CN108452839A - A kind of Jie's mesoporous-microporous composite molecular sieve, catalyst and its preparation method and application - Google Patents
A kind of Jie's mesoporous-microporous composite molecular sieve, catalyst and its preparation method and application Download PDFInfo
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- CN108452839A CN108452839A CN201810234698.1A CN201810234698A CN108452839A CN 108452839 A CN108452839 A CN 108452839A CN 201810234698 A CN201810234698 A CN 201810234698A CN 108452839 A CN108452839 A CN 108452839A
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 144
- 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 144
- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000002283 diesel fuel Substances 0.000 claims abstract description 19
- 238000011282 treatment Methods 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 74
- 229910052697 platinum Inorganic materials 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000002585 base Substances 0.000 claims description 27
- 239000011148 porous material Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 150000003057 platinum Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 241000238370 Sepia Species 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000010970 precious metal Substances 0.000 abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 13
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 241001120493 Arene Species 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000000499 gel Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000007142 ring opening reaction Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 210000002659 acromion Anatomy 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000004996 alkyl benzenes 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
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229940069328 povidone Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000012690 zeolite precursor Substances 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- 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
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/52—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/54—Hydrogenation of the aromatic hydrocarbons 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
- 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
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of Jie's mesoporous-microporous composite molecular sieves, catalyst and its preparation method and application.The molecular sieve, by the way that alkali source, template, silicon source is added, is carried out obtained from Crystallizing treatment using USY molecular sieve as raw material；The catalyst includes carrier and uniform load in the active component Pt of carrier, and the carrier is above-mentioned molecular sieve, and the particle diameter distribution of the active component Pt is 1.0~5.0nm, and Pt load capacity is the 0.1~1.0% of catalyst gross mass.The present invention also provides the preparation method and application of above-mentioned molecular sieve and catalyst.Catalyst of the present invention using Jie's micro porous molecular sieve of high-specific surface area as carrier, can effective divided active component, under the premise of low precious metal content, catalyst still has higher catalytic activity, be particularly suitable for arylhydrocarbon in diesel oil selective opening reaction.
Description
Technical field
The present invention relates to molecular sieve and field of catalyst preparation more particularly to a kind of Jie's mesoporous-microporous composite molecular sieve, catalysis
Agent and its preparation method and application.
Background technology
Arenes selectivity adds hydrogen open loop technique that aromatic hydrocarbons can be made to be converted to alkylbenzene or the cycloalkane with side chain, significantly carries
The Cetane number of high catalytic diesel oil, the core of the technology, which is exploitation, has the bifunctional catalyst for adding hydrogen and open-loop performance.
Arenes selectivity adds in hydrogen open loop technique, and noble metal catalyst has higher hydrogenation activity than other metals, but
Its resistance to SO_2 of the catalyst of carried noble metal component is poor, and the sulphur of very low levels may result in catalyst inactivation in usual raw material.
And due to the load of a certain amount of noble metal, increase the cost of catalyst.In addition, the Acidity and pore structure of carrier, catalysis
Preparation method of agent etc. is all an important factor for influencing catalyst performance.
Chinese patent CN201510083128.3 discloses a kind of bicyclic above arenes selectivity and adds hydrogen ring opening catalyst
Preparation method includes the following steps：(1) by modified aluminas, extrusion aid and modified molecular screen, (Beta or ZSM-5/SAPO-5 are multiple
Close molecular sieve) it is uniformly mixed, catalyst carrier is prepared after extrusion；(2) salting liquid of VIB and group VIII metal is prepared as dipping
Solution；(3) use the method for incipient impregnation or step impregnation that active component is supported on carrier；(4) alcoholic solution is impregnated, into
The redisperse of row active component, then dry, roasting obtain catalyst prod.The active component content of the catalyst is higher, by
10~20wt% vib metals and 5~10wt% group VIII metals composition.It is prepared in the method disclosed in the patent simultaneously
Catalyst improve diesel cetane-number ability it is limited.
Chinese patent CN201210194486.8 discloses a kind of diesel oil distillate oil hydrogenation catalysts and its system containing rare earth
Standby and application, includes the following steps：(1) molecular sieve containing rare earth element is prepared；(2) amorphous silicon aluminium material is prepared；(3) it prepares
Macroporous aluminium oxide；(4) material prepared by step (1), (2) and (3) is mixed with extrusion aid and pore creating material, extrusion, dry, roasting
Obtain catalyst carrier；(5) in supported on carriers active component, then through drying, roasting, activate to obtain catalyst.The proprietary catalysts
Although Cetane number can be significantly improved, the second segment aromatic hydrocarbons depth saturation and the choosing that are only applicable in two-stage hydrogenation upgrading processes
The open loop of selecting property.
Chinese patent CN200810104303.2 discloses a kind of de- virtue of modified molecular screen base precious metal diesel oil deepness hydrogenation
Catalyst and preparation method thereof.Include the following steps：(1) HY molecular sieves are prepared by the method for ion exchange；(2) to HY molecules
Sieve carries out dealumination complement silicon modification, prepares carrier；(3) VIII group precious metal salt solution is impregnated, through drying, roasting, activates to obtain catalysis
Agent.The catalyst uses the active component system of noble metal adding assistant, although with preferable open loop activity, it is in raw material
S, the heteroatomic resistance such as N is weaker.
