CN108067290A - Carrier and catalyst of a kind of sieve containing bimolecular and its preparation method and application - Google Patents
Carrier and catalyst of a kind of sieve containing bimolecular and its preparation method and application Download PDFInfo
- Publication number
- CN108067290A CN108067290A CN201611011394.6A CN201611011394A CN108067290A CN 108067290 A CN108067290 A CN 108067290A CN 201611011394 A CN201611011394 A CN 201611011394A CN 108067290 A CN108067290 A CN 108067290A
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- Prior art keywords
- molecular sieve
- catalyst
- sba
- modified
- sieve
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 106
- 239000002808 molecular sieve Substances 0.000 claims abstract description 105
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000000853 adhesive Substances 0.000 claims description 15
- 230000001070 adhesive effect Effects 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000428 triblock copolymer Polymers 0.000 claims description 6
- 241001502050 Acis Species 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 239000000320 mechanical mixture Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- 238000005336 cracking Methods 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 238000004523 catalytic cracking Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000004517 catalytic hydrocracking Methods 0.000 description 7
- 229910052681 coesite Inorganic materials 0.000 description 7
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229910052682 stishovite Inorganic materials 0.000 description 7
- 229910052905 tridymite Inorganic materials 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000011959 amorphous silica alumina Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 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 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- -1 VIB metal oxide Chemical class 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical class [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000002101 lytic effect Effects 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone 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
- 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
- B01J29/0333—Iron group metals or copper
-
- 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
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- 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
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B01J35/615—
-
- B01J35/635—
-
- 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
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
-
- 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
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides carrier and catalyst of a kind of sieve containing bimolecular and its preparation method and application.For the carrier in terms of vehicle weight, modified Y molecular sieve accounts for 48.5wt% ~ 89.9wt%, and 15 molecular sieves of SBA account for 0.1wt% ~ 1.5wt%, and aluminium oxide accounts for 10wt% ~ 50wt%.For the catalyst in terms of the weight of catalyst, modified Y molecular sieve accounts for 28.5wt% ~ 74.9wt%, and 15 mesopore molecular sieves of SBA account for 0.1wt% ~ 1.5wt%；Group VIB metal accounts for 10.0 ~ 25.0wt% based on oxide, and group VIII metal accounts for 3.0 ~ 8.0wt% based on oxide, and aluminium oxide meter accounts for 10 ~ 30wt%.The carrier is particularly suitable for preparing light oil type hydrogen cracking catalyst, has high catalytic cracking activity and high purpose product selectivity.
Description
Technical field
The present invention relates to a kind of carrier of sieve containing bimolecular and catalyst and its preparation method and application, relate in particular to
Carrier and catalyst of a kind of sieve containing bimolecular and preparation method thereof and the application for producing light fraction oil.
Technical background
With being done step-by-step for Chinese dream, people’s lives quality is also higher and higher, demand and day to light-weight fuel oil
While all increasings, the requirement to clean fuel oil is also increasingly harsh.The quality and quantity of oil time processing is not satisfied by people
Demand, heavy distillate by hydrocracking process carry out secondary operation be converted into good light Fuel not only sufficiently
Limited petroleum resources are make use of, alleviate the market demand of light fraction oil, and product quality is high, it is environmentally friendly.Add
Hydrogen cracking technology key is hydrocracking catalyst, and the quality of catalyst carrier properties then determines activity, the mesh of catalyst
Product selectivity and product quality.
Carrier is the diversification of markets for carrying acidic cleavage component and providing hydrogenation active component for hydrocracking catalyst
Institute is that reactant contacts generation cracking reaction with active sites, and product is in the reaction platform of hydrogenation center hydrogenation saturation.
