CN108144602A - A kind of preparation method of high abrasion micron noble-metal-supported silica support catalyst - Google Patents
A kind of preparation method of high abrasion micron noble-metal-supported silica support catalyst Download PDFInfo
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- CN108144602A CN108144602A CN201611094282.1A CN201611094282A CN108144602A CN 108144602 A CN108144602 A CN 108144602A CN 201611094282 A CN201611094282 A CN 201611094282A CN 108144602 A CN108144602 A CN 108144602A
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- metal
- noble
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- silica support
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000005299 abrasion Methods 0.000 title claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000003921 oil Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 34
- 239000002002 slurry Substances 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical group 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000005234 chemical deposition Methods 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- 238000001802 infusion Methods 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 239000011268 mixed slurry Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- -1 Ammoniom-Acetate Chemical compound 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005662 Paraffin oil Substances 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 229940031098 ethanolamine Drugs 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 229960004011 methenamine Drugs 0.000 claims 1
- 150000007524 organic acids Chemical class 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 15
- 238000001035 drying Methods 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000008187 granular material Substances 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 229920006335 epoxy glue Polymers 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 15
- 239000011258 core-shell material Substances 0.000 description 13
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 12
- 235000013339 cereals Nutrition 0.000 description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- 150000004056 anthraquinones Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 235000020985 whole grains Nutrition 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of high abrasion micron noble-metal-supported silica support catalyst.This method is mainly pre-mixed by silicon oxide powder, acid, additive, dispersant, Ludox after noble metal active component is impregnated etc., epoxy glue is injected aging in high temperature oil column and is molded by the fluidic generator through certain pore size again, after by washing, drying, roasting and obtain the high micron spherical shape metal carrying catalyst of wearability.Using the catalyst that the method obtains, with the structure not only with mesoporous characteristic, (aperture is adjustable, and scale is in 2~50nm, and specific surface area is in 200~450m2Between/g, Kong Rong is between 0.5~1.5mL/g), and its abrasion resistance is also high, and contained noble metal dispersion degree is high.In addition, use the Hydrogenation catalyst granule scale for preparing of the present invention controllable for 30~100 μm, heterogeneous catalytic reaction of the uniformity height suitable for fluidized-bed reactor.
Description
Technical field
The present invention relates to a kind of preparation methods of noble metal catalyst, and in particular to a kind of high abrasion micron noble-metal-supported
The preparation method of silica support catalyst.
Background technology
The preparation method and its preparation condition of catalyst can generate significantly affecting to its performance.The variation of preparation method, meeting
Change structure, composition, granular size and its dispersion degree of catalyst, then catalyst activity is impacted.At present, in industry
Noble metal catalyst is mostly prepared using infusion process, ion-exchange, the chemical deposition precipitation method.Its main thinking be as
Where further noble-metal-supported is carried out on the carrier of forming.Its active component prepared is generally being present in carrier
Surface.For the catalyst of general fluidized-bed process, the wearability of catalyst and the leachability for preventing noble metal
Be improve catalyst activity, stability key factor.However above-mentioned conventional preparation method is used, inevitably exist
The loss of catalyst surface active component noble metal is caused to cause subsequent reactions efficiency due to collision, friction between catalyst
Decline.
Active component is wrapped in the inside of the inorganic oxides such as silica, core-shell type structure catalyst can be formed.Due to
The particularity of its structure, core-shell structure catalyst can not only realize that controlled catalytic is reacted, can also protect in-core by shell
Active component is not corroded by external environment, while the problems such as can also solve the reunion of active component, therefore can realize catalyst
High activity, high stability and highly selective.
Nucleocapsid metal load type catalyst belongs to inorganic-inorganic nucleocapsid compound particle.Inorganic-inorganic nucleocapsid knot
Structure compound particle, the inorganic layer of covering is typically silica, metal sulfide, titanium dioxide, zirconium oxide and some are expensive
Metal.Silica holds adjustable property since it has than table, hole, and important function has been played in catalysis and separation field.
According to the definition of International Association for Pure and Applied Chemistry (IUPAC), aperture is known as micropore less than 2nm's；Aperture 2 to 50nm it
Between referred to as mesoporous (or mesoporous)；Aperture is known as macropore more than 50nm's.Since duct is important to being diffused with for substance
It influences, therefore prepares selectivity of the silica for catalytic process of special pore size distribution, the separative efficiency of separating-purifying with very
Important meaning.