For the above-mentioned relevant issues pointed out, currently no effective solution has been proposed.
Invention content
The application first technical problem to be solved is to provide a kind of Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve.This point
Son sieve large specific surface area and duct is uniform, has suitable acid amount, can effectively divided active component, thermal stability are good.
The application second technical problem to be solved is to provide a kind of system of Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve
Preparation Method.The preparation method controls micropore phase and mesoporous phase in Jie's porous carrier by adding the micro porous molecular sieve of different quality
Ratio, so as to adjust complex carrier acid amount distribution.
The application third technical problem to be solved is to provide a kind of Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve and is urging
Application in agent preparation field.Mesoporous-micropore canals structure in the molecular sieve and higher specific surface area, can be effective
Divided active component, to provide more hydrogenation activity positions.
The application the 4th technical problem to be solved is to provide a kind of platinum base Jie mesoporous-microporous composite molecular sieve catalyst.This is urged
Agent has catalysis open loop and adds the difunctional of hydrogen, and the nanoscale platinum grain of uniform particle diameter is capable of providing more open loops and hydrogen is added to live
Property position, under the premise of low precious metal content, catalyst still has higher open loop hydrogenation activity, is particularly suitable for catalytic diesel oil
Arenes selectivity ring-opening reaction.
The application the 5th technical problem to be solved is to provide a kind of system of platinum base Jie mesoporous-microporous composite molecular sieve catalyst
Preparation Method.Active component content is low in catalyst prepared by this method, and nano level active component is uniformly dispersed；It ensure that relatively low
Bullion content under the premise of, catalyst still has higher catalysis open loop and Hydrogenation, and it is fragrant to be particularly suitable for catalytic diesel oil
Hydrocarbon-selective ring-opening reaction..
The application the 6th technical problem to be solved is to provide a kind of platinum base Jie mesoporous-microporous composite molecular sieve catalyst in bavin
Application in oily arenes selectivity open loop catalytic field.
In order to solve the first technical problem mentioned above, the present invention adopts the following technical scheme that：
A kind of Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve, the molecular sieve has mesoporous and micropore canals structure, mesoporous
Pore-size distribution is 2.0~4.0nm, and micropore size is distributed as 0.3~1.0nm；The specific surface area of the molecular sieve be 600~
1200m2/ g, total pore volume are 0.3~1.2cm3The ratio that/g, mesoporous Kong Rong account for total pore volume is 30~90%.
Given an account of mesoporous-microporous composite molecular sieve, by the way that alkali source, template, silicon source is added, is carried out using USY molecular sieve as raw material
Obtained from Crystallizing treatment.
To solve above-mentioned second technical problem, the present invention adopts the following technical scheme that：
The preparation method of Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve as described above, includes the following steps：
USY molecular sieve is uniformly mixed in aqueous solution with alkali source, obtains the first solution；
Template is dissolved in the water, the second solution is obtained；
First solution and the second solution are mixed, it is 7~12 to adjust pH, obtains third solution；
Silicon source is added in third solution, Crystallizing treatment is carried out；
Product after Crystallizing treatment is filtered, washed, dry, is roasted, USY/MCM-48 composite molecular screens are made.
As being further improved for technical solution, the mixing temperature of the USY molecular sieve and alkali source is 15~45 DEG C, preferably
35℃。
As being further improved for technical solution, the mass ratio of the USY molecular sieve and silicon source is 1：(5~120).
As being further improved for technical solution, the template is CTAB and P123, wherein the CTAB's and P123
Usage ratio is 1:(0.1~0.3).
As being further improved for technical solution, the pH value is 10~11；The silicon source and the molar ratio of template are
1：(0.08~0.3).
As being further improved for technical solution, the Crystallizing treatment temperature is 90-150 DEG C, and the Crystallizing treatment time is 12-
72h；Preferably, the Crystallizing treatment time is 48h.
As being further improved for technical solution, the roasting condition is：0.5~2h is roasted at 150~300 DEG C, then
300~450 DEG C of 1~3h of roasting are warming up to, 450~650 DEG C of 3~6h of roasting are finally warming up to.
To solve above-mentioned third technical problem, the invention discloses USY/MCM-48 composite molecular screens as described above to exist
Application in field of catalyst preparation.
To solve above-mentioned 4th technical problem, the present invention adopts the following technical scheme that：
A kind of platinum base Jie mesoporous-microporous composite molecular sieve catalyst, the catalyst include the work of carrier and uniform load in carrier
Property component Pt, the carrier USY/MCM-48 composite molecular screens as described above, the particle diameter distribution of the active component Pt is 1.0
~5.0nm, load capacity are the 0.1~1.0% of catalyst gross mass.
To solve above-mentioned 5th technical problem, the present invention adopts the following technical scheme that：
The preparation method of platinum base Jie's mesoporous-microporous composite molecular sieve catalyst as described above, the method includes：
Platinum salt, Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve and polyvinylpyrrolidone are mixed in aqueous solution
It is even, obtain solution A；
Excess sodium borohydrate solution is added into solution A, until solution becomes sepia；
Brown solution is dry, roasting, obtains platinum base Jie's mesoporous-microporous composite molecular sieve catalyst.
