CN110292947A - A kind of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst and its preparation method and application - Google Patents
A kind of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst and its preparation method and application Download PDFInfo
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- CN110292947A CN110292947A CN201910641100.5A CN201910641100A CN110292947A CN 110292947 A CN110292947 A CN 110292947A CN 201910641100 A CN201910641100 A CN 201910641100A CN 110292947 A CN110292947 A CN 110292947A
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- precious metal
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 239000010970 precious metal Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000005119 centrifugation Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000002808 molecular sieve Substances 0.000 claims description 25
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical group CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- XKUTVNLXHINPAP-UHFFFAOYSA-N azane platinum Chemical compound N.[Pt] XKUTVNLXHINPAP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- 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 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- KFIKNZBXPKXFTA-UHFFFAOYSA-N dipotassium;dioxido(dioxo)ruthenium Chemical compound [K+].[K+].[O-][Ru]([O-])(=O)=O KFIKNZBXPKXFTA-UHFFFAOYSA-N 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000001802 infusion Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 238000006317 isomerization reaction Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 239000002608 ionic liquid Substances 0.000 description 5
- 238000002803 maceration Methods 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- -1 carbonium ion Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 1
- 229910001630 radium chloride Inorganic materials 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000010792 warming 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
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of MCM-41/SAPO-11 composite molecular screen supported precious metal catalysts and its preparation method and application, the catalyst the preparation method comprises the following steps: by silica MCM-41 original powder, phosphorus source, silicon source, template and water are mixed and stirred for obtaining uniform gel mixture, then successively through standing crystallization, centrifugation, deionized water washing, drying and calcination are activated, tabletting is carried out again, broken and sieving obtains MCM-41/SAPO-11 composite molecular screen particle, using the MCM-41/SAPO-11 composite molecular screen particle as catalyst carrier, pass through infusion process carried noble metal presoma, then calcining makes noble metal precursor body be changed into precious metal simple substance, obtain the MCM-41/SAPO-11 composite molecular screen carried noble metal Catalyst.Catalyst provided by the invention has micropore-mesopore composite pore structural, in the hydroisomerization reaction of catalysis n-alkane, has good catalytic activity and catalytic stability.
Description
Technical field
The present invention relates to a kind of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst and preparation method thereof and
Using.
Background technique
As international community increasingly increases fuel (gasoline, kerosene and diesel oil) demand and to every property of bio-fuel
(such as boiling range, stability, flash-point and freezing point etc.) index is increasingly stringent, obtained by grease or fatty acid methyl ester hydrogenation deoxidation
The isomerization processes of long chain alkane are necessarily obtained improving and be promoted.In the process, zeolite molecular sieve often plays a key effect.It is right
For gasoline, converts linear paraffin or few branched paraffin to multibranched paraffin and can improve octane number significantly；For
For kerosene and diesel oil, its condensation point or pour point can then be reduced by converting branched paraffin for linear paraffin, to improve its low temperature properties
Energy.But another critical issue of above-mentioned reaction process is the yield of target product, since cracking reaction is converted into reaction mass
The low-carbon alkanes of small molecule, and then the yield of target product can be reduced, so being answered while increasing isomerization reaction as far as possible
Cracking reaction is reduced as far as possible.
From thermodynamic (al) viewpoint, cracking reaction needs catalyst to have stronger acid centre and higher reaction temperature,
And acid centre weaker in catalyst and lower reaction temperature are conducive to isomerization reaction.But in order to improve reactivity,
The low disadvantage of reaction efficiency caused by overcoming weak acid center catalyst activity low to reduce with reaction temperature, needing to be loaded into has plus hydrogen
With the metal active constituent of dehydrogenation, it is prepared into difunctional catalyst.In addition, hydro condition can also improve catalyst
Activity stability.It is an object of the invention to provide one kind to have high reaction activity, high isomerization selectivity and isomerization product
The catalyst of yield.