In heterogeneous catalytic reaction field, the pore structure property of catalyst and its carrier be determine catalyst performance it is important because
Element.The pore structure parameter of catalyst and its carrier includes specific surface area, aperture and hole appearance etc., can directly affect the work of catalyst
Property and reaction system in each substance mass transfer, and then determine catalyst performance.Adjusting catalyst and its carrier hole knot
While structure, the macroparameters such as material granule pattern, size, uniformity coefficient are controlled, enable to the material granule prepared
It is expanded in application range field.
In catalytic reaction process, for catalyst is made to give full play to efficiency, the granulated of catalyst in the reactor should be made
Situations such as shape, size, is in optimum state, could promote catalyst efficiency to greatest extent.For silica, as catalysis
When agent or catalyst carrier, common shape has bar shaped, cylindricality, Raschig ring, honeycomb, spherical shape etc..When spherical silica is as solid
When bed catalyst or catalyst carrier, due to contacting with each other between particle with point, bed resistance can be both reduced, while big
Improve mass transfer and catalytic effect greatly；When the volume of reactor is certain, when institute's catalyst filling is as much as possible, spherical shape is most
(during general spheric granules filling reactor, the spacial volume of particle can reach 70%, and diameter and height for suitable shape
Equal cylindrical particle, only reaches 63~68%).As fluid catalyst or catalyst carrier in use, tiny ball
Shape particles benefit improves catalytic, also allows for conducting heat, be conducive to controlling reaction temperature, can make anti-in the diffusion of substance
Temperature is answered close within the temperature range of optimum, while spheric granules wear-resisting property is also preferable.
The method for preparing spheric catalyst at present has spray drying process, spherical whole grain method, micro emulsion method, rotational forming method etc..
1660489 A of patent CN are to prepare Cu-series catalyst for synthesizing methanol using spray drying process, and this method has input and output material temperature height
The shortcomings that.The method that prior art spherical shape whole grain prepares spheric catalyst typically will add in peptizing agent and molding in material
Auxiliary agent.Peptizing agent generally is nitric acid, citric acid, acetic acid or tartaric acid etc..Shaping assistant is generally sesbania powder or polyethylene glycol
Deng.The adhesive of cylindrical bars, the rheological characteristic squeezed out by cylinder orifice plate is bad, causes shaping efficiency not high.CN101497044B
Disclose a kind of teeth spherical heavy oil hydrotreating catalyst and preparation method thereof.The preparation of alumina support precursor：Hydrogen-oxygen
Change and peptizing agent, expanding agent and shaping assistant are added in aluminium, after mixing, add in deionized water and nitric acid, be uniformly mixed, be made
Magma shape plastic；The peptizing agent is nitric acid, citric acid, acetic acid or tartaric acid or aforementioned arbitrary two or more mixture.
With aluminium oxide stronger interaction will certainly occur for strong acid in this way, and Kong Rong and specific surface can be caused to lose seriously, make finally to urge
The Kong Rong and specific surface area of agent are reduced.
Invention content
The technical problem to be solved in the present invention is to provide a kind of micron ball noble-metal-supported silica supports of high-wearing feature
The preparation method of catalyst, the active component dispersion degree of the catalyst is high, catalyst aperture is adjustable, wearability is high, active
High, the characteristics of stability is good.In addition the invention solves second technical problem be to provide a kind of micron of spherical metal active
The one step preparation method of core-shell type granular metal supported catalyst that component is wrapped, this method is simple and practicable, efficient, holds
Easily realize large-scale production.
To solve above-mentioned two technical problem, a kind of preparation of high abrasion micron noble-metal-supported silica support catalyst
Method follows the steps below：
(1) using noble metal active component is carried on silica support first, solid powder is obtained；
(2) step (1) described powder is added in certain density Ludox, then adds in acid, dispersant, addition
Agent, organic amine form slurry after being sufficiently mixed；
(3) mixed slurry in step (2) is injected by the certain fluidic generator in aperture in high temperature oil column and be molded；
(4) by the above-mentioned presoma in step (3) in oil column after aging, washed, dry, roasting obtains metal and bears
Carried catalyst.
Noble metal is mainly one or more of Pd, Pt, Au, Rh, Ru in step (1), and the matter of silicon oxide powder
Amount is than being 0.1~5%.
The particle scale for the silicon oxide powder selected in step (1) is preferably 2~15 μm.