CN101618347A discloses a kind of carrier of hydrocracking catalyst containing Y molecular sieve.The carrier is by being modified Y molecules
Sieve and aluminium oxide composition.The Y type molecular sieve is obtained with after the mixed aqueous solution of aluminium salt and acid processing hydro-thermal process, property
Matter is as follows：750 ~ 850m of specific surface2/ g, 0.35 ~ 0.48ml/g of total pore volume, relative crystallinity 90 ~ 130%, lattice constant 2.437 ~
2.445nm, silica alumina ratio 15 ~ 70, meleic acid amount 0.5 ~ 1.0mmol/g, B acid/L are sour more than 7.0, and sodium oxide content≤
0.05wt%.The catalyst carrier contains 30 ~ 70% modified molecular screens and 30 ~ 70% aluminium oxide (in terms of the weight of carrier)；Large pore volume,
Specific surface area is high.The carrier, which is used to prepare hydrocracking catalyst, has good catalytic activity, heavy naphtha high selectivity, scheelite brain
The features such as oily arene underwater content is high, but fluorine-containing by-product can be discharged when preparing modified Y molecular sieve, it is not friendly enough to environment,
And C5 +Liquid yield is not high.
US4,672,048 describe a kind of light oil type hydrogen cracking catalyst, and molecular sieve used is LZ-210,
SiO2/Al2O3Molar ratio is preferably 11 ~ 15, and its preparation method is：Ammonium hexafluorosilicate handles NH in acidic buffer solution4NaY
Molecular sieve, fluorine-containing accessory substance enter liquid phase, and sodium reaches balance with solution in product LZ-210, so LZ-210 sodium contents are higher,
Generally in 0.5w% or so, if obtaining low sodium content, it is also necessary to which further ammonium exchanges.There is the catalyst higher light oil to select
Selecting property and anti-nitrogen performance, but the activity of catalyst is not very high.
CN101269343A discloses a kind of composite mesoporous molecular sieve hydrocracking catalyst.The catalyst amorphous silica-alumina
20 ~ 50%, aluminium oxide 5 ~ 30%, adhesive 10 ~ 20%, VI B races metal (Mo and/or W) oxide 10 ~ 40%, VIII race metal (Co
And/or Ni) oxide 1 ~ 20%, nonmetallic (P) oxide 0.1 ~ 10% of V A races, the composition of composite mesoporous molecular sieve 1 ~ 40%；It is compound
Mesopore molecular sieve is mesopore molecular sieve AlSBA-15 and/or AlSBA-15/Y composite molecular screen.Due to compound point of AlSBA-15/Y
Son sieve is the mixed solution modification of SBA-15 aluminium isopropoxides and hydrochloric acid, is then mixed into NH4Prepared by Y molecular sieve.SBA-15 is used
The modified acidity of the mixed solution of aluminium isopropoxide and hydrochloric acid is weak, the NH of preparation4Y molecular sieve sodium oxide content is high, acid low, and heat
Stability is poor；The acidic cleavage component that AlSBA-15/Y composite molecular screens are used as hydrocracking catalyst causes cracking catalyst to live
Property it is poor, catalyst heat and hydrothermal stability it is poor.
CN101590424A introduces a kind of catalyst used for hydrogenation of distilled oil fraction and preparation method thereof.The catalyst used for hydrogenation of distilled oil fraction
It forms as (with weight)：Group VIII metal (oxide 2 ~ 16%, group VIB metal oxide 10 ~ 30%, remaining
The carrier formed for SBA-15 and alumina composite.The catalyst is free of acidic cleavage component, is a kind of Hydrobon catalyst.
