CN103990453A - Preparation method of catalyst for catalytic hydrogenation - Google Patents
Preparation method of catalyst for catalytic hydrogenation Download PDFInfo
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- CN103990453A CN103990453A CN201410240918.3A CN201410240918A CN103990453A CN 103990453 A CN103990453 A CN 103990453A CN 201410240918 A CN201410240918 A CN 201410240918A CN 103990453 A CN103990453 A CN 103990453A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 28
- 239000000919 ceramic Substances 0.000 claims abstract description 18
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 57
- 229910052763 palladium Inorganic materials 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- -1 amino silicane Chemical compound 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 abstract 1
- 229910000077 silane Inorganic materials 0.000 abstract 1
- 239000010408 film Substances 0.000 description 41
- 239000002105 nanoparticle Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 210000002808 connective tissue Anatomy 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000006424 Flood reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
Abstract
The invention relates to a preparation method of a catalyst for catalytic hydrogenation, belonging to the field of a catalysis technique. The catalyst takes a ceramic membrane as a carrier; the preparation method comprises the steps of firstly, modifying the surface of the membrane by amino silane, and impregnating by metal nanoparticle sol to obtain the catalyst. The preparation method has the advantage that the nanoscale catalyst particles are supported on the surface of the ceramic membrane modified by the silane, so that the problem that subsequent separation between the catalyst and the product is difficult can be solved. The catalyst is simple in preparation technology, high in activity and good in stability, thus being widely applied to the hydrogenation reaction process.
Description
Technical field
The present invention relates to a kind of preparation method of loaded catalyst, relate in particular to the method for preparing catalyst for hydrogenation process, belong to catalysis technical field.
Background technology
Nanocatalyst, because its grain diameter is little, specific area is large, blemish is many, shows excellent catalytic performance, causes people's extensive concern.Nanocatalyst, in liquid-phase catalysis reaction, can suspended state be distributed in reactor or be fixed on carrier as formed loaded catalyst on glass, quartz or film.Although the catalyst efficiency of suspended state will, higher than loaded catalyst, in actual applications, exist the problem of nanocatalyst and separation of products, catalyst recovery, catalytic active component is fixed on and on film, forms effectively head it off of film catalyst.
Film catalyst normally loads on palladium, platinum isoreactivity component on the surface of film or immerses in fenestra by methods such as surface impregnation, ion-exchange and chemical depositions, film forms catalyst together with catalytic active component, and film plays the effect of separation and catalyst carrier.Although researcher has done to study in great detail to preparation method, the preparation technology etc. of film catalyst, also there are some key issues, as: one, in unit bodies integrated membrane, active component content is few; Two, a little less than the adhesion between catalytic activity component and film.Patent (ZL201010617062.9) has been reported a kind of preparation method of film catalyst, first ceramic membrane carrier is carried out amino modifiedly, be then immersed in the anion solutions of active component palladium, and then electronation makes film catalyst.In this process, palladium nano-particles size, pattern, composition etc. are difficult to control.
Summary of the invention
The object of the invention is to provide in order to overcome nanoparticle catalyst and a separation of products difficult problem preparation method of a kind of catalytic hydrogenation catalyst, metal nanoparticle is directly carried on to tubular ceramic membrane surface and prepares film catalyst, avoid catalyst and separation of products, optimized production process.
Technical scheme of the present invention is: the preparation method of catalyst for a kind of catalytic hydrogenation, and its concrete steps are as follows: the modification of A. ceramic membrane surface: ceramic-film tube is immersed in amino silicane coupling agent solution, carry out surface modification, take out washing, dry;
B. metal nanoparticle colloidal sol preparation: metal salt powder and stabilizing agent are added in organic solvent and be mixed with reaction system, add thermal agitation, controlled concentration, temperature, time, stabilizing agent and metal molar ratio, make metal nanoparticle colloidal sol;
C. dipping: the ceramic-film tube after steps A modification is immersed in metal nanoparticle colloidal sol prepared by step B, controls temperature, time;
D. washing is dry: use ethanol that the ceramic-film tube after dipping is thoroughly cleaned, and natural drying, make catalytic hydrogenation catalyst.
