyst was recorded as comparative examples 1 to 3, and then used for catalyzing hydrochlorination of acetylene to prepare vinyl chloride according to the above method, and the results are shown in table 1.
TABLE 1 test results for mercury-free catalysts prepared in examples 1-7 and comparative examples 1-3
As can be seen from Table 1, the gold-based mercury-free catalyst prepared by using the ionic liquid modified activated carbon as a carrier can efficiently catalyze the hydrochlorination of acetylene, and can greatly reduce the attenuation speed of the catalyst in use, thereby prolonging the service life of the catalyst and reducing the production cost. And the preparation process of the ionic liquid modified activated carbon is simple and pollution-free, and is suitable for industrial mass production.
FIG. 1 is a graph comparing the acetylene conversion for mercury-free catalysts prepared from the ionic liquid modified activated carbon of example 1 of the present invention and the unmodified activated carbon of comparative example 1. As can be seen from the figure, the acetylene conversion of the catalyst of example 1 is always higher than that of comparative example 1 as the reaction continues, and the decay continues to slow and tends to stabilize, which indicates that the ionic liquid-modified activated carbon of the present invention improves the activity of the catalyst and prolongs the service life of the catalyst.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (10)
1. An ionic liquid modified activated carbon supported gold catalyst is characterized in that: the catalyst takes ionic liquid modified activated carbon as a carrier, and an active component gold is loaded by adopting an impregnation method; the loading amount of gold is 0.05-0.2% by taking the mass of the catalyst as 100%; the mass content of the ionic liquid in the ionic liquid modified activated carbon is 5.0-25.0%, and the balance is activated carbon; the ionic liquid is any one of 1-ethyl-3-methylimidazole chloride salt, 1-ethyl-3-methylimidazole borofluoride salt, 1-ethyl-3-methylimidazole phosphorus fluoride salt, N-ethylpyridine bromide salt, tributylmethyl ammonium chloride, tributylethyl phosphonium bromide and tetraphenylphosphonium bromide.
2. The ionic liquid modified activated carbon supported gold catalyst of claim 1, wherein: the mass content of the ionic liquid in the ionic liquid modified activated carbon is 10.0-20.0%, and the balance is activated carbon; the ionic liquid is any one of 1-ethyl-3-methylimidazole chloride salt, 1-ethyl-3-methylimidazole borofluoride salt and 1-ethyl-3-methylimidazole phosphofluoride salt.
3. The ionic liquid modified activated carbon supported gold catalyst of claim 1 or 2, wherein: the active carbon is any one of wood active carbon, coconut shell active carbon and coal active carbon, and is in any one of a columnar shape and a sheet shape.
4. The ionic liquid modified activated carbon supported gold catalyst of claim 1 or 2, wherein: the preparation method of the ionic liquid modified activated carbon comprises the following steps: firstly, performing alkali washing on the activated carbon to remove floating dust and impurities on the surface, then dissolving the ionic liquid in a corresponding solvent and spraying the solvent on the activated carbon after the alkali washing, and finally performing vacuum drying to obtain the ionic liquid modified activated carbon.
5. The ionic liquid modified activated carbon supported gold catalyst of claim 4, wherein: the alkali is any one of sodium hydroxide aqueous solution, sodium carbonate aqueous solution and ammonia water, wherein the mass fraction of the sodium hydroxide, the sodium carbonate and the ammonia is 5-20%.
6. The ionic liquid modified activated carbon supported gold catalyst of claim 4, wherein: the corresponding solvent is any one of water, methanol and ethanol, and the mass fraction of the ionic liquid in the corresponding solvent is 10-50%.
7. The ionic liquid modified activated carbon supported gold catalyst according to claim 4, wherein the temperature of vacuum drying is 40-80 ℃, the vacuum degree is less than 20Pa, and the vacuum drying time is 6-12 h.
8. The use of the ionic liquid modified activated carbon supported gold catalyst of claim 1 in the preparation of vinyl chloride by the catalytic hydrochlorination of acetylene.
9. The application of the ionic liquid modified activated carbon supported gold catalyst in preparing vinyl chloride by catalyzing hydrochlorination of acetylene according to claim 8 is characterized in that: filling a catalyst into a fixed bed tubular reactor, introducing acetylene gas and hydrogen chloride gas, and controlling the volume airspeed of acetylene to be 20-100 h-1The flow rate ratio of the hydrogen chloride to the acetylene is 1.02-1.2: 1, and the reaction is carried out at the temperature of 140-220 ℃.
10. The application of the ionic liquid modified activated carbon supported gold catalyst in preparing vinyl chloride by catalyzing hydrochlorination of acetylene according to claim 9 is characterized in that: controlling the volume space velocity of acetylene to be 40-60 h-1The flow rate ratio of the hydrogen chloride to the acetylene is 1.05-1.1: 1, and the temperature is 180-200 ℃.
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