CN103769194A discloses a kind of catalytic hydro-dearomatization catalyst and preparation method thereof.The main active component of the catalyst
For Pt, adjuvant component Pd, carrier is amorphous silica-alumina and SBA-15/Y composite molecular screens, on the basis of the weight of catalyst,
The content of Pt is 0.1wt%~0.5wt%, and the content of Pd is 0.3wt%~0.8wt%, the content of amorphous silica-alumina for 50wt%~
The content of 90wt%, SBA-15/Y composite molecular screen is 5wt%~20wt%, and the content of adhesive is 9wt%~30wt%；
Y type molecular sieve weight content is 50wt%~90wt% in SBA-15/Y composite molecular screens；SBA-15/Y composite molecular screens used
Property it is as follows：SiO2/A12O3Molar ratio is 40 ~ 85, specific surface area 400m2/ g~1000m2/ g, pore volume 0.5cm3/ g~
2.0cm3/ g, infrared acidity are 0.3~0.6mmol/g.The preparation process of catalyst is as follows：By SBA-15/Y composite molecular screens with
Through kneading, shaping, dry and roasting obtains catalyst carrier for amorphous silica-alumina and adhesive；It is carried using infusion process in catalyst
After loading Pd and Pt on body, through dry and roasting, catalytic hydro-dearomatization catalyst is obtained.Wherein SBA-15/Y composite molecular screens use
It is prepared by following method,（a）Silicon source is added in acid solution, is stirred until clear solution is become；（b）Cationic surface is lived
Property agent, which is dissolved in the water, to stir evenly；（c）Y type molecular sieve carries out hydro-thermal process, and the hydro-thermal process temperature is 350 ~ 650
DEG C, pressure for 0.5 ~ 3.0MPa, reaction time 1 ~ 6 it is small when；（d）By step（a）The solution of gained is added to step（b）Gained
In the mixed solution of compositions comprising cationic surfactants, then stirring adds in step（c）The molecular sieve of gained, after mixing,
When hydro-thermal process 24 ~ 72 is small at 70 ~ 150 DEG C, filtered, washing, then through drying, obtain mesoporous-microporocomposite composite molecular sieve.The party
Although SBA-15/Y composite molecular screens have meso-hole structure as an entirety in method, different ducts are situated between in composite molecular screen
Matching degree between the SBA-15- micropores Y of hole is poor, is unfavorable for the transmission of material, SBA-15/Y composite molecular screens are the same as unformed silicon
The duct of aluminium is even more that can not be connected, it is impossible to really play the role of passage, additionally, there may be that preparation process is complicated, of high cost etc. asks
Topic.
The content of the invention
In order in place of overcome the deficiencies in the prior art, the present invention provides a kind of sieve containing bimolecular carrier and catalyst and
Its preparation method and application.The carrier is particularly suitable for preparing light oil type hydrogen cracking catalyst, has high catalytic pyrolysis
Active and high purpose product selectivity.
A kind of carrier of the sieve containing bimolecular, is made of modified Y molecular sieve, SBA-15 molecular sieves and aluminium oxide, to contain double points
The vehicle weight meter of son sieve, modified Y molecular sieve account for 48.5wt% ~ 89.9wt%, and SBA-15 molecular sieves account for 0.1wt% ~ 1.5wt%, oxygen
Change aluminium and account for 10wt% ~ 50wt%, the specific surface area of the carrier of the sieve containing bimolecular is 280 ~ 480m2/ g, pore volume for 0.32 ~
0.52ml/g, the property of the modified Y molecular sieve are as follows：Relative crystallinity 90 ~ 110%, 2.435 ~ 2.446nm of lattice constant, than
750 ~ 850m of surface2/ g, 0.40 ~ 0.50ml/g of total pore volume, silica alumina ratio 8 ~ 20,0.8 ~ 1.2mmol/g of meleic acid amount；It is described
The property of SBA-15 molecular sieves is as follows：4.6 ~ 30nm of aperture, preferably 6 ~ 20nm, pore volume >=0.75ml/g, be preferably >=