It is well known that the particle scale of the silicon oxide powder added in has the intensity of micron silicon oxide particle very big shadow
Ring, when particle be more than 10 μm, be that cannot prepare the small micron silica gel particle of particle first, secondly prepare silica gel particle machinery
Intensity is poor, it is difficult to meet the application in later stage.Therefore, the particle scale of the preferred silicon oxide powder of patent of the present invention for 2~
15μm。
Although the present invention claims carrier be silicon oxide powder, in fact can also include aluminium oxide, titanium oxide, zirconium oxide,
Cerium oxide, zinc oxide, magnesia etc. or above-mentioned hopcalite.In addition, the silica required in this patent
Grain scale is 2~15 μm, however can select bigger for other oxides either oxide mixture, this range
Scale or the smaller scale of selection.
The mode of silicon oxide powder carried noble metal can be infusion process, ion-exchange, the chemical deposition precipitation method, gas phase
One kind in the methods of sedimentation.
It is 10~50% that mass ratio of step (1) the obtained solid powder in whole slurry is added in step (2).
If the silicon oxide powder amount ＜ 10% added in, silicon oxide microsphere is difficult to be molded.On the contrary, if silicon oxide powder adds in
＞ 50% is measured, the viscosity that can cause suspension is higher, can not spray ball.
Ludox in step (2), contained SiO2Mass fraction for 20~40%, particle scale is 2~50nm；And
The quality of Ludox used is 10~60% in the mass ratio of whole slurry.
In addition the particle scale for adding in Ludox has the mechanical strength of prepared catalyst bigger influence.Generally
For, the particle scale of Ludox is smaller, and the mechanical strength of particle is higher；Conversely, the mechanical strength of micron particles can be deteriorated.This
Silicon oxide particle scale is 2~50nm in the preferred Ludox of patent of invention, and the Ludox used can be alkaline silica sol
Or it is acidic silicasol.
Acid is organic for inorganic acids and salicylic acid, acetic acid, ethanedioic acid, citric acid etc. such as hydrochloric acid, nitric acid, phosphoric acid in step (2)
The one or more of acid.
Dispersant described in step (2) is methanol, ethyl alcohol, isopropanol, Ammoniom-Acetate, ammonium citrate, polyethylene glycol, poly- horse
Carry out one or more of sour mixture, addition is 0.1~5% of the representative fraction of solid masses in slurry system.
Organic amine described in step (2) is mainly ethylenediamine, ethanol amine, triethylene diamine, diethylenetriamines, six methylenes
One or more of urotropine, urea.The mass ratio of solid masses and organic amine is 1 in slurry system:0.05~0.2.
Additive described in step (2) is one in wollastonite, kaolin, silicon carbide fibre, glass fibre, talcum powder
Kind is several, and addition is SiO in slurry system2The 0.1~5% of mass fraction.
Molding oil described in step (3) is pumping fluid, transformer oil, paraffin oil, solvent naphtha, vegetable oil, mineral oil
It is one or more in C10~C13 mixing linear paraffins, and oil column is controlled at 80~150 DEG C.
Molding fluidic generator nozzle bore is 0.1~1.0mm employed in step (3)；The speed of jet stream is preferably
0.1~10m/s.
Ageing time in step (4) for 3~r for 24 hours.
A kind of high-wearing feature micron spherical shape metal carrying catalyst prepared by the present invention, spherical silica particle aperture are 2
~50nm, specific surface area are 200~450m20.5~1.5ml/g of/g, Kong Rongwei.A diameter of 30~100 μm of catalyst individual particle.
Micron spherical nuclei-core-shell particles metal carrying catalyst prepared by the present invention has the following advantages：Core active group
Subpackage is wrapped in silica shell, so that active component possesses higher dispersion degree and the particle diameter distribution more concentrated；Together
When silica shell there is the meso-hole structure of suitable specific surface area and Kong Rong so that the catalyst possesses higher activity, choosing
Selecting property and stability.Such catalyst is suitable in the paste state bed reactor that anthraquinone hydrogenation prepares hydrogen peroxide process, and also is adapted for
During other slurry bed system liquid-phase hydrogenatins and gas phase FCC techniques.
Description of the drawings
Fig. 1 is the TEM photos of catalyst prepared by embodiment 1,
Fig. 2 is 1 catalyst hydrogenation Evaluation results of embodiment；
Fig. 3 is the TEM photos of catalyst prepared by embodiment 2,
Fig. 4 is 2 catalyst hydrogenation Evaluation results of embodiment；
Fig. 5 is the TEM photos of catalyst prepared by embodiment 3,
Fig. 6 is 3 catalyst hydrogenation Evaluation results of embodiment；
Fig. 7 is the TEM photos of catalyst prepared by embodiment 4,
Fig. 8 is 4 catalyst hydrogenation Evaluation results of embodiment；
Fig. 9 is the TEM photos of catalyst prepared by embodiment 5,
Figure 10 is 5 catalyst hydrogenation Evaluation results of embodiment；
Figure 11 is the TEM photos of catalyst prepared by embodiment 6,
Figure 12 is 6 catalyst hydrogenation Evaluation results of embodiment.