In preferred steps A, ceramic-film tube is tubular inorganic membrane, zirconium oxide film pipe, silicon oxide film pipe or oxidation titanium film pipe.
Amino silicane coupling agent in preferred steps A in amino silicane coupling agent solution is (APTS) γ-aminopropyltrimethoxysilane, (EDA) N-(β-aminoethyl)-γ-aminopropyl trimethoxy silicon, (DETA) 3-[2-(2-aminoethylamino) ethylamino] propyl group-trimethoxy silane or (APS) gamma-aminopropyl-triethoxy-silane; Solvent in amino silicane coupling agent solution is carrene, toluene or absolute ethyl alcohol; The concentration of amino silicane coupling agent solution is 0.1～6g/L; Modification time is 1～36h; Modification temperature is normal temperature, generally at 0～40 DEG C.
Metal in preferred steps B in metal salt powder is palladium, platinum or silver; Slaine is metallic acetate, nitrate or hydrochloride; Stabilizing agent is polyvinylpyrrolidone (PVP) or polystyrene (PSt); Organic solvent is methyl alcohol, ethanol, ethylene glycol and ethene; Metal nanoparticle collosol concentration is 0.01～0.1mol/L; Heating-up temperature is 30～100 DEG C; Mixing time is 1～24h; The mol ratio of the metal in stabilizing agent and metal salt powder is 1～40:1.
In preferred steps C, dip time is 1～48h, and dipping temperature is 0～70 DEG C.
It is the catalytic performance that model reaction is evaluated prepared catalyst that the present invention adopts p-nitrophenol catalytic hydrogenation to prepare para-aminophenol.
P-nitrophenol catalytic hydrogenation reaction carries out in autoclave.14g p-nitrophenol, 143mL absolute ethyl alcohol are added in reactor together with 20mL deionized water, by membrane module, film pipe is fixed in still; After sealing, check air-tightness, with after hydrogen exchange 5～6 times, pass into the hydrogen of 0.4～0.5MPa and heat up, temperature stops heating while reaching setting value; Regulate speed of agitator to test after rising to 1.7MPa to 200rpm and by pressure, record pressure drop 0.1MPa used time ask that and hydrogen make-up in time stops after reaction 60min.After getting product dilution, use efficient liquid phase chromatographic analysis, calculate feed stock conversion and selectivity of product according to calibration curve, and the amount of the hydrogen being consumed with unit interval elementary membrane surface area represents catalyst activity.
Beneficial effect:
1. the present invention loads to nanoparticle catalyst on ceramic membrane, to prepare film catalyst and be applied in catalytic hydrogenation reaction, can avoid the problem of catalyst and separation of products.
2. first the present invention prepares nano particle colloidal sol in the time preparing film catalyst, then floods amino modified ceramic-film tube and prepares film catalyst.In the preparation process of nano particle colloidal sol, can effectively control particle size, pattern and composition, improve the activity of catalyst.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) figure: (a) ceramic membrane carrier, (b) palladium/ceramic membrane catalyst.
Fig. 2 is ESEM (FESEM) figure: (a) ceramic membrane carrier, (b) palladium/ceramic membrane catalyst.
Detailed description of the invention
Illustrate the result of use of the inventive method and catalyst below by embodiment.
Embodiment 1 Pd/Al
2o
3the preparation of film catalyst
(1) preparation of palladium particle colloidal sols
Weigh 0.224g palladium and 0.555g polyvinylpyrrolidone (PVP and palladium mol ratio are 5) and join in 25mL ethanol, at 70 DEG C, stirring 2h, to make concentration be 0.04mol/L palladium nano-particles colloidal sol.
(2) preparation of catalyst
First soak film pipe (length: 6cm, external diameter: 12mm, internal diameter: 8mm, material: Al by deionized water
2o
3, membrane aperture: 200nm, adventitia), dry for standby.Film pipe is immersed in the EDA/ dichloromethane solution of 50mL0.2g/L, after dipping 2h, take out with absolute ethyl alcohol and clean and dry.At 30 DEG C, the tubular inorganic membrane after modification is immersed in 25mL0.04mol/L palladium nano-particles colloidal sol, after 12h, take out with alcohol flushing number time, naturally dry.