0.8ml/g, 600 ~ 900m of specific surface2/ g is preferably 650 ~ 850m2/g。
A kind of catalyst of the sieve containing bimolecular, by modified Y molecular sieve, SBA-15 molecular sieves, aluminium oxide and hydrogenation activity gold
Belong to composition, the hydrogenation active component be group VIB metal and group VIII metal, group VIB metal be molybdenum and/or tungsten, the VIIIth
Race's metal is cobalt and/or nickel, and in terms of the weight of catalyst, modified Y molecular sieve accounts for 28.5wt% ~ 74.9wt%, mesoporous point of SBA-15
Son sieve accounts for 0.1wt% ~ 1.5wt%；Group VIB metal accounts for 10.0 ~ 25.0wt% based on oxide, and group VIII metal is based on oxide
3.0 ~ 8.0wt% is accounted for, aluminium oxide meter accounts for 10 ~ 30wt%, and the BET specific surface area of catalyst is 260 ~ 450m2/ g, pore volume is 0.25 ~
0.50ml/g, the property of the modified Y molecular sieve are as follows：Relative crystallinity 90 ~ 110%, 2.435 ~ 2.446nm of lattice constant, than
750 ~ 850m of surface2/ g, 0.40 ~ 0.50ml/g of total pore volume, silica alumina ratio 8 ~ 20,0.8 ~ 1.2mmol/g of meleic acid amount；It is described
The property of SBA-15 molecular sieves is as follows：4.6 ~ 30nm of aperture, preferably 6 ~ 20nm, pore volume >=0.75ml/g, be preferably >=
0.8ml/g, 600 ~ 900m of specific surface2/ g is preferably 650 ~ 850m2/g。
In the present invention, the modified Y molecular sieve is with NH4NaY molecular sieve is raw material via hydrothermal dealumination and chemical dealuminization
Modifying process and be made.SBA-15 molecular sieves are to use triblock copolymer P123 as template, using positive esters of silicon acis as silicon source, in
The pure silicon mesopore molecular sieve that hydrothermal synthesis comes out under acid condition
The preparation method of present invention sieve carrier containing bimolecular, including following content：By modified Y molecular sieve, template is not burnt
Adhesive made from SBA-15 molecular sieves and dilute nitric acid solution peptized alumina carries out mechanical mixture, rolls, is molded, Ran Hougan
Dry, roasting obtains the carrier of the sieve containing bimolecular.
The preparation method of present invention sieve catalyst containing bimolecular, including following content：By modified Y molecular sieve, template is not burnt
It is mixed that the SBA-15 mesopore molecular sieves of agent, hydrogenation active metals and adhesive made from dilute nitric acid solution peptized alumina carry out machinery
It closes, roll, extruded moulding, then dry, roasting obtains the catalyst of the sieve containing bimolecular.
During the present invention sieves carrier containing bimolecular or sieved containing bimolecular, the preparation of the modified Y molecular sieve is including as follows
Step：
（1）Commercially available NH4NaY molecular sieve (relative crystallinity >=90%, lattice constant 2.466 ~ 2.470nm, SiO2/Al2O3
>=5.0, Na2O≤2.5w%, butt 75 ~ 90%) raw material is placed in hydro-thermal process stove, hydro-thermal process temperature is risen to 500 ~ 750
DEG C, preferably 550 ~ 700 DEG C；Control system pressure (steam partial pressure PH2OP is divided with ammoniaNH3The sum of) in 0.01 ~ 0.3MPa, it is excellent
Select 0.05 ~ 0.15MPa, PNH3/(PNH3+PH2O) >=0.1, best PNH3/(PNH3+PH2O)=0.2~0.5；Carry out hydrothermal dealumination 0.5 ~ 5
Hour, preferably 1 ~ 3 it is small when；
（2）To step（1）Obtained material is used containing H+And NH4 +Mixed solution carry out chemical dealuminization, dealuminzation condition is：H+With
NH4 +Mixed solution and step（1）The weight ratio of obtained material is 5:1~15:1, H+Concentration be 0.1 ~ 1mol/L, NH4 +It is dense
It spends for 0.2 ~ 2mol/L；60 ~ 130 DEG C of temperature, preferably 80 ~ 100 DEG C；When time 0.2 ~ 5 is small, preferably 0.5 ~ 2 it is small when；Then cross
Filter is washed to pH >=6.5, and filter cake is dry to butt >=80% at 100 ~ 120 DEG C, obtains modified Y molecular sieve.
