CN114345338B - High-selectivity catalyst for converting mercaptan compound and preparation method and application thereof - Google Patents
High-selectivity catalyst for converting mercaptan compound and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- -1 mercaptan compound Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 76
- 239000002184 metal Substances 0.000 claims abstract description 55
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001962 electrophoresis Methods 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims description 26
- 238000011068 loading method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 14
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 150000002019 disulfides Chemical class 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- CETBSQOFQKLHHZ-UHFFFAOYSA-N Diethyl disulfide Chemical compound CCSSCC CETBSQOFQKLHHZ-UHFFFAOYSA-N 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 229910000510 noble metal Inorganic materials 0.000 abstract description 8
- 230000009471 action Effects 0.000 abstract description 3
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 125000001741 organic sulfur group Chemical group 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 230000005684 electric field Effects 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 description 22
- 150000004706 metal oxides Chemical class 0.000 description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- SRRKNRDXURUMPP-UHFFFAOYSA-N sodium disulfide Chemical compound [Na+].[Na+].[S-][S-] SRRKNRDXURUMPP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Catalysts (AREA)
Abstract
The invention belongs to the technical field of organic sulfur pollutant treatment, and discloses a high-selectivity catalyst for converting mercaptan compounds, a preparation method and application thereof, wherein metal salt is dissolved in water, and TiO is added under stirring 2 And a reducing agent to produce a metal/TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Dispersing it in a solution containing inorganic salt and surfactant to prepare metal/TiO 2 Sol; using porous net film as cathode, applying external electric field to metal/TiO 2 Electrophoresis of the sol to obtain metal/TiO 2 Is loaded on the porous net film. Under the action of the film catalyst, the thiol compound can be catalyzed and oxidized into the disulfide compound with high selectivity at normal temperature, wherein the conversion rate of the thiol compound is close to 100%, the selectivity of the disulfide compound is more than 95%, and the problems of easiness in poisoning of a noble metal catalyst, low conversion rate of the thiol compound and poor catalytic conversion selectivity of the disulfide compound are solved.
Description
Technical Field
The invention belongs to the technical field of treatment of malodorous organic sulfur pollutants, and in particular relates to a high-selectivity catalyst for converting mercaptan compounds, and a preparation method and application thereof.
Background
Thiol is a typical malodorous gas, which not only has the dual properties of malodorous pollution and toxic pollution, but also is an important precursor of secondary organic aerosol, ozone and particulate matters, and is a focus of pollution in the current environmental field research. Mercaptans are mainly derived from petroleum refining, wood pulping industry, sewage treatment, and landfill industry processes. The search for an economically efficient and environmentally friendly thiol prevention and control scheme has important significance for protecting the ecological environment and maintaining the health of people.
The pollution control of mercaptan mainly comprises a chemical adsorption method, a solution absorption method, a biological method, a catalytic oxidation method and the like, but the methods still have the problem of secondary pollution. In contrast, the method for converting the mercaptan into the disulfide compound which is an important chemical raw material with lower toxicity is the most ideal treatment mode, so that the environmental pollution can be reduced, and the reasonable utilization of the mercaptan odor can be realized. The method for converting the mercaptan into the disulfide compound mainly comprises a vulcanization method and an oxidation method, wherein the mercaptan vulcanization method mainly uses sulfur or sodium disulfide as raw materials to prepare the disulfide compound, but hydrogen sulfide (H) is generated as a byproduct in the reaction process 2 S), and the like, and has the defects of poor selectivity, low yield and the like of the disulfide compound. Compared with the mercaptan vulcanization method, the mercaptan oxidation method has the advantages of mild reaction condition, simple operation and no H generation 2 S by-products and the like, and the equation of the reaction is as follows:
the currently reported catalyst for thiol oxidation mainly uses noble metals such as Pd, pt and the like, but the noble metal active components are sensitive to the concentration of sulfides in the raw materials, are easy to generate strong chemical bonds with the sulfides, so that the catalyst is poisoned and deactivated, and the noble metal cost is high, thereby being not beneficial to industrial utilization. The transition metal catalysts such as Ni, co and the like which are developed at present need to oxidize mercaptan at higher temperature and pressure, and the generated disulfide compound has poor selectivity and low yield. Therefore, development of a green, efficient and low-cost transition metal catalyst and application of the catalyst to efficient conversion of mercaptan into disulfide compounds are necessary, and the catalyst has great social and economic benefits on comprehensive utilization of mercaptan odor and reduction of environmental pollution.