Si-Al molecular sieve or silicoaluminophosphamolecular molecular sieves are due to becoming with the Phi nsted sour position of unique cellular structure and Br
Important acid carrier.Wherein, SAPO-11 molecular sieve is because having suitable micropore canals and the moderate Phi nsted acid strength of Br,
The bifunctional catalyst of its carried noble metal Pt or Pd shows excellent catalytic performance in hydroisomerization reaction.However,
Micropore canals easily cause serious diffusion to limit, and largely hinder mass transfer, heat transfer efficiency, cause it in hydro-refining isomery reaction
In application be significantly restrained.Therefore, the SAPO-11 molecular sieve containing micropore-mesopore compound pore passage structure is increasingly becoming people
Research hotspot.
102874829 A of CN discloses a kind of cavitation effect generated using ultrasonic wave, first by micro-pore zeolite and alkali soluble
Liquid mixing, carries out ultrasonication, then be heat-treated in a closed system to micro-pore zeolite in the presence of an organic, finally
The method that sour processing prepares mesoporous-microporous zeolite molecular sieve is carried out, the mesoporous content in material is increased, improves material
BET surface area, but the preparation step of this method is complicated, it is at high cost.
Technical solution disclosed in 1834015 A of CN under normal pressure, uses ionic liquid as solvent and will be in ionic liquid
Contained cation synthesizes SAPO-11 molecular sieve as template, this scheme is a kind of green chemical synthesis method, is used
Ionic liquid steam force down, the crystallization process of molecular sieve can carry out in atmospheric conditions；Secondly ionic liquid can return
It is reused after receipts processing, there is certain economic benefit, but this method uses ionic liquid to close as medium and template
At SAPO-11 molecular sieve in contain more stray crystal, the properties of product being prepared are poor.
Summary of the invention
For above-mentioned technical problem of the existing technology, the purpose of the present invention is to provide a kind of MCM-41/SAPO-11
Composite molecular screen supported precious metal catalyst and its preparation method and application, catalyst of the invention have high heterogeneous activity, light
The advantages of spending cracking performance etc. good combination property.
A kind of preparation method of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst, feature exist
In the following steps are included:
1) silica MCM-41 original powder is add to deionized water and is stirred evenly, obtain silica MCM-41 aqueous dispersions；Then to
Phosphorus source, silicon source and template are sequentially added in obtained silica MCM-41 aqueous dispersions and is stirred continuously, until obtaining uniformly
Gel mixture；
2) after gel mixture obtained by step 1) being stood 12 ~ 48 h of crystallization at a temperature of 170 ~ 200 DEG C, centrifugation, centrifugation gained
Solid is washed with deionized to neutrality, after dry, be placed in calcining and activating in Muffle furnace, obtain the MCM- of template agent removing
41/SAPO-11 composite molecular screen original powder, then tabletting, broken, sieving, obtain MCM-41/SAPO-11 composite molecular screen particle；
3) by MCM-41/SAPO-11 composite molecular screen particle incipient impregnation obtained by step 2 in the water-soluble of noble metal precursor body
It in liquid, is dried after the completion of dipping, the solid after drying, which is placed in Muffle furnace, to be calcined, and makes dip loading in MCM-41/
Noble metal precursor body on SAPO-11 composite molecular screen particle is changed into precious metal simple substance, obtains the MCM-41/SAPO-
11 composite molecular screen supported precious metal catalysts.
A kind of preparation method of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst, feature exist
In step 1), the silica MCM-41 is the MCM-41 molecular sieve of the non-removed template method of pure silicon；Source of aluminium be selected from it is following it
One: aluminium isopropoxide, aluminum nitrate, boehmite, aluminium oxide, aluminum sulfate, sodium metaaluminate, aluminium chloride.
A kind of preparation method of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst, feature exist
In step 1), the template is di-n-propylamine or diisopropylamine；Phosphorus source is phosphoric acid.
A kind of preparation method of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst, feature exist
In step 1), the silica MCM-41, phosphorus source, silicon source and template mass ratio be 2.5 ~ 7.5: 15 ~ 20: 10 ~ 15:
10~15。
A kind of preparation method of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst, feature exist
In step 2, the process of calcining and activating in Muffle furnace are as follows: in air atmosphere, in 450 ~ 700 DEG C of 4 ~ 8h of temperature calcination.
