CN108246350A - A kind of mesoporous molecular sieve catalyst material and its in-situ preparation method for coating noble metal - Google Patents
A kind of mesoporous molecular sieve catalyst material and its in-situ preparation method for coating noble metal Download PDFInfo
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- CN108246350A CN108246350A CN201810023443.0A CN201810023443A CN108246350A CN 108246350 A CN108246350 A CN 108246350A CN 201810023443 A CN201810023443 A CN 201810023443A CN 108246350 A CN108246350 A CN 108246350A
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- molecular sieve
- noble metal
- situ preparation
- stirring
- pvp
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 100
- 239000000463 material Substances 0.000 title claims abstract description 75
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 75
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 20
- 239000011248 coating agent Substances 0.000 title claims abstract description 12
- 238000000576 coating method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000002425 crystallisation Methods 0.000 claims abstract description 17
- 230000008025 crystallization Effects 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 239000003292 glue Substances 0.000 claims abstract description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010457 zeolite Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 31
- 238000005253 cladding Methods 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 25
- 238000007789 sealing Methods 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000010703 silicon Substances 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 19
- 239000010970 precious metal Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000002178 crystalline material Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000003840 hydrochlorides Chemical class 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 239000000376 reactant Substances 0.000 abstract description 8
- 229920002521 macromolecule Polymers 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 14
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 9
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000004679 hydroxides Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 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
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- -1 quaternary ammonium alkaloid compound Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000005406 washing Methods 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0354—Noble metals
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B01J35/396—
-
- B01J35/51—
-
- B01J35/647—
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Abstract
The invention discloses a kind of mesoporous molecular sieve catalyst materials and its in-situ preparation method for coating noble metal, prepare the nucleocapsid precursor solution of " noble metal nano particles@PVP " first；Then a certain amount of structure directing agent, Zeolite synthesis material system are added in precursor solution, is stirred at room temperature to dry glue, then through the processing such as steam auxiliary crystallization and roasting, the mesoporous molecular sieve catalyst material of noble metal must be coated.The present invention is using the method being prepared in situ, noble metal is coated on inside molecular sieve crystal, utilize the crystal structure limitation noble metal nano particles reunion during the reaction of molecular sieve and obscission, noble metal active component and severe external reaction condition are isolated by molecular sieve shell closely knit simultaneously, ensure the catalytic activity of active component, extend the service life of catalyst；High-temperature roasting can leave certain mesopore orbit after removing PVP templates in material internal, improve the catalytic efficiency of catalysis macromolecule reactant.
Description
Technical field
The invention belongs to inorganic compounding technical fields, and in particular to a kind of mesoporous molecular sieve catalyst material for coating noble metal
Material and its in-situ preparation method.
Background technology
Catalyst material and catalyst carrier material of the molecular sieve as a kind of function admirable, be widely used in catalysis,
The fields such as adsorbing separation and environmental protection.The unique nano pore structure having inside molecular sieve imparts it and unique shape-selective urges
The characteristics of change, can modulation duct is acid, excellent thermal stability and chemical stability are provided for abundant catalysis again
Activated centre.And the noble metal nano particles material of nano-scale size is imparted noble metal and is received due to its high surface energy
The catalytic oxidation performance and Catalytic Hydrogenation Properties of the distinctive high activity of rice corpuscles.Molecular screen material has the function of shape selective catalysis and acid
Property site, but do not have catalysis oxidation and Catalytic Hydrogenation Properties, noble metal nano particles have good catalysis oxidation and catalysis
Hydrogenation, but do not have shape selective catalysis function and acidic site so the two is carried out compound, is prepared novel difunctional
Catalyst is an important topic of current researchers.
Traditional complex method uses wet impregnation or ion exchange, but the noble metal nano particles that these methods introduce more
It due to being limited by microporous molecular sieve pore size size, and cannot be introduced into inside the duct of molecular sieve, most of activity
Component is all adsorbed in the outer surface of material.Easily reunite or take off which results in metal nanoparticle in catalytic reaction process
It falls, so as to affect the catalytic activity of catalyst and service life.