The present invention does inferior distillate oil containing the catalyst that bimolecular sieves for working process height, can obtain high catalysis and split
Solution activity and high purpose product selectivity.
Modified Y molecular sieve of the present invention is with NH4NaY molecular sieve is raw material via hydrothermal dealumination and chemical dealuminization
The distribution of modifying process appropriateness dealuminzation, modulation molecular sieve acid site concentration and acid strength and B acid and L acid；Improve molecular sieve
Skeleton Si/Al shrinks structure cell, improves the stability of molecular sieve；Abundant secondary mesoporous is generated simultaneously, is conducive to improve molecule
The adsorption and desorption performance of sieve reduces reactant, the diffusional resistance of product, improves reaction rate；It is higher so as to make it have
Catalytic pyrolysis performance.SBA-15 molecular sieves of the present invention are to use triblock copolymer P123 as template, with positive silicon
Acid esters is silicon source, and hydrothermal synthesis comes out pure silicon mesopore molecular sieve under acid condition.A small amount of not providing is added in catalyst to urge
Change the SBA-15 molecular screen primary powders of activity, on the premise of catalyst activity is not influenced, make the duct of each component in catalyst have
Effect links up, and the template in SBA-15 molecular sieve pore passages is removed in the last just fired removing of catalyst preparation process,
Its duct is made to become unobstructed so that generate the micropore of 1 ~ 3nm of many on the hole wall of SBA-15, the duct with modified Y molecular sieve can
To be well matched with, the diffusional resistance of reactant, product is advantageously reduced.SBA-15 is equivalent in catalysis material body phase
" bridge formation of paving the way ", the probability that the reactant of macromolecular is contacted by the macropore of SBA-15 molecular sieves with the active sites of catalysis material
It is greatly improved with speed, so as to improve the reactivity of catalysis material；In addition the product for reacting generation is expanded rapidly by " road and bridge "
It dissipates and leaves, overreaction is avoided, so as to improve the liquid yield of product.
Specific embodiment
Below by embodiment, the present invention will be further described, but following embodiment is not construed as limiting the invention,
% is mass percent unless otherwise specified in following embodiment and comparative example.
Embodiment 1
Take commercially available NH4NaY molecular sieve (relative crystallinity 92%, lattice constant 2.469nm, SiO2/Al2O3=5.1, Na2O=
2.5w%, butt 80%) 300g is placed in hydro-thermal process stove, gives electricity heating, hydro-thermal process temperature is risen to 580 DEG C, control system
Pressure of uniting (steam partial pressure PH2OP is divided with ammoniaNH3The sum of) in 0.1MPa, PNH3/(PNH3+PH2O)=0.25；It carries out at hydro-thermal
Manage 2.5 it is small when.Sieve sample the 100g nitric acid containing 0.3M and the NH containing 1.8M after water intaking heat treatment4NO3Mixed solution
0.8L is filtered when chemical dealuminization reaction 1.5 is small under the conditions of 95 DEG C, and the same terms repeat reaction once, Washing of Filter Cake to filtrate
PH=6.8, filter cake is dry to butt=80% at 120 DEG C, obtains the modified Y molecular sieve A of the present invention.It is as follows to measure A properties：Relatively
Crystallinity 97%, lattice constant 2.441nm, specific surface 786m2/ g, total pore volume 0.44ml/g, silica alumina ratio 12.7, Na2O=
0.11w%, meleic acid amount 1.09mmol/g.