Specific embodiment
The preparation of high-wearing feature spherical shape high dispersive noble-metal-supported catalyst is made further specifically with embodiment below
It is bright, but the range that this should not be interpreted as to the claims of the present invention is only limitted to following embodiments.Unless otherwise noted, at this
All numbers occurred in description of the invention and claims, such as dry, calcination temperature, operating condition, the quality of composition
The numerical value such as percentage are not construed as absolute exact value, which is that those of ordinary skill in the art is understood
, in the permitted error range of known technology.
A kind of high-wearing feature micron spherical shape metal carrying catalyst prepared by the present invention is using Quanta companies of the U.S.
The specific surface area of determination sample, pore size and pore size distribution on NOVA2200e types specific surface-pore-size distribution instrument.
Micron spherical nuclei-core-shell particles metal carrying catalyst prepared by the present invention is using Jeol Ltd.
JEM-2100 type 200kV high resolution transmission electron microscopies measure the size of active component particles contained by catalyst.
The performance evaluation of catalyst then produces hydrogen peroxide by anthraquinone hydrogenation, is carried out using slurry bed system perfectly mixed reactor.It is real
Test the working solution of evaluation use as shown in Table 1
1 anthraquinone working solution component list of table
The slurry bed system perfectly mixed reactor volume is 200ml, built-in stirring blade and gas distributor.It is about 1ml to take volume
Catalyst be placed in inside reactor.Using continuous feeding and discharging mode, total liquid measure is 150ml, charging rate 0.3ml/ for evaluation
Min, hydrogen flowing quantity 30ml/min.
Embodiment 1
(1-1) weighs the SiO that average grain diameter is 2 μm2Powder 21g, by the Pd (NO of a concentration of 20mg/mL of 11.5mL3)2It is molten
Liquid is carried on above-mentioned SiO in a manner of incipient impregnation2On powder；
(1-2) takes the alkaline silica sol of concentrated hydrochloric acid 15mL and 126g 30%wt, and (wherein silica average grain scale is
After 25nm) mixing, slurry main body is obtained, then 15g hexamethylenetetramines are added in slurry, stirring makes it fully dissolve.
(1-3) chooses the nozzle that internal diameter is 0.25mm and installs to fluidic generator, and the slurry that (1-2) is obtained is with 0.1m/s
Speed be injected into 95 DEG C of 25# transformer oil and be molded, after standing aging 4 hours, molding core-shell structure copolymer is isolated from oil and is urged
Agent microballoon is dried in vacuo 12 hours in 60 DEG C.
(1-4) washs obtained product to neutrality, and then 140 DEG C of dryings 10 hours, obtain for 12 hours in 550 DEG C of roastings
Spherical nuclei-core-shell particles metal carrying catalyst.
TEM photos are shown in Fig. 1, and catalyst hydrogenation Evaluation results are shown in Fig. 2.
Embodiment 2
(2-1) weighs the SiO that average grain diameter is 5 μm2Powder 21g, by the Pd (NO of a concentration of 20mg/mL of 4.6mL3)2Solution
Above-mentioned SiO is carried in a manner of incipient impregnation2On powder；
(2-2) takes the alkaline silica sol of concentrated hydrochloric acid 15mL and 126g 30%wt, and (wherein silica average grain scale is
After 25nm) mixing, slurry main body is obtained, then 15g hexamethylenetetramines are added in slurry, stirring makes it fully dissolve.
(2-3) chooses the nozzle that internal diameter is 0.25mm and installs to fluidic generator, and the slurry that (2-2) is obtained is with 0.1m/s
Speed be injected into 95 DEG C of 25# transformer oil and be molded, after standing aging 4 hours, molding core-shell structure copolymer is isolated from oil and is urged
Agent microballoon is dried in vacuo 12 hours in 60 DEG C.
(2-4) washs obtained product to neutrality, and then 140 DEG C of dryings 10 hours, obtain for 12 hours in 550 DEG C of roastings
Spherical nuclei-core-shell particles metal carrying catalyst.