Can the mentality of designing of part researcher be to utilize the crystal structure or pore passage structure of molecular sieve at present, and metal is received
Rice corpuscles is coated on inside molecular sieve, is prevented the reunion of protection activity component to put using molecular sieve shell and come off, ensures to live
Property component dispersibility with activity.Such as stablize palladium (Pd) ion using organic amine in Ji Hong team, by itself and Zeolite synthesis
Precursor liquid mixes, and the Silicalite-1 type molecular sieves (DOI of cladding Pd nano-particles has been prepared in situ:10.1021/
Jacs.6b03518), wherein Pd is closely sized to monatomic rank, in microporous molecular sieve duct.Although they use for the first time
Method is prepared in situ monatomic rank metal nanoparticle is introduced into MFI-type molecular sieve for formic acid production hydrogen reaction, but due to
Its used noble metal source raw material is difficult to prepare, expensive, can not produce in enormous quantities.And material entirety pore passage structure list
One, it can not be applied well in the catalysis reaction of macromolecule reactant.Mielby et al. is by the way of alkali process pure
Duct is constructed in si molecular sieves, and CTAB is added in as duct template and structural stabilizing agent in processing procedure China and foreign countries, using leaching
Gold nano grain is introduced into (DOI inside molecular sieve by stain method:10.1002/anie.201406354).Although the method is successfully
Noble metal nano particles and mesoporous system are introduced into molecular sieve, and raw material are all simple and easy to get, but simultaneously at the alkali of early period
The introducing of reason process and Surfactant CTAB so that regulation process is difficult control, and entire synthesis cycle is long, is also unfavorable for
The mass production of material.Easily reunite in current complex method or there is active component in conventional composite mode, come off
The problem of or there is cost price is high in cladding package method, be difficult to and can not produce in enormous quantities the problems such as, therefore,
The complex method further explored between completely new, inexpensive, regulatable noble metal nano particles and molecular sieve carrier has
There are important research and application value.
Invention content
The invention discloses a kind of mesoporous molecular sieve catalyst materials and its in-situ preparation method for coating noble metal, will be expensive
Metallic cover inside molecular sieve crystal, using molecular sieve crystal structure limitation noble metal nano particles during the reaction
Reunion and obscission, ensure that active component is uniformly distributed on carrier material；Closely knit molecular sieve shell is by noble metal simultaneously
Active component is isolated with severe external reaction condition, ensure that the catalytic activity of active component, extends the use of catalyst
Service life；Mesoporous system is introduced into the circulation diffusivity that can be effectively improved reactant in catalysis reaction, and it is anti-to improve catalysis macromolecular
Answer the catalytic efficiency of object；The synthetic method raw material are simple and easy to get, and synthesis condition is mild, and reaction is easily controllable, can in high volume close
Into suitable commercial introduction.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method for the mesoporous molecular sieve catalyst material for coating noble metal, it includes the following steps：
1) precious metal salt solution is prepared, under conditions of ice bath stirring, PVP is added in, and be sealed ice bath stirring, obtains mixed
Close solution I；
2) sodium borohydride solution is prepared, rapid sealing, obtains aterrimus mixed solution after rapidly joining in mixed solution I, and
Sealing ice bath stirring is kept, precursor solution (the nucleocapsid structure precursor solution of " noble metal nano particles@PVP ") is made；
3) a certain amount of precursor solution is taken, structure directing agent, Zeolite synthesis are sequentially added under the conditions of being stirred at room temperature
Material system obtains mixed solution I I, open stirring after sealing stirring a period of time, until stirring into xerogel state；Then by institute
It obtains xerogel and is dried into dry glue, obtain grey black solid I；
4) gained grey black solid I is subjected to steam auxiliary crystallization processing (SAC) and obtains molecular sieve crystalline material；
5) after reaction, product is taken to be washed, alcohol is washed, progress high-temperature roasting removing template after drying, with furnace cooling
But to taking out after room temperature, the mesoporous molecular sieve catalyst material of the cladding noble metal is obtained.
In said program, the precious metal salt is the corresponding hydrochloride of Pt, Pd, Ag, Au, Ru, Rh, Re or Ir, nitrate
Or one or more of sulfate etc..
In said program, step 1), step 2) ice bath temperature are 0~5 DEG C, and mixing time is 1~24 hour.
Preferably, the ice bath temperature is 0~3 DEG C, and mixing time is 2~6h.
In said program, the step 1) PVP is preferably PVP-K15.
In said program, the precious metal element, PVP and the H that are introduced in the step 1) precious metal salt2The molar ratio of O is 1:
(15~350):(1.5*104~1.5*105)。
Preferably, precious metal element, PVP, H2The molar ratio of O is 1:(50~200):(2*104~1*105)。
In said program, the molar concentration of sodium borohydride is 0.2~0.4mol/L in the step 2) sodium borohydride solution.
In said program, the precious metal element and the molar ratio of sodium borohydride that are introduced in the step 2) precious metal salt are 1:
(10~70).
Preferably, the molar ratio of precious metal element and sodium borohydride is 1:50.
In said program, the Molecular sieve raw material system is pure silicon system, sial system or silicon titanium system；The pure silicon body
System is using silicon source as raw material；Sial system includes silicon source and silicon source；Silicon titanium system includes titanium source and silicon source.