As being further improved for technical solution, the concentration ratio of the polyvinylpyrrolidone and platinum salt is 20~100；Institute
It is 0.1~1.0% to state the mass ratio of platinum and USY/MCM-48 composite molecular screens in platinum salt；The drying temperature of the brown solution
Be 90~120 DEG C, drying time be 12~for 24 hours；The temperature of the roasting is 300~450 DEG C, preferably 350~400 DEG C；It is described
The time of roasting is 4~8h.
To solve above-mentioned 6th technical problem, the invention also discloses platinum base Jie mesoporous-microporous composite molecular sieves as described above
Application of the catalyst in arylhydrocarbon in diesel oil selective opening catalytic field.
Any range recorded in the present invention includes any numerical value between end value and end value and end value or end value
Between the arbitrary subrange that is constituted of any number.
Unless otherwise specified, each raw material in the present invention can be obtained by commercially available purchase, equipment used in the present invention
The conventional equipment in fields can be used or carried out with reference to the prior art of fields.
Compared with prior art, the present invention has the advantages that：
(1) Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve of the present invention, large specific surface area and mesopore orbit is evenly distributed have
Suitable acid amount, can effectively divided active component.
(2) Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve of the present invention has been significantly greatly increased multiple by the addition of USY molecular sieve
Close the hydrothermal stability of molecular sieve.
(3) Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve preparation method of the present invention, by the micropore point for adding different quality
Son sieves to control the ratio of micropore phase and mesoporous phase in Jie's porous carrier, so as to adjust the acid amount distribution of complex carrier.
(4) Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve preparation method of the present invention, can be by changing making for P123 templates
Dosage can be effectively increased the pore wall thickness of mesoporous MCM-48 molecular sieves, to which the hydro-thermal for improving compound Jie's micro porous molecular sieve is steady
It is qualitative.
(5) platinum base Jie's mesoporous-microporous composite molecular sieve catalyst of the invention has catalysis open loop and adds the difunctional of hydrogen,
It is particularly suitable for catalytic diesel oil arenes selectivity ring-opening reaction, open loop is efficient.
(6) platinum base Jie's mesoporous-microporous composite molecular sieve catalyst of the invention, Jie's micro porous molecular sieve of high-specific surface area can have
The nanoscale platinum grain of the divided active component of effect, uniform particle diameter is capable of providing more hydrogenation activity positions, contains in low noble metal
Under the premise of amount, catalyst still has higher hydrogenation activity, is particularly suitable for catalytic diesel oil arenes selectivity open loop and adds hydrogen anti-
It answers.That is, when the content of Pt is 0.1~1.0%, open loop hydrogenation catalyst efficiency still is able to reach 95% or more.
(7) platinum base Jie's mesoporous-microporous composite molecular sieve catalyst of the invention, bullion content is low, active component high degree of dispersion,
And with excellent catalysis open loop hydrogenation activity, selectivity, stability, lower production cost.
(8) in the preparation method of molecular sieve and catalyst of the present invention, the P123 templates added can reduce biology
Nondegradable CTAB templates usage amount, it is small to environmental hazard, reduce production cost.
(9) building-up process of molecular sieve and catalyst of the present invention is simple, synthesis cycle is short, largely reduces life
The usage amount of the nondegradable CTAB templates of object has potential using value to heavy oil catalytic hydrocracking.
Description of the drawings
Fig. 1 is the SEM figures of gained molecular sieve in the embodiment of the present invention 2.
Fig. 2 is the TEM figures of gained molecular sieve in the embodiment of the present invention 2.
Fig. 3 is that catalyst TEM prepared in the embodiment of the present invention 4 schemes.
Fig. 4 is the embodiment of the present invention 1,2, in comparative example 1 gained molecular sieve through the small angle XRD before and after boiling water treating to comparison
Figure.
Fig. 5 is the wide-angle XRD spectrums of gained molecular sieve and USY molecular sieve (purchase gained) in the embodiment of the present invention 1,2,3
Figure.
Fig. 6 is the small angle XRD spectra of gained molecular sieve in the embodiment of the present invention 1,2,3, comparative example 1.
Fig. 7 is the graph of pore diameter distribution of gained molecular sieve in the embodiment of the present invention 1,2,3, comparative example 1.
Specific implementation mode
In order to illustrate more clearly of the present invention, with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection domain of invention.
A kind of Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve, the molecular sieve is using USY molecular sieve as raw material, by the way that alkali is added
Source, template, silicon source carry out what Crystallizing treatment was prepared；The molecular sieve has mesoporous and micropore canals structure, mesoporous hole
Diameter is distributed as 2.0~4.0nm, and micropore size is distributed as 0.3~1.0nm；The specific surface area of the molecular sieve be 600~
1200m2/ g, total pore volume are 0.3~1.2cm3The ratio that/g, mesoporous Kong Rong account for total pore volume is 30~90%.
Above-mentioned Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve is prepared by outgrowth method, using USY as kernel, surface covering
One layer of MCM-48 particle, to keep the combination of two-phase even closer.