A kind of preparation method of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst, feature exist
In step 3), the temperature of dipping is room temperature, and the time of dipping is 12 ~ 48h；In step 3), the process calcined are as follows: first
In air atmosphere in 400 ~ 600 DEG C of 2 ~ 5h of temperature calcination, subsequent cooled to room temperature, then in H2Under atmosphere in 350 ~
400 DEG C of 2 ~ 4h of temperature calcination, then cooled to room temperature.
A kind of preparation method of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst, feature exist
In step 3), the noble metal precursor body is the soluble-salt of at least one of Pt, Pd, Rh, Ru；Made from step 3)
In MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst, the noble metal is in MCM-41/SAPO-11 compound molecule
Load capacity on sieve is 0.1% ~ 2.0%.
A kind of preparation method of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst, feature exist
In the noble metal precursor body be four ammonia platinum of nitric acid, chloroplatinic acid, Tetrachloroplatinate ammonium, palladium acetate, ruthenic chloride, radium chloride, potassium ruthenate
At least one of.
The MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst prepared according to above-mentioned method.
The MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst catalysis n-alkane to face hydrogen different
Application in structureization reaction.
The beneficial effects of the present invention are: provided by the present invention for n-alkane hysomer liquid fuel was prepared
Catalyst has micropore-mesopore composite pore structural.The introducing of MCM-41/SAPO-11 composite molecular screen intermediary hole makes alkane point
Diffusion rate of the son in MCM-41/SAPO-11 composite molecular screen crystal is improved, and molecule is made to be easier access to catalyst
Activated centre, the utilization rate of active sites inside micropore in MCM-41/SAPO-11 composite molecular screen crystal is improved, to make
Reaction speed significantly improves.In addition, it is more smoothly to have to introduce mesoporous rear diffusion of the carbonium ion in catalyst duct
Effect inhibits the generation of by-product, achievees the purpose that extend catalyst life.
Detailed description of the invention
Fig. 1 is that the nitrogen for the MCM-41/SAPO-11 composite molecular screen original powder for removing template agent removing that embodiment 2 is prepared is inhaled
Attached-desorption curve and BJH graph of pore diameter distribution；
Fig. 2 is MCM-41/SAPO-11 composite molecular screen and XRD spectrum of the SAPO-11 molecular sieve under 0~40 ° of the angle of diffraction；
Fig. 3 is the XRD of MCM-41/SAPO-11 composite molecular screen, SAPO-11 molecular sieve and MCM-41 under 0~10 ° of the angle of diffraction
Map.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
In following embodiment and comparative example:
Acidic silicasol (SiO2), technical grade, SiO2Mass fraction 31.5% is purchased from Guangzhou Yang Mei Chemical Co., Ltd..
The MCM-41 original powder of the non-removed template method of pure silicon, the silica MCM-41 point purchased from Tianjin Yuan Li Chemical Co., Ltd.
Son sieve.
Comparative example 1
By di-n-propylamine (DPA), boehmite, phosphoric acid, acidic silicasol and water according to mole of 1.25:1:0.8:0.4:50
It than mixing, is stirred continuously after forming uniform gel mixture, stands crystallization 12 hours at a temperature of 180 DEG C, be centrifuged, be centrifuged institute
Solid is washed with deionized to neutrality, after drying at room temperature, be placed in Muffle furnace, in 600 DEG C of temperature under air atmosphere
Lower calcining 5h obtains the SAPO-11 molecular screen primary powder of template agent removing, and gained original powder is carried out tabletting, broken, sieving (sieving
Mesh number is 20 mesh and 40 mesh), particle size is obtained in 20 mesh ~ 40 mesh SAPO-11 carrier granular.