Embodiment 2
Take commercially available NH4NaY molecular sieve (relative crystallinity 92%, lattice constant 2.469nm, SiO2/Al2O3=5.1, Na2O=
2.5w%, butt 80%) 600g is placed in hydro-thermal process stove, gives electricity heating, hydro-thermal process temperature is risen to 630 DEG C, control system
Pressure of uniting (steam partial pressure PH2OP is divided with ammoniaNH3The sum of) in 0.08MPa, PNH3/(PNH3+PH2O)=0.3；It carries out at hydro-thermal
Manage 2.0 it is small when.Sieve sample the 200g nitric acid containing 0.1M and the NH containing 2.0M after water intaking heat treatment4NO3Mixed solution 2L
When chemical dealuminization reaction 1.0 is small under the conditions of 90 DEG C, filtering, the same terms repeat reaction twice, Washing of Filter Cake to filtrate pH=
6.5, filter cake is dry to butt=80% at 120 DEG C, obtains the modified Y molecular sieve B of the present invention.It is as follows to measure B properties：Opposite crystallization
Degree 95%, lattice constant 2.439nm, specific surface 775m2/ g, total pore volume 0.46ml/g, silica alumina ratio 13.6, Na2O=0.09w%,
Meleic acid amount 1.05mmol/g.
Comparative example 1
Modified Y molecular sieve C is prepared by the Chinese patent 90102645.X methods recorded.It is as follows to measure C properties：Relative crystallinity
97%, lattice constant 2.450nm, specific surface 775m2/ g, total pore volume 0.38ml/g, silica alumina ratio 10.7, Na2O=0.03w% is red
Outer acid amount 1.12mmol/g.
Embodiment 3
Take it is commercially available use triblock copolymer P123 as template, using positive esters of silicon acis as silicon source, under acid condition hydro-thermal close
The mesopore molecular sieve D used into pure silicon mesoporous molecular sieve SBA-15 original powder 300g out as the present invention.Measure its property (roasting
Detected after burning removed template method) it is as follows：Aperture 11.2nm, pore volume >=0.82ml/g, specific surface 783m2/g。
Embodiment 4
Mesoporous point not roasted that 74.1 grams of modified Y molecular sieve A (butt 80wt%) that embodiment 1 obtains, embodiment 3 are obtained
(molar ratio of butt 30wt%, nitric acid and small porous aluminum oxide is placed in for 0.3) 66 grams in roller mixes D0.9 grams of son sieve with adhesive
It grinds, is pressed into paste, extruded moulding, and when 110 DEG C of dryings 4 are small, then when 560 DEG C of roastings 4 are small, obtains catalyst carrier
ZA, physico-chemical property are shown in Table 1.
Embodiment 5
The mesopore molecular sieve D0.5 that 207 grams of modified Y molecular sieve B (butt 80wt%) that embodiment 2 obtains, embodiment 3 are obtained
Gram (butt 30wt%, the molar ratio of nitric acid and small porous aluminum oxide are placed in mixed grind in roller for 0.3) 100 grams, are pressed into adhesive
Paste, extruded moulding, and when 110 DEG C of dryings 4 are small, then when 560 DEG C of roastings 4 are small, obtain catalyst carrier ZB, materialization
Property is shown in Table 1.
Comparative example 2
97.5 grams of modified Y molecular sieve C (butt 80wt%) that comparative example 1 is obtained, with adhesive (butt 30wt%, nitric acid with it is small
The molar ratio of porous aluminum oxide is placed in mixed grind in roller for 0.3) 66 grams, is pressed into paste, extruded moulding, and 110 DEG C dry 4 small
When, then when 550 DEG C of roastings 4 are small, catalyst carrier ZC is obtained, physico-chemical property is shown in Table 1.
Comparative example 3
Catalyst carrier ZD is prepared by the method for CN101618347A embodiments 4, physico-chemical property is shown in Table 1.