TEM photos are shown in Fig. 3, and catalyst hydrogenation Evaluation results are shown in Fig. 4.
Embodiment 3
(3-1) weighs the SiO of 7 μm of average out to2Powder 31g, by the Pd (NO of a concentration of 20mg/mL of 15mL3)2Solution with etc.
The mode of volume impregnation is carried on above-mentioned SiO2On powder；
(3-2) takes concentrated phosphoric acid 10ml, 30%wt alkaline silica sol 126g (wherein silica average grain scale is 25nm)
And polyethylene glycol 8ml is sufficiently mixed to obtain mixed slurry, then by silicon carbide fibre 2.5g (500 mesh) and hexa
14g is added in slurry, is fully dissolved.
(3-3) chooses aperture and is installed for 0.35mm nozzles to fluidic generator, and the slurry that (3-2) is obtained is with the speed of 5m/s
Degree is injected into 90 DEG C of 25# transformer oil and is molded, molding bead is isolated from oil, is dried in vacuo 16 hours in 80 DEG C.
(3-3) washs obtained product to neutrality, and then 140 DEG C of dryings 10 hours, obtain for 12 hours in 550 DEG C of roastings
Spherical nuclei-core-shell particles metal carrying catalyst.
TEM photos are shown in Fig. 5, and catalyst hydrogenation Evaluation results are shown in Fig. 6.
Embodiment 4
(4-1) weighs the SiO that average grain diameter is 10 μm2Powder 21g, by the Pd (NO of a concentration of 20mg/mL of 1.05mL3)2It is molten
Liquid is carried on above-mentioned SiO in a manner of incipient impregnation2On powder；
(4-2) take concentrated hydrochloric acid 5ml, 30%wt alkaline silica sol 126g (wherein silica average grain scale be 12nm) with
And isopropanol 10ml is sufficiently mixed to obtain slurry, then adding in hexa 15g into slurry, fully dissolves.
(4-3) chooses aperture and is installed for 0.2mm nozzles to fluidic generator, and the slurry that (4-2) is obtained is with the speed of 1m/s
Degree is injected into 85 DEG C of 25# transformer oil and is molded, and molding bead is isolated from oil, is dried in vacuo 12 hours in 60 DEG C.
(4-4) washs obtained product to neutrality, and then 140 DEG C of dryings 10 hours, obtain for 12 hours in 550 DEG C of roastings
Spherical nuclei-core-shell particles metal carrying catalyst.
TEM photos are shown in Fig. 7, and catalyst hydrogenation Evaluation results are shown in Fig. 8.
Embodiment 5
(5-1) weighs the SiO that average grain diameter is 15 μm2Powder 47.1g, by the Pd of a concentration of 20mg/mL of 117.75mL
(NO3)2Solution is carried on above-mentioned SiO in a manner of incipient impregnation2On powder；
(5-2) weighs concentrated hydrochloric acid 15ml, 30%wt alkaline silica sol 126g, and (wherein silica average grain scale is
12nm) and ethyl alcohol 5ml is sufficiently mixed to obtain slurry, then adding in hexa 14g into slurry, fully dissolves.
(5-3) chooses aperture and is installed for 1mm nozzles to fluidic generator, and the slurry that (5-3) is obtained is with the speed of 2m/s
It is injected into 95 DEG C of 25# transformer oil and is molded, molding bead is isolated from oil, be dried in vacuo 12 hours in 80 DEG C.
(5-4) washs obtained product to neutrality, and then 110 DEG C of dryings 20 hours, obtain for 12 hours in 550 DEG C of roastings
Spherical nuclei-core-shell particles metal carrying catalyst.
TEM photos are shown in Fig. 9, and catalyst hydrogenation Evaluation results are shown in Figure 10.
Embodiment 6
(6-1) weighs the SiO of 5 μm of average out to2Powder 18.1g, by the Pd (NO of a concentration of 20mg/mL of 0.905mL3)2Solution
Above-mentioned SiO is carried in a manner of incipient impregnation2On powder；
(6-2) weighs concentrated hydrochloric acid 15ml, 30%wt alkaline silica sol 126g, and (wherein silica average grain scale is
12nm) and ethyl alcohol 10ml is sufficiently mixed to obtain slurry, then adding in hexa 14g into slurry, fully dissolves.
(6-3) chooses aperture and is installed for 0.3mm nozzles to fluidic generator, and the slurry that (6-1) is obtained is with the speed of 20m/s
Degree is injected into 95 DEG C of 25# transformer oil and is molded, and molding bead is isolated from oil, is dried in vacuo 12 hours in 80 DEG C.