In said program, methyl orthosilicate, ethyl orthosilicate, sodium metasilicate or Ludox etc. can be selected in the silicon source；It is described
Silicon source is sodium metaaluminate, boehmite, aluminium isopropoxide, aluminum nitrate, aluminum sulfate, alundum (Al2O3), alchlor or hydroxide
Aluminium etc.；The titanium source is butyl titanate, isopropyl titanate, tetraethyl titanate, titanium tetrachloride, titanium sulfate or titanium valve etc..
In said program, the structure directing agent is quaternary ammonium alkaloid compound, and general formula is (R1)4NOH, R1For have 1~
The alkyl of 4 carbon atoms, preferably propyl.
In said program, the silica alumina ratio (elemental mole ratios) in the sial system is 10~100, silicon titanium in silicon titanium system
It is 10~500 than (elemental mole ratios)；Loading time interval between structure directing agent, silicon source (or titanium source), silicon source is respectively
30min~6h.
Preferably, ranging from the 20~50 of silica alumina ratio, silicon titanium than ranging from 50~300；Structure directing agent, silicon source (titanium
Source), the loading time interval of silicon source be respectively 2~4h.
In said program, introduced in the step 3) precursor solution, structure directing agent, Zeolite synthesis material system
The volume ratio of silicon source is 1:(0.05~0.25):(0.25~2).
Preferably, precursor solution, structure directing agent, silicon source volume ratio be 1:(0.1~0.2):(0.5~1.5).
In said program, ambient temperature described in step 3) is 20~25 DEG C, and sealing mixing time is 1~12h；Opening is stirred
The time is mixed as 6~48h；Drying temperature is 30~100 DEG C, and drying time is 2~48h.
Preferably, it is 4~6h that mixing time is sealed described in step 3), open mixing time for 12~for 24 hours.
Preferably, drying temperature described in step 3) is 60~90 DEG C, drying time for 12~for 24 hours.
In said program, step 4) the SAC methods are：In the polytetrafluoroethyllining lining (specification of hydrothermal reaction kettle：
150ml) a 25ml small beaker that 5~10ml deionized waters are housed is placed in middle position, and polytetrafluoroethyl-ne is placed on small beaker
Alkene gasket is covered with filter paper on gasket, and grey black solid I is placed in above filter paper, and the quality of grey black solid I is 0.1g~2g,
Stainless steel outer lining is inserted in after sealing, is placed in high temperature oven and is reacted.
In said program, the reaction temperature in the steam auxiliary crystallization treatment process is 160~180 DEG C, the reaction time
For 24~72h；Reaction temperature is preferably 180 DEG C, and the reaction time is preferably 48h.
Preferably, water is 10ml in 25ml small beakers in the steam auxiliary crystallization treatment process, grey black solid I
Quality is 1g~1.5g.
In said program, the number that the step 5) washing, alcohol are washed is 1~5 time, it is preferred that preferably 2~3 times；Drying
Temperature is 40~100 DEG C, preferably 80~100 DEG C；Drying time for 2~for 24 hours, preferably 6~12h.
In said program, high-temperature roasting temperature described in step 5) is 450~550 DEG C, and roasting time is 4~12h, is heated up
Rate is 1~5 DEG C/min.
Preferably, high-temperature roasting temperature described in step 5) is 500~550 DEG C, and roasting time is 4~8h.
The mesoporous molecular sieve catalyst material of cladding noble metal prepared according to said program, it is whole that ball-type shape is presented
Looks, size are concentrated at 2~5 μm, and spherome surface is accumulated by molecular sieve nanometer sheet；Material internal has abundant Jie
Hole duct, mesoporous pore size are evenly distributed, and are concentrated mainly on 4.47nm；Noble metal nano particles are uniformly coated in molecular sieve
Portion, size is consistent in the size of presoma, concentrates on 2~5nm；Noble metal is coated on inside molecular sieve crystal, profit
With the reunion during the reaction of the crystal structure of molecular sieve limitation noble metal nano particles and obscission, ensure active component
It is uniformly distributed on carrier material；Closely knit molecular sieve shell is by noble metal active component and severe external reaction condition simultaneously
It is isolated, ensure that the catalytic activity of active component, extend the service life of catalyst；The introducing of mesoporous system can effectively change
The circulation diffusivity of reactant in kind catalysis reaction improves the catalytic efficiency of catalysis macromolecule reactant.
The benefit structural model of opening up of the mesoporous molecular sieve catalyst material of cladding noble metal prepared by the present invention includes MFI type
(Silicalite-1, ZSM-5, TS-1 molecular sieve), FAU types (X-type, Y type molecular sieve), BEA types (beta molecular sieves), MOR,
LTA (NaA molecular sieve), LTL (L molecular sieves), SOD, GIS, OFF, ZSM-22, MTN, AEL etc.；For different types of point of synthesis
Son sieve, can according to circumstances add in a certain amount of isopropanol (99.0%) auxiliary agent in right amount, and additive amount is precursor solution total volume
20~60%.