" USY molecular sieve " of the present invention, the silica alumina ratio for example, by using the production of Tianjin Nan Hua catalyst Co., Ltd are
5.2~30, specific surface area >=680m20.35~0.45cm of/g, Kong Rongwei3/ g, aperture are the H-type molecular sieve of 0.7~5nm.
A kind of preparation method of Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve, the preparation method include the following steps：
USY molecular sieve is uniformly mixed in aqueous solution with alkali source, obtains the first solution；
Template is dissolved in the water, the second solution is obtained；
First solution and the second solution are mixed, it is 7~12 to adjust pH, obtains third solution；
Silicon source is added in third solution, Crystallizing treatment is carried out；
Product after Crystallizing treatment is filtered, washed, dry, is roasted, Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve is made.
The preparation method is by outgrowth, using USY as kernel, enables its surface cover one layer of MCM-48 particle, to make
The combination of two-phase is even closer.
Meanwhile controlling micropore phase and mesoporous phase in Jie's porous carrier by adding the USY micro porous molecular sieves of different quality
Ratio, so as to adjust complex carrier acid amount distribution, the hydrothermal stability of composite molecular screen can also be improved.
According to the certain embodiments of the application, the mixing temperature of the USY molecular sieve and alkali source is 15~45 DEG C, stirring
0.5~3h；It is preferred that 35 DEG C.Uniform gel solution is advantageously formed in this way to get to USY molecular sieve micropore precursor liquid.
According to the certain embodiments of the application, the template is CTAB and P123, wherein the dosage of CTAB and P123
Ratio is 1:(0.1~0.3).By using mixed templates, the use of the nondegradable CTAB templates of biology can be reduced
Amount.And it can be effectively increased the pore wall thickness of mesoporous MCM-48 molecular sieves by the usage amount of change P123 templates, from
And improve the hydrothermal stability of compound Jie's micro porous molecular sieve.
According to the certain embodiments of the application, CTAB and P123 templates are dissolved in distilled water, are formed transparent
Template micellar solution stirs 0.5~6h under the conditions of 15~45 DEG C, two kinds of templates is made to be sufficiently mixed uniformly.
According to the certain embodiments of the application, the pH value is 10~11, and it is equal can to generate crystal form, pore passage structure at this time
One precipitated product.
According to the certain embodiments of the application, the molar ratio of the silicon source and template is 1：(0.08~0.3), favorably
The generation of Jie's Yu micro porous molecular sieve.
According to the certain embodiments of the application, the mass ratio of the USY molecular sieve and silicon source is 1：(5~120).
According to the certain embodiments of the application, silicon source solution is added drop-wise to formation white gels solution in third solution,
1~8h is stirred, is fitted into the crystallizing kettle of 50~1000mL, 12~72h of crystallization in 90~150 DEG C of baking ovens, when preferred crystallization
Between be 48h, to promote the generation of USY/MCM-48.
According to the certain embodiments of the application, above-mentioned crystallization product is subjected to three sections of program roastings, 150~300 DEG C of roastings
0.5~2h is burnt, 300~450 DEG C of 1~3h of roasting are then heated to, is finally warming up to 450~650 DEG C of 3~6h of roasting；Preferably,
0.5~2h is roasted at 250 DEG C, then heats to 350 DEG C of 1~3h of roasting, is finally warming up to 450~650 DEG C of 3~6h of roasting.It should
Calcination procedure is conducive to template removal is clean.
Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve of this method synthesis, large specific surface area and mesopore orbit is evenly distributed,
It, can effectively divided active component with suitable acid amount.
USY/MCM-48 composite molecular screens as described above are used to prepare Jie's mesoporous-microporous composite molecular sieve catalyst.
A kind of platinum base Jie mesoporous-microporous composite molecular sieve catalyst, the catalyst include the work of carrier and uniform load in carrier
Property component Pt, the carrier be Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve as described above, the grain size of the active component Pt
It is distributed as 1.0~5.0nm, load capacity is the 0.1~1.0% of catalyst gross mass.
The Pt crystal grain of platinum base Jie's mesoporous-microporous composite molecular sieve catalyst is uniformly dispersed, in catalyst surface in Nano type point
It dissipates, advantageously reduces the load capacity of Pt.
The platinum based catalyst has catalysis open loop and adds the difunctional of hydrogen, is particularly suitable for catalytic diesel oil arenes selectivity and opens
Ring reacts, and open loop is efficient.
A kind of preparation method of platinum base Jie mesoporous-microporous composite molecular sieve catalyst, the method includes：
Platinum salt, Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve and polyvinylpyrrolidone are mixed in aqueous solution
It is even, obtain solution A；
Excess sodium borohydrate solution is added into solution A, until solution becomes sepia；
Brown solution is dry, roasting, obtains platinum base Jie's mesoporous-microporous composite molecular sieve catalyst.
The catalyst of this method synthesis, Jie's micro porous molecular sieve of high-specific surface area can effective divided active component, grain
The uniform nanoscale platinum grain of diameter is capable of providing more hydrogenation activity positions, under the premise of low precious metal content, catalyst according to
So there is efficient hydrogenation activity, is particularly suitable for arylhydrocarbon in diesel oil selective opening hydrogenation reaction.