Disclosure of Invention
In order to solve the above-mentioned disadvantages and drawbacks of the prior art, the present invention provides a high selectivity catalyst for converting a thiol compound. The high-selectivity catalyst has stable performance, high activity and high selectivity in the long-time reaction process, can convert mercaptan into disulfide compounds, and overcomes the defects of easy poisoning, poor selectivity, low yield and the like of the catalyst in the mercaptan catalysis process.
It is another object of the present invention to provide a method for producing the above-mentioned high selectivity catalyst for conversion of thiol compounds. The method comprises the steps of firstly loading metal to TiO by using a reducing agent 2 On to obtain metal/TiO 2 Catalyst, metal/TiO 2 Mixing the catalyst, inorganic salt and surfactant to obtain metal/TiO 2 A sol supported on a porous mesh film carrier by electrophoresis.
It is another object of the present invention to provide the use of the above-described high selectivity catalyst for converting thiol compounds in the preparation of disulfide compounds.
The aim of the invention is achieved by the following scheme:
a high-selectivity catalyst for converting thiol compounds is porous net-shaped film catalyst, which is prepared by stirring TiO 2 And a reducing agent are added into the metal salt solution, and the metal/TiO is obtained by centrifugation, washing and drying in sequence 2 The loading amount of the metal is 0.1-15 wt%; metal/TiO 2 Dissolving in water, adding inorganic salt and surfactant, and ultrasonic dispersing to obtain metal/TiO 2 Sol; taking the porous net-shaped film as a cathode or wrapping the porous net-shaped film on the outer surface of the cathode, taking a titanium sheet as an anode, and applying voltage to metal/TiO 2 Electrophoresis of the sol to obtain metal/TiO 2 Loading on porous net film, washing, drying, calcining at 200-600 deg.C; the metal/TiO 2 The load capacity is a porous net0.1-5 mg/cm of film 2 。
Preferably, the metal salt solution is one or more of copper salt solution, manganese salt solution, nickel salt solution and cobalt salt solution; the TiO 2 And the mass ratio of metal ions in the metal salt solution is 100 (0.01-15); the mol ratio of the reducing agent to the metal ions in the metal salt solution is 1 (0.1-20); the concentration of the metal salt solution is 0.01-1 mol/L.
More preferably, the copper salt in the copper salt solution is more than one of copper chloride, copper sulfate, copper nitrate and copper acetate; the manganese salt in the manganese salt solution is one or more of manganese nitrate, manganese sulfate and manganese chloride; the nickel salt in the nickel salt solution is more than one of nickel nitrate and nickel sulfate, and the cobalt salt in the cobalt salt solution is more than one of cobalt nitrate and cobalt sulfate.
Preferably, the reducing agent is more than one of sodium borohydride, potassium borohydride and ammonia borane; the inorganic salt is more than one of sodium nitrate, sodium sulfate, sodium perchlorate, potassium sulfate and potassium nitrate; the surfactant is more than one of polyvinylpyrrolidone, polyethylene glycol, hexadecyl trimethyl ammonium bromide or sodium dodecyl sulfonate.
Preferably, the metal/TiO 2 The mass ratio of the inorganic salt to the surfactant is (1-5): 0.01-1; the metal/TiO 2 The mass to volume ratio of water is (1-5) g to 50mL.
Preferably, the porous net-shaped film is textile, foam nickel, glass fiber paper or ceramic fiber paper.
Preferably, the electrophoresis time is 1-60 min, and the applied voltage is 1-20V.
The preparation method of the high-selectivity catalyst for converting the mercaptan compound comprises the following specific steps:
s1, fully dissolving metal salt in water, and adding TiO under the stirring condition 2 Stirring for 0.5-24 h, adding a reducing agent, stirring for 15-120 min, centrifuging, washing and drying in sequence to obtain metal/TiO 2 The loading of the metal is 0.1-15 wt%;
s2, metal/TiO 2 Dissolving in water, adding inorganic salt and surfactant, and ultrasonic dispersing to obtain metal/TiO 2 Sol;
s3, taking the porous net-shaped film as a cathode or wrapping the porous net-shaped film on the outer surface of the cathode, taking a titanium sheet as an anode, and carrying out metal/TiO (titanium oxide) treatment under the action of an external voltage 2 Electrophoresis of the sol to obtain metal/TiO 2 Loading on porous net film, washing, drying, calcining at 200-600 deg.C for 2-6 hr to obtain metal/TiO 2 Supported porous reticulated film, i.e. high selectivity catalyst for conversion of mercaptans, metal/TiO 2 The load is 0.1-5 mg/cm 2 。
The high-selectivity catalyst for converting the mercaptan compound is applied to the preparation of the disulfide compound, and the mercaptan compound is an organic matter containing-SH groups.