Preparation 0.5wt(i.e. load capacity of the Pt on SAPO-11 carrier granular is 0.5 to % Pt/SAPO-11 catalystwt%),
Preparation process are as follows: impregnate SAPO-11 carrier granular at room temperature in the aqueous solution of four ammonia platinum of nitric acid with equi-volume impregnating
For 24 hours, then at a temperature of 100 DEG C dry (being evaporated the moisture in maceration extract), then the solid after drying is calcined, is forged
Burning process are as follows: first in air atmosphere in 500 DEG C of temperature calcination 3h, subsequent cooled to room temperature, then in H2Under atmosphere
In 380 DEG C of temperature calcination 3h, then cooled to room temperature, it is made 0.5wt%Pt/SAPO-11 catalyst.
Embodiment 1
The MCM-41 original powder of the 2.5 non-removed template methods of g pure silicon is added in 45g deionized water, stirs 0.5h at 25 DEG C,
Obtain the MCM-41 aqueous solution of the non-removed template method of pure silicon；It is quasi- that 16.15g phosphoric acid, 13.6g are sequentially added into MCM-41 aqueous solution
Boehmite, 12.2g DPA and 45g water, and be stirred continuously, until obtaining uniform initial gel mixture；The gel is mixed
Centrifugation after object stands crystallization 12h at a temperature of 170 DEG C is closed, obtained solid is centrifuged and is washed with deionized to neutrality, at room temperature
It after drying, is placed in Muffle furnace, in 450 DEG C of temperature lower calcination 4h under air atmosphere, obtains the MCM-41/ of template agent removing
Gained original powder is carried out tabletting, broken, sieving (crossing grit number is 20 mesh and 40 mesh), obtained by SAPO-11 composite molecular screen original powder
Particle size is labeled as M/S-W-2.5 in 20 mesh ~ 40 mesh MCM-41/SAPO-11 complex carrier particle.
Preparation 0.1wt%Pt/M/S-W-2.5 catalyst, process are as follows: by M/S-W-2.5 with equi-volume impregnating in nitric acid
In the aqueous solution of four ammonia platinum, 12h is impregnated at room temperature, then at a temperature of 50 DEG C dry (being evaporated the moisture in maceration extract), so
The solid after drying is calcined afterwards, calcination process are as follows: first in air atmosphere in 400 DEG C of temperature calcination 2h, then certainly
It is so cooled to room temperature, then in H2In 380 DEG C of temperature calcination 3h, then cooled to room temperature under atmosphere, it is made 0.1wt%Pt/M/
S-W-2.5 catalyst.
Embodiment 2
The MCM-41 original powder of the non-removed template method of 5g pure silicon is added in 45g deionized water, 1.0h is stirred at 35 DEG C, obtains
The MCM-41 aqueous solution of the non-removed template method of pure silicon；16.15g phosphoric acid is sequentially added into MCM-41 aqueous solution, 13.6g intends thin water
Aluminium stone, 12.2g DPA and 45g water, and be stirred continuously, until obtaining uniform initial gel mixture；By the gel mixture
After standing crystallization 24 hours at a temperature of 180 DEG C, centrifugation, centrifugation obtained solid is washed with deionized to neutrality, is done at room temperature
It after dry, is placed in Muffle furnace, in 600 DEG C of temperature lower calcination 5h under air atmosphere, obtains the MCM-41/ of template agent removing
Gained original powder is carried out tabletting, broken, sieving (crossing grit number is 20 mesh and 40 mesh), obtained by SAPO-11 composite molecular screen original powder
Particle size is labeled as M/S-W-5 in 20 mesh ~ 40 mesh MCM-41/SAPO-11 complex carrier particle.
Preparation 0.5wt%Pt/M/S-W-5 catalyst, process are as follows: by M/S-W-5 with equi-volume impregnating in four ammonia of nitric acid
It in the aqueous solution of platinum, impregnates for 24 hours, then at a temperature of 110 DEG C dry (being evaporated the moisture in maceration extract), then will at room temperature
Solid after drying is calcined, calcination process are as follows: then naturally cold first in air atmosphere in 500 DEG C of temperature calcination 3h
But to room temperature, then in H2In 380 DEG C of temperature calcination 3h, then cooled to room temperature under atmosphere, it is made 0.5wt%Pt/M/S-W-
5 catalyst.