According to the certain embodiments of the application, platinum salt is dissolved in distilled water, measures the platiniferous solution of certain volume
It is added in a certain amount of aqueous povidone solution, adds Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve powder, stirring is equal
It is even, wherein the concentration ratio of the polyvinylpyrrolidone and platinum salt is 20~100.Be conducive to being uniformly dispersed for Pt in this way.
According to the certain embodiments of the application, the mass ratio of platinum and USY/MCM-48 composite molecular screens is in the platinum salt
0.1~1.0%.Even if when the additive amount of Pt is only 0.1~1.0%, the open loop hydrogenation catalyst efficiency of obtained catalyst, especially
It is the catalytic efficiency of arenes selectivity open loop, still is able to reach 95% or more.According to the certain embodiments of the application, incited somebody to action
The sodium borohydride solution of amount is slowly dropped in solution A, until solution becomes sepia, it is on a rotary evaporator that sepia is molten
Liquid is evaporated, and by sample drying, drying temperature is 90~120 DEG C, and drying time is 12~for 24 hours, be conducive to Pt in catalyst surface
Dispersion.
According to the certain embodiments of the application, the temperature of the roasting is 300~450 DEG C, preferably 350~400 DEG C；Institute
The time for stating roasting is 4~8h, this baking modes makes the interaction of Pt and carrier strong, while avoiding the burning of Pt crystal grain
Knot.
Platinum base Jie's mesoporous-microporous composite molecular sieve catalyst as described above has catalysis open loop and adds the difunctional of hydrogen, especially suitable
For in catalytic diesel oil arenes selectivity ring-opening reaction.Arylhydrocarbon in diesel oil selective opening technique is at a kind of oil hydrogenation of maturation
Science and engineering skill, technical process have been well known to those of ordinary skill in the art, and the present invention handles the hydrogenation selectivity open loop
The condition of process is not particularly limited, and can be carried out under the conditions of various rational.
The invention will be further described for the following examples.
Embodiment 1
There is a kind of Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve mesoporous and micropore canals structure, mesoporous pore size to be distributed as
2.0~4.0nm, micropore size are distributed as 0.4~1.0nm；Specific surface area is 1000~1200m2/ g, total pore volume be 1.0~
1.2cm3The ratio that/g, mesoporous Kong Rong account for total pore volume is 80~90%.
The preparation method of above-mentioned USY/MCM-48 composite molecular screens is as follows：
6gNaOH is dissolved in 60mL water first, is then added thereto the 0.5g USY molecular sieve powder dried, 35
DEG C water-bath in stir 1h, form USY molecular sieve precursor liquid；
4g CTAB and 7g P123 templates are dissolved in 80mL distilled water, 1h is stirred under the conditions of 35 DEG C, are formed transparent
Solution, it is 10 to be used in combination ammonium hydroxide to adjust the pH value of solution；
USY molecular sieve precursor liquid is added in template solution, 2h is stirred.Then toward mixed solution and dripping 24gTEOS,
6h is stirred, gel solution is formed, white gels solution is fitted into 200mL crystallizing kettles, is put into 100 DEG C of baking ovens crystallization for 24 hours；
Product after crystallization is washed with distilled water three times, then the dry 12h in 80 DEG C of baking oven.It is roasted using three sections
Mode roasted, i.e.,：1h is roasted at 250 DEG C first, 350 DEG C of roasting 2h is then heated to, is finally warming up to 550 DEG C of roastings
5h, final sample are denoted as Y (0.5) M.
Embodiment 2
There is a kind of Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve mesoporous and micropore canals structure, mesoporous pore size to be distributed as
2.0~4.0nm, micropore size are distributed as 0.4~1.0nm；Specific surface area is 1000~1200m2/ g, total pore volume be 0.8~
1.0cm3The ratio that/g, mesoporous Kong Rong account for total pore volume is 70~80%.
The preparation method of above-mentioned USY/MCM-48 composite molecular screens is as follows：
6gNaOH is dissolved in 60mL water first, is then added thereto the 1g USY molecular sieve powder dried, at 35 DEG C
Water-bath in stir 1h, form USY molecular sieve precursor liquid；
4g CTAB and 7g P123 templates are dissolved in 80mL distilled water, 1h is stirred under the conditions of 35 DEG C, are formed transparent
Solution, it is 10 to be used in combination ammonium hydroxide to adjust the pH value of solution；USY molecular sieve precursor liquid is added in template solution, 2h is stirred；
Then toward mixed solution and dripping 18g TEOS, 6h is stirred, forms gel solution.White gels solution is packed into
In 200mL crystallizing kettles, it is put into 100 DEG C of baking ovens crystallization for 24 hours；
Product after crystallization is washed with distilled water three times, then the dry 12h in 80 DEG C of baking oven.It is roasted using three sections
Mode roasted, i.e.,：1h is roasted at 250 DEG C first, 350 DEG C of roasting 2h is then heated to, is finally warming up to 550 DEG C of roastings
5h, final sample are denoted as Y (1.0) M.
Fig. 1 is the SEM figures of gained molecular sieve in the embodiment of the present invention 2.
From figure 1 it appears that Y (1.0) the M molecular sieves polyhedral structure in the form of sheets generated, crystallite dimension 100~
Between 600nm.