Noble metal is coated on inside molecular sieve crystal using the method being prepared in situ, is utilized the crystalline substance of molecular sieve by the present invention
The limitation noble metal nano particles reunion during the reaction of body structure and obscission, ensure that active component is uniformly distributed in load
On body material；Noble metal active component and severe external reaction condition are isolated by molecular sieve shell closely knit simultaneously, are ensured
The catalytic activity of active component extends the service life of catalyst；High-temperature roasting can be in material internal after removing PVP templates
Certain mesopore orbit is left, mesoporous system is introduced into the circulation diffusivity that can be effectively improved reactant in catalysis reaction, carries
The catalytic efficiency of height catalysis macromolecule reactant.
Raw material of the present invention are simple and easy to get, and synthesis condition is mild, and reaction is easily controllable, can in high volume synthesize.
The deoxidation of petrochemical industry, especially biodiesel adds hydrogen, catalysis oxidation, the comprehensive utilization of biodiesel by-product etc.
Aspect has good application prospect, is suitable for commercial introduction.
Compared with prior art, beneficial effects of the present invention are：
1) the mesoporous molecular sieve catalyst material of cladding noble metal is prepared using simple, high yield SAC methods in situ,
Noble metal is coated on inside molecular sieve crystal, and noble metal nano particles are limited during the reaction using the crystal structure of molecular sieve
Reunion and obscission, ensure that active component is uniformly distributed on carrier material；Closely knit molecular sieve shell is by your gold simultaneously
Belong to active component to be isolated with severe external reaction condition, ensure the catalytic activity of active component, extend the use of catalyst
Service life.
2) the nucleocapsid structure presoma of " noble metal nano particles@PVP " is introduced into synthetic system by made from, is closed first
Into the presoma for going out nucleocapsid, PVP can also be used as template while stabilizer function is played, and nucleocapsid is more advantageous to
It is dispersed in the precursor liquid of Zeolite synthesis；High-temperature roasting can leave certain mesoporous hole in material internal after removing PVP templates
Road, mesoporous system are introduced into the circulation diffusivity that can be effectively improved reactant in catalysis reaction, improve catalysis macromolecular reaction
The catalytic efficiency of object；The shell thickness of " noble metal nano particles@PVP " can be adjusted by regulating and controlling the introduction volume of PVP simultaneously,
And then play the purpose in adjustment and control system intermediary hole aperture.
3) raw material of the present invention are simple and easy to get, synthesis condition is mild and is easy to regulate and control, and operating process is simple, is convenient for
It repeats, can largely synthesize.
Description of the drawings
" noble metal is received in precursor solutions of the Fig. 1 for the nucleocapsid structure of 1 gained noble metal nano particles@PVP of embodiment
The X-ray diffractogram of the nucleocapsid structure presoma dried powder of rice corpuscles@PVP ".
Fig. 2 is the scanning electron microscope (SEM) photograph of the nucleocapsid structure presoma of 1 gained " noble metal nano particles@PVP " of embodiment.
Fig. 3 is the transmission electron microscope picture of the nucleocapsid structure presoma of 1 gained " noble metal nano particles@PVP " of embodiment.
Fig. 4 is the X-ray diffraction of 1 gained common molecular sieve catalyst material of 1 gained final product of embodiment and comparative example
Figure.
Fig. 5 is the scanning electron microscope (SEM) photograph of 1 gained common molecular sieve catalyst material of comparative example.
Fig. 6 is the scanning electron microscope (SEM) photograph of the mesoporous molecular sieve catalyst material of 2 gained cladding noble metal of the embodiment of the present invention.
Fig. 7 is the transmission electron microscope picture of the mesoporous molecular sieve catalyst material of 2 gained cladding noble metal of the embodiment of the present invention.
Fig. 8 is the electron diffraction pattern of the mesoporous molecular sieve catalyst material of 2 gained cladding noble metal of the embodiment of the present invention.
Fig. 9 is the pore size distribution curve of the mesoporous molecular sieve catalyst material of 3 gained cladding noble metal of the embodiment of the present invention.
Figure 10 is the N of the mesoporous molecular sieve catalyst material of 3 gained cladding noble metal of the embodiment of the present invention2Adsorption desorption is bent
Line.
Figure 11 is the X-ray diffractogram of the mesoporous molecular sieve catalyst material of 4 gained cladding noble metal of the embodiment of the present invention.
Figure 12 is the X-ray diffractogram of the mesoporous molecular sieve catalyst material of 5 gained cladding noble metal of the embodiment of the present invention.