The MCM-41/SAPO-11 composite molecular screen original powder for removing template agent removing that embodiment 2 is prepared is characterized,
Its nitrogen adsorption-desorption curve and BJH graph of pore diameter distribution are as shown in Figure 1.It will be seen from figure 1 that sample shows typical IV
Type adsorption isothermal curve, in relative pressure p/p0Desorption curve has precipitous rising, its corresponding microcellular structure when < 0.02；?
p/p0When larger, there is 1 apparent hysteresis loop to occur, illustrate the presence of mesopore orbit.Sample has at 2 ~ 3nm and 4 ~ 16nm
Wider pore-size distribution illustrates not only successfully to synthesize SAPO-11 molecular sieve by silicon source of MCM-41, but also draws in molecular sieve
Mesopore orbit is entered.
The MCM-41/ with micropore-mesopore composite pore structural has been prepared in order to further verify method of the invention
SAPO-11 composite molecular screen removes template agent removing to prepared by the MCM-41 original powder of the non-removed template method of pure silicon, comparative example 1
The MCM-41/SAPO-11 composite molecular screen original powder of template agent removing is prepared in SAPO-11 molecular screen primary powder and embodiment 2
Carry out XRD characterization.Wherein the MCM-41/SAPO-11 composite molecular screen and the SAPO-11 molecular sieve the angle of diffraction 0 ~
XRD spectrum under 40 ° is the MCM-41/SAPO-11 composite molecular screen, described respectively as shown in the curve a and curve b in Fig. 2
Curve a, curve b and the curve c of SAPO-11 molecular sieve and MCM-41 in the XRD spectrum under 0 ~ 10 ° of the angle of diffraction respectively such as Fig. 3
It is shown.
Figure it is seen that MCM-41/SAPO-11 composite molecular screen and two kinds of samples of the SAPO-11 molecular sieve are 2θ
=8.1 °, 9.4 °, 13.1 °, 15.6 °, 20.3 ° and 21.2 ° etc. of characteristic diffraction peak belongs to typical AEL crystal configuration.
MCM-41/SAPO-11 composite molecular screen does not occur other miscellaneous peaks but peak intensity weakens, and illustrates with the non-removed template method of pure silicon
MCM-41 can synthesize the SAPO-11 molecular sieve of pure phase as silicon source, but crystallinity is declined.
From figure 3, it can be seen that sample MCM-41 is 2θThere are the features of crystal at=2.16 °, 3.73 °, 4.31 ° and 5.71 °
Diffraction maximum respectively corresponds (1 0 0), (1 1 0), (2 0 0) and (2 1 0) crystal face.And in SAPO-11 molecular sieve and MCM-
Do not occur the characteristic peak of MCM-41 crystal in 41/SAPO-11 composite molecular screen sample, illustrates MCM-41 skeleton in crystallization process
It is completely dissolved, long-range order meso-hole structure has been destroyed, and the composite molecular screen of synthesis is the micropore-mesopore composite pore structural of pure phase
SAPO-11 molecular sieve.
Embodiment 3
The MCM-41 original powder of the non-removed template method of 7.5g pure silicon is added in 45g deionized water, 1.5 h are stirred at 45 DEG C,
Obtain the MCM-41 aqueous solution of the non-removed template method of pure silicon；It is quasi- that 16.15g phosphoric acid, 13.6g are sequentially added into MCM-41 aqueous solution
Boehmite, 12.2g DPA and 45g water, and be stirred continuously, until obtaining uniform initial gel mixture；The gel is mixed
After conjunction object stands crystallization 48h at a temperature of 200 DEG C, centrifugation, centrifugation obtained solid is washed with deionized to neutrality, is done at room temperature
It after dry, is placed in Muffle furnace, in 700 DEG C of temperature lower calcination 8h under air atmosphere, obtains the MCM-41/ of template agent removing
Gained original powder is carried out tabletting, broken, sieving (crossing grit number is 20 mesh and 40 mesh), obtained by SAPO-11 composite molecular screen original powder
Particle size is labeled as M/S-W-7.5 in 20 mesh ~ 40 mesh MCM-41/SAPO-11 complex carrier particle.