Fig. 2 is the TEM figures of gained molecular sieve in the embodiment of the present invention 2.
From figure 2 it can be seen that Y (1.0) M zeolite crystals are by USY molecular sieve kernel (the deeper region of color in figure),
Surface MCM-48 particles (the shallower region of color in figure) composition.
Embodiment 3
There is a kind of Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve mesoporous and micropore canals structure, mesoporous pore size to be distributed as
2.0~4.0nm, micropore size are distributed as 0.4~1.0nm；Specific surface area is 800~1000m2/ g, total pore volume be 0.8~
1.0cm3The ratio that/g, mesoporous Kong Rong account for total pore volume is 70~80%.
The preparation method of above-mentioned USY/MCM-48 composite molecular screens is as follows：
6gNaOH is dissolved in 60mL water first, is then added thereto the 1.5g USY molecular sieve powder dried, 35
DEG C water-bath in stir 1h or more, formed USY molecular sieve precursor liquid；
4g CTAB and 7g P123 templates are dissolved in 80mL distilled water, 1h is stirred under the conditions of 35 DEG C, are formed transparent
Solution, it is 10 to be used in combination ammonium hydroxide to adjust the pH value of solution；USY molecular sieve precursor liquid is added in template solution, 2h is stirred；
Then toward mixed solution and dripping 16g TEOS, 6h is stirred, forms gel solution；White gels solution is packed into
In 200mL crystallizing kettles, it is put into 100 DEG C of baking ovens crystallization for 24 hours；
Product after crystallization is washed with distilled water three times, then the dry 12h in 80 DEG C of baking oven.It is roasted using three sections
Mode roasted, i.e.,：1h is roasted at 250 DEG C first, 350 DEG C of roasting 2h is then heated to, is finally warming up to 550 DEG C of roastings
5h, final sample are denoted as Y (1.5) M.
Comparative example 1
A kind of MCM-48 molecular sieves have mesopore orbit structure.
The preparation method of the molecular sieve is as follows：
4g CTAB and 7g P123 are dissolved in 90mL distilled water, 40min is stirred under the conditions of 35 DEG C；Measuring volume is
The 2.5moL/LNaOH solution of 10mL is added in mixed templates, 20g TEOS is added dropwise to above-mentioned mixed liquor after 20min
In enter, and stir 4h, be fitted into 200mL crystallizing kettles crystallization for 24 hours.Product after crystallization is washed with distilled water three times, is then existed
Dry 12h in 80 DEG C of baking oven.It is roasted by the way of three sections of roastings, i.e.,：1h is roasted at 250 DEG C first, is then heated up
To 350 DEG C of roasting 2h, 550 DEG C of roasting 5h are finally warming up to, final sample is denoted as MCM-48.
Embodiment 4
A kind of platinum base Jie mesoporous-microporous composite molecular sieve catalyst, the catalyst are situated between micro- with USY/MCM-48 prepared by embodiment 2
Hole composite molecular screen is carrier, and on carrier, the average grain diameter of active component Pt is nano level active component Pt uniform loads
4.0nm, Pt load capacity are the 0.4% of catalyst gross mass.
The preparation method of above-mentioned platinum base Jie mesoporous-microporous composite molecular sieve catalyst is as follows：
4g Y (1.0) M catalyst is taken, 160mL distilled water is added, stirring at room temperature is measured respectively to without apparent solid particle
Take the platinum acid chloride solution 8.5mL of the polyvinylpyrrolidonesolution solution 9.0mL and 0.005g/mL of 0.1g/mL that molecular sieve is added molten
In liquid, after stirring 1h, a concentration of 1.0g/L sodium borohydride solutions of 30mL are slowly added dropwise.After reaction, on a rotary evaporator
Solvent is evaporated, sample is put into 100 DEG C of baking ovens dry 12h after being evaporated, is finally roasted in the Muffle furnace for being connected with air
4h is burnt, calcination temperature is 350 DEG C.Catalyst is denoted as Pt0.4/Y (1.0) M.
Fig. 3 is that catalyst TEM prepared in the embodiment of the present invention 4 schemes.
From figure 3, it can be seen that Pt0.4In/Y (1.0) M catalyst, it is compound that Pt crystal grain is uniformly dispersed in USY/MCM-41
In molecular sieve.
Comparative example 2
A kind of platinum base MCM-48 molecular sieve catalysts, the step of the preparation method of the catalyst with reference to described in embodiment 4
Suddenly, different places is：Carrier by MCM-48 molecular sieves (preparation of comparative example 1) as the catalyst.The catalyst is remembered
For Pt0.4/MCM-48。
Comparative example 3
A kind of the step of platinum base USY molecular sieve catalyst, the preparation method of the catalyst is with reference to described in embodiment 4,
Different places are：Carrier by USY molecular sieve (raw material used in embodiment 2) as the catalyst.By the catalysis
Agent is denoted as Pt0.4/USY。
Embodiment 5
The hydrothermal stability of molecular sieve is analyzed：
1g MCM-48 (preparation of comparative example 1), Y (0.5) M (preparation of embodiment 1) and Y (1.0) M (embodiments 2 are weighed respectively
Preparing) polytetrafluoroethylene beaker is added in molecular sieve, then beaker is fitted into the 100mL crystallizing kettles for filling 70mL distilled water, it is put into
In 100 DEG C of baking ovens, it is respectively washed with distilled water three times after 48h, then the dry 12h in 80 DEG C of baking oven, sample is remembered
For MCM-48-T, Y (0.5) M-T and Y (1.0) M-T.