(6-4) washs obtained product to neutrality, and then 110 DEG C of dryings 20 hours, obtain for 12 hours in 550 DEG C of roastings
Spherical nuclei-core-shell particles metal carrying catalyst.TEM photos are shown in Figure 11, and catalyst hydrogenation Evaluation results are shown in Figure 12.
Claims (13)
1. a kind of preparation method of high abrasion micron noble-metal-supported silica support catalyst, it is characterised in that according to following step
It is rapid to carry out：
(1) noble metal active component is carried on silica support first, obtains solid powder；
(2) step (1) described powder is added in certain density Ludox, then adds in acid, dispersant, additive, has
Machine amine forms slurry after being sufficiently mixed；
(3) mixed slurry in step (2) is injected by the certain fluidic generator in aperture in high temperature oil column and be molded；
(4) by the above-mentioned presoma in step (3) in oil column after aging, washed, dry, roasting obtains Metal Supported and urges
Agent.
2. a kind of preparation method of high abrasion micron noble-metal-supported silica support catalyst according to claim 1,
It is characterized in that：Noble metal is one or more of for Pd, Pt, Au, Rh or Ru in step (1), noble metal and silicon oxide powder
Mass ratio be 0.1%~5%.
3. a kind of preparation method of high abrasion micron noble-metal-supported silica support catalyst according to claim 1,
It is characterized in that：The particle scale for the silicon oxide powder selected in step (1) is 2~15 μm.
4. a kind of preparation method of high abrasion micron noble-metal-supported silica support catalyst according to claim 1,
It is characterized in that：The mode of silicon oxide powder carried noble metal is infusion process, ion-exchange, the chemical deposition precipitation method, gas phase
One kind in sedimentation.
5. a kind of preparation method of high abrasion micron noble-metal-supported silica support catalyst according to claim 1,
It is characterized in that：It is 10~50% that mass ratio of the solid powder in whole slurry in step (1) is added in step (2)；Institute
With Ludox account for whole slurry mass ratio be 10~60%；The dispersant addition is solid matter in slurry system
The 0.1~5% of amount；The organic amine is 5~20% of solid masses in slurry system；The additive is solid in slurry system
The 0.1~5% of weight score.
6. a kind of preparation of the micron ball noble-metal-supported silica support catalyst of high-wearing feature according to claim 1
Method, it is characterised in that：Ludox in step (2), contained SiO2Mass fraction for 20~40%, particle scale 2
~50nm.
7. a kind of preparation method of high abrasion micron noble-metal-supported silica support catalyst according to claim 1,
It is characterized in that：In step (2) acid for hydrochloric acid, nitric acid, phosphoric acid, other inorganic acids, salicylic acid, acetic acid, ethanedioic acid, citric acid or
The one or more of other organic acids.
8. a kind of preparation method of high abrasion micron noble-metal-supported silica support catalyst according to claim 1,
It is characterized in that：Dispersant described in step (2) is methanol, ethyl alcohol, isopropanol, Ammoniom-Acetate, ammonium citrate, polyethylene glycol,
It is one or more in poly.
9. a kind of preparation method of high abrasion micron noble-metal-supported silica support catalyst according to claim 1,
It is characterized in that：Organic amine described in step (2) is mainly ethylenediamine, ethanol amine, triethylene diamine, diethylenetriamines, six
One or more of methenamine or urea.
10. a kind of preparation method of high abrasion micron noble-metal-supported silica support catalyst according to claim 1,
It is characterized in that：Additive described in step (2) is wollastonite, in kaolin, silicon carbide fibre, glass fibre, talcum powder
It is one or more.
11. a kind of preparation method of high abrasion micron noble-metal-supported silica support catalyst according to claim 1,
It is characterized in that：Oil is molded in oil column described in step (3) as pumping fluid, transformer oil, paraffin oil, solvent naphtha, plant
It is one or more in oil, mineral oil C10~C13 mixing linear paraffins, and oil column is controlled at 80~150 DEG C.
12. a kind of preparation method of high abrasion micron noble-metal-supported silica support catalyst according to claim 1,
It is characterized in that：Molding fluidic generator nozzle bore is 0.1~1.0mm employed in step (3)；The speed of jet stream is preferred
For 0.1~10m/s.
13. a kind of preparation method of high abrasion micron noble-metal-supported silica support catalyst according to claim 1,
It is characterized in that：Ageing time in step (4) for 3~r for 24 hours.
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