Fig. 1 is the XRD collection of illustrative plates of ceramic membrane carrier and palladium/ceramic catalytic film.Contrast ceramic membrane and catalytic membrane, can find at 2=40.1 °, 44.7 °, occurred the characteristic diffraction peak of palladium crystal, corresponding Pd (111) crystal face and Pd (200) crystal face respectively.This shows that palladium successfully loads to ceramic membrane surface with the form of nano particle, and diffraction maximum a little less than the particle diameter of wider explanation palladium less, disperse better.The size that can be calculated palladium particle according to Scherrer formula is 3.7nm.Fig. 2 is the FESEM figure of ceramic membrane carrier and palladium/ceramic catalytic film.The particle surface of contrast ceramic membrane mulch film (a) Smooth, after loaded palladium catalyst, obviously roughening of surface, but particle not obvious, may be because the parcel of PVP causes.
By Pd/Al
2o
3film catalyst is applied in p-nitrophenol catalytic hydrogenation reaction, and hydrogenation speed is 20.4mol/ (h × m
2), higher than the hydrogenation speed 15.6mol/ (h × m of patent (ZL201010617062.9) report
2).
Embodiment 2 Pd/ZrO
2the preparation of film catalyst
(1) preparation of palladium particle colloidal sols
Weigh 0.0560g palladium and 1.0400g polystyrene (PSt and palladium mol ratio are 40) and join in 25mL methyl alcohol, at 30 DEG C, stirring 12h, to make concentration be 0.01mol/L palladium nano-particles colloidal sol.
(2) Pd/ZrO
2the preparation of film catalyst
First soak film pipe (length: 6cm, external diameter: 12mm, internal diameter: 8mm, material: ZrO by deionized water
2,, membrane aperture: 500nm, adventitia), dry for standby.Film pipe is immersed in the APS/ ethanolic solution of 50mL6g/L, after dipping 36h, take out with absolute ethyl alcohol and clean and dry.At 50 DEG C, the zirconium oxide film pipe after modification is immersed in 25mL0.01mol/L palladium nano-particles colloidal sol, after 2h, take out with alcohol flushing number time, naturally dry.
By Pd/ZrO
2film catalyst is applied in p-nitrophenol catalytic hydrogenation reaction, and hydrogenation speed is 17.5mol/ (h × m
2).
Embodiment 3 Pt/Al
2o
3the preparation of film catalyst
(1) preparation of Pt nanoparticle colloidal sol
Weigh 0.443g platinum chloride and 0.1111g polyvinylpyrrolidone (PVP and palladium mol ratio are 1) and join in 25mL ethylene glycol, at 100 DEG C, stirring 24h, to make concentration be 0.1mol/L Pt nanoparticle colloidal sol.
(2) preparation of catalyst
First soak film pipe (length: 6cm, external diameter: 12mm, internal diameter: 8mm, material: Al by deionized water
2o
3, membrane aperture: 200nm, adventitia), dry for standby.Film pipe is immersed in the EDA/ dichloromethane solution of 50mL0.1g/L, after dipping 12h, take out with absolute ethyl alcohol and clean and dry.At 0 DEG C, the tubular inorganic membrane after modification is immersed in 25mL0.1mol/L Pt nanoparticle colloidal sol, after 36h, take out with alcohol flushing number time, naturally dry.
By Pt/Al
2o
3film catalyst is applied in p-nitrophenol catalytic hydrogenation reaction, and hydrogenation speed is 16.4mol/ (h × m
2).
Claims (5)
1. a preparation method for catalyst for catalytic hydrogenation, its concrete steps are as follows:
A. ceramic membrane surface modification: ceramic-film tube is immersed in amino silicane coupling agent solution, carry out surface modification, take out washing, dry;
B. metal nanoparticle colloidal sol preparation: metal salt powder and stabilizing agent are added in organic solvent and be mixed with reaction system, add thermal agitation, controlled concentration, temperature, time, stabilizing agent and metal molar ratio, make metal nanoparticle colloidal sol;
C. dipping: the ceramic-film tube after steps A modification is immersed in metal nanoparticle colloidal sol prepared by step B, controls temperature, time;
D. washing is dry: use ethanol that the ceramic-film tube after dipping is thoroughly cleaned, and natural drying, make catalytic hydrogenation catalyst.