Preferably, the high selectivity catalyst is placed in mercaptan with the flow rate of 10-1000 mL/min and dry air with the flow rate of 10-5000 mL/min, and the disulfide compound is prepared by catalytic reaction under the conditions that the humidity is 0-90RH and the temperature is 0-45 ℃; the organic matter containing the-SH group is more than one of methyl mercaptan, ethyl mercaptan or phenyl mercaptan; the concentration of the mercaptan compound is 10-10000 ppm; the disulfide compound is one or more of dimethyl disulfide, diethyl disulfide or diphenyl disulfide.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention is characterized in that the metal/TiO is 2 Under the action of the supported porous net-shaped film catalyst, the metal/TiO is regulated and controlled 2 The components and the loading capacity of the metal active site in the porous reticular film can realize the high-efficiency conversion of methyl mercaptan, ethyl mercaptan, phenyl mercaptan and other compounds containing-SH groups into corresponding disulfide compounds, the thiol compounds can be catalyzed and oxidized into disulfide compounds with high selectivity at normal temperature, wherein the conversion rate of the thiol compounds is close to 100%, the selectivity of the disulfide compounds is more than 95%, the catalyst still keeps high activity and high selectivity after multiple recycling, and the catalyst has the advantages of wide application range, high selectivity, stable performance and the like. Effectively solves the problems of easy poisoning of Pd and Pt noble metal catalysts, low conversion rate of mercaptan compounds and poor catalytic conversion selectivity of disulfide compounds.
2. The metal/TiO provided by the invention 2 Compared with noble metal catalysts such as Pd, pt and the like, the porous reticular film catalyst has better sulfur resistance, greatly reduces the cost and has better catalytic conversion application prospect in the mercaptan etherification process.
3. The invention provides a load metal/TiO 2 The porous net-shaped film catalyst can convert mercaptan into disulfide compound at room temperature, and only uses mercaptan and O in the reaction process 2 Can be used as raw material to complete catalytic conversion at normal temperature, avoiding the use of I 2 、Br 2 、H 2 O 2 The constant-strength oxidant and sulfur reduce the secondary pollution of the product in the reaction process, and have the advantages of mild reaction conditions, green process and the like.
Drawings
FIG. 1 is a supported CuO prepared in example 1 x /TiO 2 Scanning electron micrographs of the porous reticulated film catalyst of (c).
Detailed Description
The present invention is further illustrated below in conjunction with specific examples, but should not be construed as limiting the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
1. 0.095g of copper nitrate trihydrate was weighed into 300mL of ultra pure water, sonicated at room temperature for 10min, and 5g of commercial TiO was added with stirring 2 (Shanghai Meilin Biochemical technology Co., ltd.) stirring was continued for 4 hours, then 5845mL of 0.02mol/L NaBH was added 4 Stirring the solution for 15min, centrifuging and washing sequentially, and drying at 60deg.C for 6 hr to obtain CuO x /TiO 2 (x=0 or 1/2), cuO x The Cu loading was 0.5wt%.
2. 1g of CuO was weighed out x /TiO 2 Dissolving in 50mL of water, adding 2.65g of sodium carbonate and 0.01g of polyethylene glycol, and performing ultrasonic dispersion to obtain CuO x /TiO 2 Sol;
3. cutting porous reticular film (textile, foam nickel, glass fiber paper or ceramic fiber paper) into 100mm 50mm, washing, drying, wrapping on the outer surface of cathode, taking titanium sheet as anode, and coating CuO on the surface of cathode x /TiO 2 Electrophoresis of the sol for 15min, and external connection of voltage stabilizing power supply for 10V to obtain CuO x /TiO 2 Loading on porous net film, washing, drying, calcining at 200 deg.C to obtain CuO-loaded film x /TiO 2 Porous network film catalyst of CuO thereof x /TiO 2 The loading was 1g/cm 2 。
FIG. 1 shows the loaded CuO prepared in this example x /TiO 2 Scanning electron microscope images of the porous reticulated film catalyst. As can be seen from FIG. 1, the CuO is supported x /TiO 2 The surface of the rear porous meshed film was observed to be visibly white granular or bulk.