Respectively to through sample MCM-48, Y (0.5) M and Y (1.0) M before boiling water treating, and the sample after boiling water treating
Product MCM-48-T, Y (0.5) M-T and Y (1.0) M-T carries out small angle XRD detections.
Fig. 4 is the embodiment of the present invention 1,2, in comparative example 1 gained molecular sieve through the small angle XRD before and after boiling water treating to comparison
Figure.Wherein, a representative samples Y (1.0) M are through the small angle XRD spectra before and after boiling water treating；B representative samples Y (0.5) M through boiling water at
The front and back small angle XRD spectra of reason；C representative samples MCM-48 is through the small angle XRD spectra before and after boiling water treating.
It can be seen that from the XRD spectra in Fig. 4 after sample is handled 48h in boiling water, the small corner characteristics of sample after processing
Diffraction maximum is declined, but still remains meso-hole structure.The front and back comparison of single sample boiling water treating is, it is specified that molecular sieve is handled
Before [220], the characteristic diffraction peak peak area corresponding to [221] crystal face be 1, then after three sample treatments, characteristic diffraction peak area
It has dropped respectively：92.73% (counter sample MCM-48), 15.56% (counter sample Y (0.5) M), 8.46% (counter sample Y
(1.0)M).Illustrate that the addition with USY molecular sieve presoma, composite molecular screen hydrothermal stability gradually increase.
Embodiment 6
The XRD and pore analysis of molecular sieve：
To sample Y (0.5) M (preparation of embodiment 1), Y (1.0) M (preparation of embodiment 2), Y (1.5) M, (embodiment 3 is made respectively
It is standby) and MCM-48 (preparation of comparative example 1), USY molecular sieve (purchase gained) progress XRD detections.
Fig. 5 is the wide-angle XRD spectrums of gained molecular sieve and USY molecular sieve (purchase gained) in the embodiment of the present invention 1,2,3
Figure.
From figure 5 it can be seen that Y (x) M (x=0.5,1.0,1.5) still remain the characteristic diffraction peak with USY molecular sieve,
But diffraction peak intensity is all declined, on the one hand due to when preparing USY zeolite precursor liquid, the part of USY under alkaline condition
It is destructurized, on the other hand, after ion exchange occurs for the Na+ and CTA+ on USY presomas, then participate in the group of meso-hole structure
Dress, therefore form part USY insertions or be embedded in MCM-48, it can equally cause the wide-angle characteristic peak of composite material to weaken.
Fig. 6 is the small angle XRD spectra of gained molecular sieve in the embodiment of the present invention 1,2,3, comparative example 1.
From fig. 6 it can be seen that Y (x) M (x=0.5,1.0,1.5) composite materials and MCM-48 samples go out peak position phase
Together, there is a stronger diffraction maximum in 2 θ=2.6 ° or so, belong to [211] crystal face of three-dimensional cubic crystallographic system, and at it
After there is an acromion, belong to [220] crystal face of three-dimensional cubic crystallographic system, it is seen that synthesized material Y (x) M has and MCM-
48 identical three-dimensional cubic meso-hole structures.And with the addition of USY precursor liquids, the diffraction maximum of each sample [211] crystal face is to low angle
Direction offset is spent, the cell parameter of MCM-48 becomes larger, mainly due to passing through MCM-48 between micro porous molecular sieve and mesoporous material
- the OH of activation is combined to form Si-O-Al structures with the Al of four-coordination in Y molecular sieve, this makes two distinct types of material knot
That closes more stablizes and in roasting process caused by composite material contraction.
To sample Y (0.5) M (preparation of embodiment 1), Y (1.0) M (preparation of embodiment 2), Y (1.5) M, (embodiment 3 is made respectively
It is standby) and MCM-48 (preparation of comparative example 1) progress N2Adsorption desorption is tested.
Fig. 7 is the graph of pore diameter distribution of gained molecular sieve in the embodiment of the present invention 1,2,3, comparative example 1.
It can be seen from figure 7 that the pore-size distribution of MCM-48 and composite material is very uniform, it is concentrated mainly on 3nm or so.
Embodiment 7
Platinum base Jie's mesoporous-microporous composite molecular sieve catalyst performance evaluation：
The evaluation of arylhydrocarbon in diesel oil selective opening catalyst activity is carried out on fixed-bed micro-reactor.First by 40~
The 2.0g Pt of 60 mesh0.4For/Y (1.0) M (preparation of embodiment 4) Catalyst packing in fixed bed reaction pipe, remaining in reaction tube is empty
Between filled with quartz sand full, wherein catalyst is fixed on constant temperature zone, and is separated catalyst and quartz sand with silica wool.System passes through
N2After purging, it is passed through H2Carry out the air-tightness of verifying attachment.After air-tightness qualification, H is passed through with the rate of 15mL/min2, at 350 DEG C
Under the conditions of reducing catalyst 1h.Using the diesel oil after pre- hydrofinishing as raw material after activation of catalyst, raw material is micro by double plunger
Metering pump conveys, after being vaporized by preheating furnace, at T=300 DEG C；P=6.0MPa；LHSV=2.0h-1；H2/ oil (volume ratio)=
Under conditions of 750,4h is fed, after reaction temperature, pressure, hydrogen flowing quantity etc. are stablized, collects 6h product liquids.In Varian
On CP-3800GC and Agilent 5973MS combined instruments, product is qualitatively and quantitatively analyzed.