Specific embodiment
In order to better understand the present invention, with reference to the specific embodiments and the drawings content that the present invention is furture elucidated,
But present disclosure is not limited solely to the following examples.Wherein, comparative example 1 is the molecular sieve catalytic without cladding noble metal
Agent material, with the difference of two kinds of comparison cladding, non-cladding systems.
In following embodiment, the PVP models PVP-K15 of use；TPAOH exists in the tetrapropylammonium hydroxide reagent of use
A concentration of 1.0M in water.
In following embodiment, the SAC methods are：In the polytetrafluoroethyllining lining (specification of hydrothermal reaction kettle：150ml) just
A 25ml small beaker that 10ml deionized waters are housed is placed in centre position, and teflon gasket, gasket are placed on small beaker
On be covered with filter paper, grey black solid I is placed in above filter paper, the quality of grey black solid I is 0.1g~2g, is inserted in not after sealing
Become rusty steel outer lining, is placed in high temperature oven and is reacted.
In following embodiment, the ice bath temperature is 0~3 DEG C.
Embodiment 1
A kind of mesoporous molecular sieve catalyst material (ZSM-5 molecular sieve) for coating noble metal, specific preparation process are as follows：
1) H of 0.05g is taken2PtCl6·6H2O solids are dissolved in 50ml H2In O, after ice bath stirring 1h, the PVP- of 0.5g is added in
K15, sealing stir to obtain mixed solution I, and keep ice bath stirring 1h；
2) NaHB of 0.1g is taken4Solid is dissolved in 10ml H2In O, stirring rapidly joins the mixed of ice bath stirring to after being completely dissolved
It closes in solution I and seals rapidly, obtain aterrimus mixed solution, and keep sealing ice bath stirring 2h, " noble metal nano grain is made
The precursor solution of the nucleocapsid structure of sub-@PVP "；
3) 25 DEG C under room temperature, take the precursor solution of 20ml, under agitation add in 2.5ml tetrapropyl hydroxides
Ammonium reagent (TPAOH, 1.0M in H2O), 0.204g sodium metaaluminates are added in, then added in after at the uniform velocity stirring 1h after at the uniform velocity stirring 1h
10.4ml ethyl orthosilicates (TEOS, 99.99%) obtain mixed solution I I, and open stirring 12h after sealing stirring 4h is kept to be coagulated to dry
Gluey state, drying and processing 12h obtains grey black solid I to dry glue state at 80 DEG C；
4) the grey black solid I of 1.5g is taken to enter kettle, steam auxiliary crystallization (SAC) is used to react 2d at 180 DEG C, makes its turn of crystalline substance
Molecular sieve crystal material for crystallization；
5) after reaction, product is taken to be washed, alcohol is washed at each 2 times, 100 DEG C after drying 12h, the high temperature at 550 DEG C
It roasts 6h and removes template, taken out after cooling to room temperature with the furnace, obtain the mesoporous molecular sieve catalyst material of the cladding noble metal.
Fig. 1 is " Pt@in the precursor solution of the nucleocapsid structure of noble metal nano particles@PVP obtained by the present embodiment
The X-ray diffractogram of the nucleocapsid structure presoma of PVP ", as can be seen from the figure material show the characteristic peak of Pt, and without it
The appearance of its miscellaneous peak.Fig. 2 is the scanning electron microscope (SEM) photograph of the nucleocapsid structure presoma of " the Pt@PVP ", it can be seen that " Pt@PVP "
Size be about 30~80nm between, focus primarily upon between 40~50nm.Fig. 3 is the core-shell structure copolymer knot of " the Pt@PVP "
The transmission electron microscope picture of structure presoma, with reference to its corresponding scanning electron microscope (SEM) photograph can be seen that " Pt@PVP " presoma of synthesis in core-
Shell structure, the particle size for being coated on internal " core " Pt nano-particles is 1~6nm, focuses primarily upon 3~5nm.
Fig. 4 is the X-ray diffractogram of final product and common ZSM-5 molecular sieve catalyst material obtained by the present embodiment, from
Two kinds of materials of it can be seen from the figure that show the characteristic peak of the molecular sieve of MFI topological classifications, and without the appearance of other miscellaneous peaks；
Illustrate that noble metal nano particles are covered by inside molecular sieve structure to a certain extent.