Example 2
1. 0.1425g copper nitrate trihydrate was weighed into 300mL of ultra pure water, sonicated at room temperature for 10min, and 5g of commercial TiO was added with stirring 2 (Shanghai Meilin Biochemical technology Co., ltd.) stirring was continued for 4 hours, then 5845mL of 0.02mol/L NaBH was added 4 Stirring the solution for 15min, centrifuging and washing sequentially, and drying at 60deg.C for 6 hr to obtain CuO x /TiO 2 (x=0 or 1/2), cuO x The Cu loading was 0.75wt%.
2. 1g of CuO was weighed out x /TiO 2 Dissolving in 50mL of water, adding 2.65g of sodium carbonate and 0.01g of polyethylene glycol, and performing ultrasonic dispersion to obtain CuO x /TiO 2 Sol;
3. cutting porous reticular film into 100mm 50mm, washing, drying, wrapping on the outer surface of cathode, taking titanium sheet as anode, and treating CuO x /TiO 2 Electrophoresis of the sol for 15min, connecting with voltage stabilizing power supply 5V, and adding CuO x /TiO 2 Loaded on a porous net film, then washed and dried at 200 DEG CCalcining to obtain the loaded CuO x /TiO 2 Porous network film catalyst of CuO thereof x /TiO 2 The loading was 1g/cm 2 。
Example 3
1. 0.095g of copper nitrate trihydrate and 0.0619g of nickel nitrate hexahydrate solution were weighed into 300mL of ultra-pure water, sonicated at room temperature for 10min, and 5g of commercial TiO was added under stirring 2 (Shanghai Meilin Biochemical technologies Co., ltd.) stirring was continued for 4 hours, and then 5.845mL of 0.02mol/L NaBH was added 4 Stirring the solution for 15min, centrifuging and washing sequentially, and drying at 60deg.C for 6 hr to obtain CuNiO x /TiO 2 (x=0-3), the loading of Cu was 0.5wt%, and the loading of Ni was 0.25wt%.
2. 1g of CuNiO was weighed out x /TiO 2 Dissolving in 50mL of water, adding 2.65g of sodium carbonate and 0.01g of polyethylene glycol, and performing ultrasonic dispersion to obtain CuNiO x /TiO 2 Sol;
3. cutting porous reticular film into 100mm 50mm, washing, drying, wrapping on the outer surface of cathode, and coating with titanium sheet as anode to obtain CuNiO x /TiO 2 Electrophoresis for 15min with external voltage-stabilized power supply 5V, and collecting CuNiO x /TiO 2 Loading on porous reticular film, washing, drying, calcining at 200 deg.C to obtain loaded CuNiO x /TiO 2 Porous network film catalyst of (2) CuNiO thereof x /TiO 2 The loading was 1g/cm 2 。
Comparative example 1
The difference from example 1 is that: in step 1, 0.117g of chloroplatinic acid hexahydrate was weighed into 300mL of ultrapure water, and in step 2, 1g of Pt/TiO was weighed 2 Dissolving in 50mL of water, and performing the reaction on Pt/TiO in the step 3 2 Electrophoresis of the sol for 15min, connecting with a regulated power supply 10V, and adding Pt/TiO 2 Loading on porous net film, washing, drying, calcining at 200 deg.C to obtain Pt/TiO loading film 2 Porous network film catalyst of (2) Pt/TiO 2 The loading was 1g/cm 2 。
Application example 1
(1) Example 1, example3. Example 4 preparation of Supported CuO x /TiO 2 Porous net-shaped film catalyst and CuNiO x /TiO 2 Porous network film catalyst, pt/TiO 2 Porous network film catalyst and TiO 2 The porous net-shaped film catalysts are respectively arranged in the normal pressure gas-solid phase photocatalytic reactor for reaction.
(2) Methyl mercaptan is taken as a catalytic oxidation object, 50mL/min methyl mercaptan (150 pm in concentration) and 150mL/min dry air are introduced, the reaction temperature is 35 ℃, the humidity is 0, and the concentration reaches 43+/-1 ppm after mixing.