Preparation 0.8wt%Pt/M/S-W-5 catalyst, process are as follows: by M/S-W-7.5 with equi-volume impregnating in nitric acid four
In the aqueous solution of ammonia platinum, 48h is impregnated at room temperature, then at a temperature of 120 DEG C dry (being evaporated the moisture in maceration extract), then
Solid after drying is calcined, calcination process are as follows: then natural first in air atmosphere in 600 DEG C of temperature calcination 5h
It is cooled to room temperature, then in H2In 380 DEG C of temperature calcination 3h, then cooled to room temperature under atmosphere, it is made 0.8wt%Pt/M/S-
W-7.5 catalyst.
Embodiment 4
The silica MCM-41 original powder of SAPO-11 molecular sieve powder (purchased from Tianjin Yuan Li Chemical Co., Ltd.) and 5g of 15g is taken,
Sesbania powder, the commercially available concentrated nitric acid of 0.7mL (mass concentration 68%) and the 10mL deionized water of 4.5g is added, carries out extruded moulding.Then
120 DEG C of drying 2h in baking oven are moved into after being dried at room temperature for 2h.The solid of drying is placed in Muffle furnace, in air atmosphere from
Room temperature is warming up to 550 DEG C with 2 DEG C/min rate program, then roasts 3h at 550 DEG C；Obtain the MCM-41/ of mechanical mixture
SAPO-11 composite molecular screen is labeled as M/S-J carrier.
Preparation 0.5wt%Pt/M/S-J catalyst, process are as follows: by M/S-J carrier with equi-volume impregnating in four ammonia of nitric acid
It in the aqueous solution of platinum, impregnates for 24 hours, then at a temperature of 110 DEG C dry (being evaporated the moisture in maceration extract), then will at room temperature
Solid after drying is calcined, calcination process are as follows: then naturally cold first in air atmosphere in 500 DEG C of temperature calcination 3h
But to room temperature, then in H2In 380 DEG C of temperature calcination 3h, then cooled to room temperature under atmosphere, it is made 0.5wt%Pt/M/S-J
Catalyst.
MCM-41/SAPO-11 compound molecule prepared by SAPO-11 molecular sieve and embodiment 1 ~ 4 prepared by comparative example 1
It sieves sample and carries out BET characterization, the results are shown in Table 1 for the specific surface area and pore structure parameter of BET characterization.
The evaluation of 5 catalyst hydrogenation isomerization activity of embodiment
The hydroisomerization activity rating of catalyst prepared by embodiment 1-4 and comparative example 1 in continuous fixed bed reactors into
Row.By Catalyst packing in continuous fixed bed reactors, it is small that reaction carries out procatalyst prereduction 3 in 380 DEG C of hydrogen
When.When reaction starts, the temperature in fixed bed reactors is controlled in reaction temperature, and the gas that will be passed through in fixed bed reactors
Body switches to the gaseous mixture of hydrogen and reaction raw materials, carries out the hygrogenating isomerization reaction of reaction raw materials.
Reaction condition: reaction raw materials C16Straight chain biology alkane, reaction temperature are 340 DEG C, reaction pressure 1.5MPa, instead
The weight (hourly) space velocity (WHSV) for answering raw material is 1.5h-1, the input material volume ratio of hydrogen and reaction raw materials is 1000.React products therefrom Shimadzu
GC-2014 chromatography is detected, and the capillary column of GC-2014 chromatography is RTx-5 column, and nitrogen is as carrier, and product is by hydrogen flame
Ionization detector detection.2h sampling analysis is reacted as a result, as shown in table 2.In table 2, C16Straight chain biology alkane hydroisomerizing
Target product after changing reaction is isomery hexadecane, and isomery hexadecane is labeled asi-C16。
The data of evaluation result can be seen that the SAPO-11 molecular sieve that synthesizes with using conventional method as carrier system from table 1
At catalyst compare, multilevel pore channel SAPO-11 molecular sieve synthesized by synthetic method of the invention be carrier made of urge
Agent conversion ratio and isomerisation selectivity with higher in hydroisomerization reaction.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated.