Embodiment 2
A kind of mesoporous molecular sieve catalyst material (Silicalite-1 molecular sieves) for coating noble metal, specific preparation process
It is as follows：
1) H of 0.05g is taken2PtCl6·6H2O solids are dissolved in 50ml H2In O, after ice bath stirring 1h, the PVP- of 0.5g is added in
K15, sealing stir to obtain mixed solution I, and keep ice bath stirring 1h；
2) NaHB of 0.1g is taken4Solid is dissolved in 10ml H2In O, stirring rapidly joins the mixed of ice bath stirring to after being completely dissolved
It closes in solution I and seals rapidly, obtain aterrimus mixed solution, and keep sealing ice bath stirring 2h, " noble metal nano grain is made
The nucleocapsid structure precursor solution of sub-@PVP "；
3) 25 DEG C under room temperature, take the precursor solution of 20ml, under agitation add in 2.5ml tetrapropyl hydroxides
Ammonium reagent (TPAOH, 1.0M in H2O), 10.4ml ethyl orthosilicates (TEOS, 99.99%) are added in after at the uniform velocity stirring 1h, are obtained mixed
Solution II is closed, keeps after sealing stirring 4h open stirring 12h to xerogel state, drying and processing 12h is to dry glue shape at 80 DEG C
State obtains grey black solid I；
4) the grey black solid I of 1.5g is taken to enter kettle, steam auxiliary crystallization (SAC) is used to react 2d at 180 DEG C, makes its turn of crystalline substance
Molecular sieve crystal material for crystallization；
5) after reaction, product is taken to be washed, alcohol is washed at each 2 times, 100 DEG C after drying 12h, the high temperature at 550 DEG C
It roasts 6h and removes template, taken out after cooling to room temperature with the furnace, obtain the mesoporous molecular sieve catalyst material of the cladding noble metal；
Fig. 6 is the scanning electron microscope (SEM) photograph of the present embodiment products therefrom, it can be seen from the figure that ball-type shape is integrally presented in material
Looks are mutually uniformly dispersed, between scantling size is about 2~5 μm.Its surface topography can be seen that by high power scanning electron microscope (SEM) photograph
It is coarse, it is formed by uniform nanometer sheet layer upon layer.Fig. 7 is the transmission electron microscope picture of the present embodiment products therefrom, can be seen
Go out precious metals pt nano-particle successfully to coat into inside molecular screen material, and high-visible wherein there are burning-off PVP templates
The mesopore orbit left afterwards.Electronics of the Fig. 8 for the mesoporous molecular sieve catalyst material of cladding noble metal obtained in the present embodiment
Diffraction pattern can verify material generally monocrystal material.
Embodiment 3
A kind of mesoporous molecular sieve catalyst material (ZSM-5 molecular sieve) for coating noble metal, specific preparation process are as follows：
1) H of 0.05g is taken2PtCl6·6H2O solids are dissolved in 100ml H2In O, after ice bath stirring 1h, add in 0.5g's
PVP-K15, sealing stir to obtain mixed solution I, and keep ice bath stirring 1h；
2) NaHB of 0.1g is taken4Solid is dissolved in 10ml H2In O, stirring rapidly joins the mixed of ice bath stirring to after being completely dissolved
It closes in solution I and seals rapidly, obtain aterrimus mixed solution, and keep sealing ice bath stirring 2h, " noble metal nano grain is made
The nucleocapsid structure precursor solution of sub-@PVP "；
3) 25 DEG C under room temperature, take the precursor solution of 20ml, under agitation add in 2.5ml tetrapropyl hydroxides
Ammonium reagent (TPAOH, 1.0M in H2O), 0.204g sodium metaaluminates are added in, then added in after at the uniform velocity stirring 1h after at the uniform velocity stirring 1h
10.4ml ethyl orthosilicates (TEOS, 99.99%) obtain mixed solution II, and open stirring 12h after sealing stirring 4h is kept to be coagulated to dry
Gluey state.Drying and processing 12h obtains grey black solid I to dry glue state at 80 DEG C；
4) the grey black solid I of 1.5g is taken to enter kettle, steam auxiliary crystallization (SAC) is used to react 2d at 180 DEG C, makes its turn of crystalline substance
Molecular sieve crystal material for crystallization；
5) after reaction, product is taken to be washed, alcohol is washed at each 2 times, 100 DEG C after drying 12h, the high temperature at 550 DEG C
It roasts 6h and removes template, taken out after cooling to room temperature with the furnace, obtain the mesoporous molecular sieve catalyst material of the cladding noble metal；
Fig. 9 is the N of the present embodiment products therefrom2Adsorption desorption curve, as can be seen from the figure in low nitrogen relative pressure (P/
P0<0.2) high adsorption capacity when shows the presence of micropore in sample；It is further in the range of relative pressure is 0.4~0.9
Absorption, and having there are one apparent hysteresis loop illustrates in sample that there is mesoporous this is also corresponding with transmission electron microscope picture.