(3) Opening a control valve of the reactor to enable the methyl mercaptan polluted gas which is uniformly mixed to continuously flow through the CuO x /TiO 2 Porous network film catalyst, pt/TiO 2 Porous net-shaped film catalyst and CuNiO x /TiO 2 Porous reticulated film catalyst or TiO 2 The surface of the porous reticular film catalyst is subjected to methyl mercaptan recycling activity test, and the test results are shown in the following table 1. As can be seen from Table 1, pt/TiO 2 After the porous reticular film catalyst reacts for 90min, the removal rate of methyl mercaptan is 31.81 percent, the generation rate of dimethyl disulfide is 32.72 percent, and CuO is generated x /TiO 2 Porous net-shaped film catalyst and CuNiO x /TiO 2 The activity of the porous net-shaped film catalyst for generating dimethyl disulfide by catalytic oxidation of methyl mercaptan is always stabilized at a higher level in the whole reaction process. Wherein CuO x /TiO 2 The porous net-shaped film catalyst has the best effect, the removal rate of methyl mercaptan is 100% after 90min of reaction, and the generation rate of dimethyl disulfide is more than 95%. Compared with noble metal catalysts such as Pt, pd and the like, the transition metal catalyst has higher activity, more stable sulfur resistance and lower cost in the process of catalyzing and oxidizing a mercaptan compound, and is a catalyst with wide application prospect in the mercaptan etherification process.
Table 1 shows the activity of methyl mercaptan recycling in examples 1 and 3 and comparative example 1
Application example 2
(1) CuO-supported prepared in example 1 x /TiO 2 The porous reticular film catalyst is arranged in a normal temperature gas-solid phase photocatalysis reactor for reaction.
(2) Methyl mercaptan is taken as a catalytic oxidation object, methyl mercaptan (with the concentration of 150 ppm) with the flow rate of 50mL/min and 150mL/min dry air are introduced, the reaction temperature is 35 ℃, the humidity is 0, and the concentration reaches the balance of 43+/-1 ppm after mixing.
(3) Opening a control valve of the reactor to enable the reaction gas which is uniformly mixed to continuously flow through the CuO x /TiO 2 The surface of the porous reticular film catalyst is catalyzed and oxidized with methyl mercaptan at room temperature to generate dimethyl disulfide.
For CuO x /TiO 2 The porous reticular film catalyst is subjected to a cycle stability test, the used catalyst is soaked in a culture dish containing ethanol for 5min, the step is repeated for three times, and then the washed catalyst is put into a vacuum drying oven at 60 ℃ for drying for 2h, and the quality of the washed catalyst is not obviously changed. According to the experimental steps, the catalytic oxidation performance of methyl mercaptan in 90min of the catalyst is tested under the same conditions, and the test is repeated. CuO after multiple cycles x /TiO 2 The removal rate of methyl mercaptan by the porous reticular film catalyst is 100%, and the generation rate of dimethyl disulfide is as high as 95%. CuO is superior to noble metal catalysts such as Pt, pd, etc x /TiO 2 The porous reticular film catalyst has better sulfur resistance and more stable catalytic oxidation performance.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. A process for the preparation of a high selectivity catalyst for the conversion of thiol compounds, characterized in that it comprises the following specific steps:
s1, fully dissolving metal salt in water to prepare a metal salt solution, and adding TiO under the stirring condition 2 Stirring for 0.5-24 h, adding a reducing agent, stirring for 15-120 min, and sequentially centrifuging, washing and drying to obtain metal/TiO 2 The metal loading is 0.1-15 wt%; the metal salt solution is one or more of copper salt solution, manganese salt solution, nickel salt solution and cobalt salt solution; the TiO 2 And the mass ratio of metal ions in the metal salt solution is 100 (0.01-15); the mol ratio of the reducing agent to the metal ions in the metal salt solution is 1 (0.1-20); the concentration of the metal salt solution is 0.01-1 mol/L;
s2. Metal/TiO 2 Dissolving in water, adding inorganic salt and surfactant, and ultrasonic dispersing to obtain metal/TiO 2 Sol; the metal/TiO 2 The mass ratio of the inorganic salt to the surfactant is (1-5) (0.01-1); the metal/TiO 2 The mass ratio of the water to the water is (1-5) g, 50 and mL; the inorganic salt is more than one of sodium nitrate, sodium sulfate, sodium perchlorate, potassium sulfate and potassium nitrate;
s3, taking the porous net-shaped film as a cathode or wrapping the porous net-shaped film on the outer surface of the cathode, taking a titanium sheet as an anode, and applying voltage of 1-20V to metal/TiO 2 Electrophoresis is carried out on the sol for 1-60 min, and metal/TiO is carried out 2 Loading on porous net film, washing, drying, calcining at 200-600 deg.C for 2-6 hr to obtain metal/TiO 2 Supported porous reticulated film, i.e. high selectivity catalyst for conversion of mercaptans, metal/TiO 2 The load is 0.1-5 mg/cm 2 metal/TiO 2 The metal loading amount is 0.1-15 wt%.