As a comparison, with reference to above-mentioned steps to platinum base Pt0.4/ MCM-48 molecular sieve catalysts carry out arylhydrocarbon in diesel oil selectivity
The catalytic performance test of open loop, the difference is that：With Pt0.4/ MCM-48 (preparation of comparative example 2) carries out performance as catalyst
Test.
As a comparison, arylhydrocarbon in diesel oil selective opening is carried out to platinum base Pt/USY molecular sieve catalysts with reference to above-mentioned steps
Catalytic performance test, the difference is that：With Pt0.4/ USY (preparation of comparative example 3) is tested for the property as catalyst.
Its analysis result is as shown in table 1 below.
1 arylhydrocarbon in diesel oil of table is through being catalyzed front and back performance parameter list
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.To those of ordinary skill in the art, it can also do on the basis of the above description
Go out other various forms of variations or variation.Here all embodiments can not be exhaustive.It is every to belong to the present invention's
Row of the obvious changes or variations that technical solution is extended out still in protection scope of the present invention.
Claims (10)
1. a kind of Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve, it is characterised in that：The molecular sieve has mesoporous and micropore canals
Structure, mesoporous pore size are distributed as 2.0~4.0nm, and micropore size is distributed as 0.3~1.0nm, and the specific surface area of the molecular sieve is
600~1200m2/ g, total pore volume are 0.3~1.2cm3The ratio that/g, mesoporous Kong Rong account for total pore volume is 30~90%.
2. the preparation method of Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve as described in claim 1, which is characterized in that the system
Preparation Method includes the following steps：
USY molecular sieve is uniformly mixed in aqueous solution with alkali source, obtains the first solution；
Template is dissolved in the water, the second solution is obtained；
First solution and the second solution are mixed, it is 7~12 to adjust pH, obtains third solution；
Silicon source is added in third solution, Crystallizing treatment is carried out；
Product after Crystallizing treatment is filtered, washed, dry, is roasted, USY/MCM-48 composite molecular screens are made.
3. the preparation method of Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve according to claim 2, which is characterized in that described
The mixing temperature of USY molecular sieve and alkali source is 15~45 DEG C；The mass ratio of the USY molecular sieve and silicon source is 1：(5~120)；
The template is that the dosage molar ratio of CTAB and P123, the CTAB and P123 are 1:(0.1~0.3).
4. the preparation method of Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve according to claim 2, which is characterized in that described
PH value is 10~11；The silicon source and the molar ratio of template are 1：(0.08~0.3)；The Crystallizing treatment temperature be 90~
150 DEG C, the Crystallizing treatment time is 12~72h.
5. the preparation method of Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve according to claim 2, which is characterized in that described
Roasting condition is：0.5~2h is roasted at 150~300 DEG C, is then heated to 300~450 DEG C of 1~3h of roasting, is finally warming up to
450~650 DEG C of 3~6h of roasting.
6. application of Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve as described in claim 1 in field of catalyst preparation.
7. a kind of platinum base Jie mesoporous-microporous composite molecular sieve catalyst, which is characterized in that the catalyst includes carrier and uniform load
In the active component Pt of carrier, the carrier is Jie's USY/MCM-48 mesoporous-microporous composite molecular sieve as described in claim 1, described
The particle diameter distribution of active component Pt is 1.0~5.0nm, and load capacity is the 0.1~1.0% of catalyst gross mass.
8. the preparation method of platinum base Jie mesoporous-microporous composite molecular sieve catalyst as claimed in claim 7, which is characterized in that the side
Method includes：
Platinum salt, USY/MCM-48 composite molecular screens and polyvinylpyrrolidone are uniformly mixed in aqueous solution, obtain solution
A；
Excess sodium borohydrate solution is added into solution A, until solution becomes brownish black；
Brown solution is dry, roasting, obtains platinum base Jie's mesoporous-microporous composite molecular sieve catalyst.
9. preparation method according to claim 8, which is characterized in that the concentration ratio of the polyvinylpyrrolidone and platinum salt
It is 20~100；The mass ratio of platinum and USY/MCM-48 composite molecular screens is 0.1~1.0% in the platinum salt；The sepia is molten
The drying temperature of liquid be 90~120 DEG C, drying time be 12~for 24 hours；The temperature of the roasting be 300~450 DEG C, preferably 350
~400 DEG C；The time of the roasting is 4~8h.
10. platinum base Jie mesoporous-microporous composite molecular sieve catalyst as claimed in claim 7 is catalyzed in arylhydrocarbon in diesel oil selective opening and leads
Application in domain.
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