Claims (10)
1. a kind of preparation method of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst, it is characterised in that including with
Lower step:
1) silica MCM-41 original powder is add to deionized water and is stirred evenly, obtain silica MCM-41 aqueous dispersions；Then to
Phosphorus source, silicon source and template are sequentially added in obtained silica MCM-41 aqueous dispersions and is stirred continuously, until obtaining uniformly
Gel mixture；
2) after gel mixture obtained by step 1) being stood 12 ~ 48 h of crystallization at a temperature of 170 ~ 200 DEG C, centrifugation, centrifugation gained
Solid is washed with deionized to neutrality, after dry, be placed in calcining and activating in Muffle furnace, obtain the MCM- of template agent removing
41/SAPO-11 composite molecular screen original powder, then tabletting, broken, sieving, obtain MCM-41/SAPO-11 composite molecular screen particle；
3) by MCM-41/SAPO-11 composite molecular screen particle incipient impregnation obtained by step 2 in the water-soluble of noble metal precursor body
It in liquid, is dried after the completion of dipping, the solid after drying, which is placed in Muffle furnace, to be calcined, and makes dip loading in MCM-41/
Noble metal precursor body on SAPO-11 composite molecular screen particle is changed into precious metal simple substance, obtains the MCM-41/SAPO-
11 composite molecular screen supported precious metal catalysts.
2. a kind of preparation side of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst according to claim 1
Method, it is characterised in that in step 1), the silica MCM-41 is the MCM-41 molecular sieve of the non-removed template method of pure silicon；Source of aluminium
Selected from one of following: aluminium isopropoxide, aluminum nitrate, boehmite, aluminium oxide, aluminum sulfate, sodium metaaluminate, aluminium chloride.
3. a kind of preparation side of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst according to claim 1
Method, it is characterised in that in step 1), the template is di-n-propylamine or diisopropylamine；Phosphorus source is phosphoric acid.
4. a kind of preparation of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst according to claim 1
Method, it is characterised in that in step 1), the silica MCM-41, phosphorus source, silicon source and template mass ratio be 2.5 ~ 7.5:
15~20 : 10~15 : 10~15。
5. a kind of preparation side of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst according to claim 1
Method, it is characterised in that in step 2, the process of calcining and activating in Muffle furnace are as follows: in air atmosphere, in 450 ~ 700 DEG C of temperature
Calcine 4 ~ 8h.
6. a kind of preparation side of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst according to claim 1
Method, it is characterised in that in step 3), the temperature of dipping is room temperature, and the time of dipping is 12 ~ 48h；In step 3), calcined
Process are as follows: first in air atmosphere in 400 ~ 600 DEG C of 2 ~ 5h of temperature calcination, subsequent cooled to room temperature, then in H2Gas
In 350 ~ 400 DEG C of 2 ~ 4h of temperature calcination, then cooled to room temperature under atmosphere.
7. a kind of preparation side of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst according to claim 1
Method, it is characterised in that in step 3), the noble metal precursor body is the soluble-salt of at least one of Pt, Pd, Rh, Ru；Step
It is rapid 3) made from MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst, the noble metal is in MCM-41/SAPO-
Load capacity on 11 composite molecular screens is 0.1% ~ 2.0%.
8. a kind of preparation side of MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst according to claim 7
Method, it is characterised in that the noble metal precursor body is four ammonia platinum of nitric acid, chloroplatinic acid, Tetrachloroplatinate ammonium, palladium acetate, ruthenic chloride, chlorine
Change at least one of rhodium, potassium ruthenate.
9. MCM-41/SAPO-11 composite molecular screen carried noble metal catalysis prepared by the method as described in claim 1 ~ 8 is any
Agent.
10. MCM-41/SAPO-11 composite molecular screen supported precious metal catalyst as claimed in claim 9 is in catalysis N-alkanes
Application in the hydroisomerization reaction of hydrocarbon.
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