2. The method for preparing a high selectivity catalyst for converting a thiol compound according to claim 1, wherein the copper salt in the copper salt solution in step S1 is one or more of copper chloride, copper sulfate, copper nitrate, and copper acetate; the manganese salt in the manganese salt solution is one or more of manganese nitrate, manganese sulfate and manganese chloride; the nickel salt in the nickel salt solution is more than one of nickel nitrate and nickel sulfate, and the cobalt salt in the cobalt salt solution is more than one of cobalt nitrate and cobalt sulfate; the reducing agent is more than one of sodium borohydride, potassium borohydride and ammonia borane.
3. The method for preparing a high selectivity catalyst for converting a thiol compound according to claim 1, wherein the surfactant in step S2 is one or more of polyvinylpyrrolidone, polyethylene glycol, cetyltrimethylammonium bromide, or sodium dodecyl sulfonate.
4. The method for preparing a high selectivity catalyst for converting thiol compounds according to claim 1, wherein the porous mesh film in step S3 is a textile, nickel foam, glass fiber paper or ceramic fiber paper.
5. A high selectivity catalyst for the conversion of thiol compounds, characterized in that it is prepared by the process according to any one of claims 1 to 4.
6. The use of a high selectivity catalyst for the conversion of thiol compounds as claimed in claim 5 for the preparation of disulfide compounds, wherein said thiol compound is an organic compound containing a-SH group.
7. The application of the high-selectivity catalyst for converting a mercaptan compound to the preparation of a disulfide compound according to claim 6, wherein the high-selectivity catalyst is placed in 10-1000 mL/min of mercaptan compound and 10-5000 mL/min of dry air, and the disulfide compound is prepared by catalytic reaction under the conditions of 0-90RH and 0-45 ℃; the organic matter containing the-SH group is more than one of methyl mercaptan, ethyl mercaptan or phenyl mercaptan; the concentration of the mercaptan compound is 10-10000 ppm; the disulfide compound is one or more of dimethyl disulfide, diethyl disulfide or diphenyl disulfide.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07328388A (en) * | 1994-06-07 | 1995-12-19 | Babcock Hitachi Kk | Deodorizing catalyst device |
| JPH10146531A (en) * | 1996-09-20 | 1998-06-02 | Daiken Kagaku Kogyo Kk | Metal superfine particle carrying photocatayst and of its production |
| CN101119933A (en) * | 2005-12-20 | 2008-02-06 | Lg化学株式会社 | Titania sol, method of preparing the same, and coating composition comprising the same |
| JP2008073571A (en) * | 2006-09-19 | 2008-04-03 | Covalent Materials Corp | Photocatalyst-supported ceramic foam and its manufacturing method |
| CN102941129A (en) * | 2012-11-06 | 2013-02-27 | 中国科学院广州地球化学研究所 | Supported photocatalyst as well as preparation method and application thereof |
| CN113385160A (en) * | 2021-07-15 | 2021-09-14 | 广东工业大学 | Photocatalyst with nonmetal substrate loaded with P25 titanium dioxide and preparation method and application thereof |
-
2021
- 2021-12-24 CN CN202111599118.7A patent/CN114345338B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07328388A (en) * | 1994-06-07 | 1995-12-19 | Babcock Hitachi Kk | Deodorizing catalyst device |
| JPH10146531A (en) * | 1996-09-20 | 1998-06-02 | Daiken Kagaku Kogyo Kk | Metal superfine particle carrying photocatayst and of its production |
| CN101119933A (en) * | 2005-12-20 | 2008-02-06 | Lg化学株式会社 | Titania sol, method of preparing the same, and coating composition comprising the same |
| JP2008073571A (en) * | 2006-09-19 | 2008-04-03 | Covalent Materials Corp | Photocatalyst-supported ceramic foam and its manufacturing method |
| CN102941129A (en) * | 2012-11-06 | 2013-02-27 | 中国科学院广州地球化学研究所 | Supported photocatalyst as well as preparation method and application thereof |
| CN113385160A (en) * | 2021-07-15 | 2021-09-14 | 广东工业大学 | Photocatalyst with nonmetal substrate loaded with P25 titanium dioxide and preparation method and application thereof |
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