Pore size distribution curves of the Figure 10 for the mesoporous molecular sieve catalyst material of cladding noble metal obtained in the present embodiment, can from figure
With find out in the present embodiment it is obtained cladding noble metal mesoporous molecular sieve catalyst material pore size distribution curve, it can be seen that
There is uniform mesoporous, average pore size 4.47nm in obtained molecular sieve.
Embodiment 4
A kind of mesoporous molecular sieve catalyst material (TS-1 molecular sieves) and its in-situ preparation method for coating noble metal, it is special
Sign is, includes the following steps：
1) H of 0.05g is taken2PtCl6·6H2O solids are dissolved in 50ml H2In O, after ice bath stirring 1h, the PVP- of 0.5g is added in
K15, sealing stir to obtain mixed solution I, and keep ice bath stirring 1h；
2) NaHB of 0.1g is taken4Solid is dissolved in 10ml H2In O, stirring rapidly joins the mixed of ice bath stirring to after being completely dissolved
It closes in solution I and seals rapidly, obtain aterrimus mixed solution, and keep sealing ice bath stirring 2h, " noble metal nano grain is made
The precursor solution of the nucleocapsid structure of sub-@PVP "；
3) 25 DEG C under room temperature, take the precursor solution of 10ml, under agitation add in 7.5ml tetrapropyl hydroxides
Ammonium reagent (TPAOH, 1.0M in H2O), 5ml is added in dissolved with 0.0625g butyl titanates (99.0%) after at the uniform velocity stirring 1h
Aqueous isopropanol, then 7.5ml ethyl orthosilicates (TEOS, 99.99%) are added in after at the uniform velocity stirring 1h, mixed solution II is obtained, is kept
The open 12h that stirs is to xerogel state after sealing stirring 4h.Drying and processing 12h obtains grey black and consolidates to dry glue state at 80 DEG C
Body I；
4) the grey black solid I of 1.5g is taken to enter kettle, steam auxiliary crystallization (SAC) is used to react 3d at 180 DEG C, makes its turn of crystalline substance
Molecular sieve crystal material for crystallization；
5) after reaction, product is taken to be washed, alcohol is washed at each 2 times, 100 DEG C after drying 12h, the high temperature at 550 DEG C
It roasts 6h and removes template, taken out after cooling to room temperature with the furnace, obtain the mesoporous molecular sieve catalyst material of the cladding noble metal；
Figure 11 is the X-ray diffractogram of the mesoporous molecular sieve catalyst material of the cladding noble metal obtained by the present embodiment,
As can be seen from the figure material shows the characteristic peak of the molecular sieve of MFI topological classifications, and without the appearance of other miscellaneous peaks.
Embodiment 5
A kind of mesoporous molecular sieve catalyst material (beta molecular sieves) and its in-situ preparation method for coating noble metal, it is special
Sign is, includes the following steps：
1) H of 0.05g is taken2PtCl6·6H2O solids are dissolved in 50ml H2In O, after ice bath stirring 1h, the PVP- of 0.5g is added in
K15, sealing stir to obtain mixed solution I, and keep ice bath stirring 1h；
2) NaHB of 0.1g is taken4Solid is dissolved in 10ml H2In O, stirring rapidly joins the mixed of ice bath stirring to after being completely dissolved
It closes in solution I and seals rapidly, obtain aterrimus mixed solution, and keep sealing ice bath stirring 2h, " noble metal nano grain is made
The nucleocapsid structure precursor solution of sub-@PVP "；
3) 25 DEG C under room temperature, take the precursor solution of 9ml, under agitation add in 9.5ml tetraethyl hydroxides
Ammonium reagent (TPAOH, 1.0M in H2O), 0.395g sodium metaaluminates are added in, then added in after at the uniform velocity stirring 1h after at the uniform velocity stirring 1h
10.4ml ethyl orthosilicates (TEOS, 99.99%) obtain mixed solution II, and open stirring 12h after sealing stirring 4h is kept to be coagulated to dry
Gluey state.Drying and processing 12h obtains grey black solid I to dry glue state at 80 DEG C；
4) the grey black solid I of 1.5g is taken to enter kettle, steam auxiliary crystallization (SAC) is used to react 2d at 180 DEG C, makes its turn of crystalline substance
Molecular sieve crystal material for crystallization；
5) after reaction, product is taken to be washed, alcohol is washed at each 2 times, 100 DEG C after drying 12h, the high temperature at 550 DEG C
It roasts 6h and removes template, taken out after cooling to room temperature with the furnace, obtain the mesoporous molecular sieve catalyst material of the cladding noble metal；
Figure 12 is the X-ray diffractogram of the mesoporous molecular sieve catalyst material of the cladding noble metal obtained by the present embodiment,
As can be seen from the figure material shows the characteristic peak of the molecular sieve of BEA topological classifications, and without the appearance of other miscellaneous peaks.