2. preparation method according to claim 1, is characterized in that in steps A, ceramic-film tube is tubular inorganic membrane, zirconium oxide film pipe, silicon oxide film pipe or oxidation titanium film pipe.
3. preparation method according to claim 1, is characterized in that in steps A that the amino silicane coupling agent in amino silicane coupling agent solution is for (APTS) γ-aminopropyltrimethoxysilane, (EDA) N-(β-aminoethyl)-γ-aminopropyl trimethoxy silicon, (DETA) 3-[2-(2-aminoethylamino) ethylamino] propyl group-trimethoxy silane or (APS) gamma-aminopropyl-triethoxy-silane; Solvent in amino silicane coupling agent solution is carrene, toluene or absolute ethyl alcohol; The concentration of amino silicane coupling agent solution is 0.1～6g/L; Modification time is 1～36h.
4. preparation method according to claim 1, is characterized in that in step B, the metal in metal salt powder is palladium, platinum or silver; Slaine is metallic acetate, nitrate or hydrochloride; Stabilizing agent is polyvinylpyrrolidone (PVP) or polystyrene (PSt); Organic solvent is methyl alcohol, ethanol, ethylene glycol and ethene; Metal nanoparticle collosol concentration is 0.01～0.1mol/L; Heating-up temperature is 30～100 DEG C; Mixing time is 1～24h; Stabilizing agent is 1～40:1 with the metal molar ratio in salt powder.
5. preparation method according to claim 1, is characterized in that in step C, dip time is 1～48h, and temperature is 0～70 DEG C.
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| CN105921173A (en) * | 2016-04-21 | 2016-09-07 | 河南大学 | Nano-silver composite textile catalyst and application thereof |
| CN108714434A (en) * | 2018-06-04 | 2018-10-30 | 中国中化股份有限公司 | A kind of light oil type hydrogen cracking catalyst and preparation method thereof |
| CN109529946A (en) * | 2018-12-19 | 2019-03-29 | 山西大学 | A kind of method that solid-carrying type Cu-Ni bimetallic catalyst and its catalysis furfural complete hydrogenation prepare tetrahydrofurfuryl alcohol |
| CN111675373A (en) * | 2020-05-20 | 2020-09-18 | 哈尔滨工业大学 | Spinel type composite metal oxide modified ceramic membrane filtration coupled ozone catalytic oxidation synergistic combination water treatment method |
| CN114797846A (en) * | 2022-05-24 | 2022-07-29 | 四川轻化工大学 | Catalyst for hydrodechlorination and preparation method thereof |
| CN115487869A (en) * | 2022-01-04 | 2022-12-20 | 浙江理工大学 | Preparation method of catalytic ozone type ceramic membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921173A (en) * | 2016-04-21 | 2016-09-07 | 河南大学 | Nano-silver composite textile catalyst and application thereof |
| CN108714434A (en) * | 2018-06-04 | 2018-10-30 | 中国中化股份有限公司 | A kind of light oil type hydrogen cracking catalyst and preparation method thereof |
| CN109529946A (en) * | 2018-12-19 | 2019-03-29 | 山西大学 | A kind of method that solid-carrying type Cu-Ni bimetallic catalyst and its catalysis furfural complete hydrogenation prepare tetrahydrofurfuryl alcohol |
| CN111675373A (en) * | 2020-05-20 | 2020-09-18 | 哈尔滨工业大学 | Spinel type composite metal oxide modified ceramic membrane filtration coupled ozone catalytic oxidation synergistic combination water treatment method |
| CN115487869A (en) * | 2022-01-04 | 2022-12-20 | 浙江理工大学 | Preparation method of catalytic ozone type ceramic membrane |
| CN114797846A (en) * | 2022-05-24 | 2022-07-29 | 四川轻化工大学 | Catalyst for hydrodechlorination and preparation method thereof |
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Application publication date: 20140820 |