Comparative example 1
A kind of preparation method of molecular sieve catalytic agent material (ZSM-5 molecular sieve), which is characterized in that include the following steps：
1) 25 DEG C under room temperature, take the deionized water of 20ml, under agitation add in 2.5ml tetrapropylammonium hydroxide
Reagent (TPAOH, 1.0M in H2O), 0.204g sodium metaaluminates are added in, then added in after at the uniform velocity stirring 1h after at the uniform velocity stirring 1h
10.4ml ethyl orthosilicates (TEOS, 99.99%) obtain mixed solution II, keep sealing stirring 4h, obtain mixed solution I；
2) mixed solution I is packed into 150mL kettles, hydrothermal crystallizing reacts 2d at 180 DEG C, makes the molecule that its turn of crystalline substance is crystallization
Sieve crystalline material；
3) after reaction, product is taken to be washed, alcohol is washed at each 2 times, 100 DEG C after drying 12h, the high temperature at 550 DEG C
It roasts 6h and removes template, taken out after cooling to room temperature with the furnace, obtain the molecular sieve catalytic agent material.
Fig. 5 is the scanning electron microscope (SEM) photograph of common molecular sieve catalyst material obtained in comparative example 1, can from figure
Go out, hexagonal configuration is integrally presented in material, is mutually uniformly dispersed, between scantling size is about 8~15 μm.
The basic principles, main features and the advantages of the invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope, various changes and improvements may be made to the invention, these variations
It is both fallen in the range of claimed invention with improvement.The claimed scope of the invention by affiliated claims and
Its equivalent thereof.
Claims (9)
1. a kind of in-situ preparation method for the mesoporous molecular sieve catalyst material for coating noble metal, it includes the following steps：
1) precious metal salt solution is prepared, under the conditions of ice bath stirring, PVP is added in, and be sealed ice bath stirring, obtains mixed solution
I；
2) sodium borohydride solution is prepared, is sealed after adding in mixed solution I, obtains aterrimus mixed solution, sealing ice bath is kept to stir
It mixes, precursor solution is made；
3) a certain amount of precursor solution is taken, structure directing agent, Zeolite synthesis raw material are sequentially added under the conditions of being stirred at room temperature
System obtains mixed solution I I, open stirring after sealing stirring a period of time, until stirring into xerogel state；Then gained is done
Gel is dried into dry glue, obtains grey black solid I；
4) gained grey black solid I progress steam auxiliary crystallizations are handled into obtain molecular sieve crystalline material；
5) washed, alcohol is washed by molecular sieve crystal material for gained, and high-temperature roasting is carried out after drying and removes template, is cooled to the furnace
It is taken out after room temperature, obtains the mesoporous molecular sieve catalyst material of the cladding noble metal.
2. preparation method according to claim 1, which is characterized in that the precious metal salt for Pt, Pd, Ag, Au, Ru, Rh,
One or more of the corresponding hydrochlorides of Re or Ir, nitrate, sulfate.
3. in-situ preparation method according to claim 1, which is characterized in that introduced in the step 1) precious metal salt expensive
Metallic element, PVP and H2The molar ratio of O is 1:(15~350):(1.5*104~1.5*105)。
4. in-situ preparation method according to claim 1, which is characterized in that the noble metal member introduced in the precious metal salt
The molar ratio of element and sodium borohydride is 1:(10~70).
5. in-situ preparation method according to claim 1, which is characterized in that the structure directing agent is quaternary ammonium bases chemical combination
Object, general formula are (R1)4NOH, R1To have the alkyl of 1~4 carbon atom.
6. in-situ preparation method according to claim 1, which is characterized in that the Zeolite synthesis material system is pure silicon
System, sial system or silicon titanium system；The pure silicon system is using silicon source as raw material；Sial system includes silicon source and silicon source；Silicon titanium
System includes titanium source and silicon source.
7. in-situ preparation method according to claim 1, which is characterized in that precursor solution described in step 3), structure
Directed agents, the volume ratio of silicon source are 1:(0.05~0.25):(0.25~2).
8. in-situ preparation method according to claim 1, which is characterized in that in the steam auxiliary crystallization treatment process
Reaction temperature is 160~180 DEG C, and the reaction time is 24~72h.
9. the mesoporous molecular sieve catalyst material of any one of claim 1~8 in-situ preparation method cladding noble metal obtained
Material, which is characterized in that ball-type pattern is integrally presented in it, and size is concentrated at 2~5 μm, and spherome surface is by molecular sieve nanometer
Piece is accumulated；Material internal has mesopore orbit, and noble metal nano particles are uniformly coated on inside molecular sieve, and size is big
It is small to concentrate on 2~5nm.
Priority Applications (1)
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