The physico-chemical property of 1 carrier of table
Embodiment 6
Respectively with containing WO3The ammonium metatungstate of 45.82g/100ml, NiO 11.49g/100ml, nickel nitrate mixed solution dipping are real
Apply the carrier ZA that example 4 obtains, the carrier that the carrier ZC that carrier ZB, the comparative example 2 that embodiment 5 obtains obtain and comparative example 3 obtain
The volume ratio of ZD, maceration extract and carrier is 2:1, excessive maceration extract, 105 DEG C of dryings are filtered off, 500 DEG C of roastings are made corresponding
Catalyst CA, CB, CC and CD.Its physico-chemical property is shown in Table 2.
The physico-chemical property of 2 catalyst of table
Embodiment 7
The present embodiment introduction is prepared into the Activity evaluation of catalyst by carrier impregnation hydrogenation metal component of the present invention.Evaluation makes
Raw material is vacuum distillate (GVO), and property is listed in table 3.Evaluation carries out on the fixed bed hydrogenation cracking unit of 200ml,
Evaluation condition is：React stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1500:1, volume space velocity 1.67h-1.Evaluation result is listed in table 4.
3 vacuum distillate of table (VGO) main character
4 COMPARATIVE CATALYST's evaluation result of table
* engler is fractionated result
From evaluation result as can be seen that catalyst is for handling the vacuum distillate (VGO) that height inferior is done, in identical technique
Under the conditions of, the catalyst activity that carrier impregnation hydrogenation metal of the present invention obtains is high, and liquid is received high.So the carrier of the present invention is suitble to use
Make light oil type hydrogen cracking catalyst, higher liquid yield is also obtained while higher lytic activity can be obtained.
Embodiment 8
Take commercially available NH4NaY molecular sieve (relative crystallinity 92%, lattice constant 2.469nm, SiO2/Al2O3=5.1, Na2O=
2.5w%, butt 80%) 300g is placed in hydro-thermal process stove, gives electricity heating, hydro-thermal process temperature is risen to 580 DEG C, control system
Pressure of uniting (steam partial pressure PH2OP is divided with ammoniaNH3The sum of) in 0.1MPa, PNH3/(PNH3+PH2O)=0.25；It carries out at hydro-thermal
Manage 2.5 it is small when.Sieve sample the 100g nitric acid containing 0.3M and the NH containing 1.8M after water intaking heat treatment4NO3Mixed solution
0.8L is filtered when chemical dealuminization reaction 1.5 is small under the conditions of 95 DEG C, and the same terms repeat reaction once, Washing of Filter Cake to filtrate
PH=6.8, filter cake is dry to butt=80% at 120 DEG C, obtains the modified Y molecular sieve A1 of the present invention.It is as follows to measure A1 properties：Phase
To crystallinity 97%, lattice constant 2.441nm, specific surface 786m2/ g, total pore volume 0.44ml/g, silica alumina ratio 12.7, Na2O=
0.11w%, meleic acid amount 1.09mmol/g.
Embodiment 9
Take commercially available NH4NaY molecular sieve (relative crystallinity 92%, lattice constant 2.469nm, SiO2/Al2O3=5.1, Na2O=
2.5w%, butt 80%) 600g is placed in hydro-thermal process stove, gives electricity heating, hydro-thermal process temperature is risen to 630 DEG C, control system
Pressure of uniting (steam partial pressure PH2OP is divided with ammoniaNH3The sum of) in 0.08MPa, PNH3/(PNH3+PH2O)=0.3；It carries out at hydro-thermal
Manage 2.0 it is small when.Sieve sample the 200g nitric acid containing 0.1M and the NH containing 2.0M after water intaking heat treatment4NO3Mixed solution 2L
When chemical dealuminization reaction 1.0 is small under the conditions of 90 DEG C, filtering, the same terms repeat reaction twice, Washing of Filter Cake to filtrate pH=
6.5, filter cake is 80% in 120 DEG C of dryings to butt, obtains the modified Y molecular sieve B1 of the present invention.It is as follows to measure B1 properties：Relatively
Crystallinity 95%, lattice constant 2.439nm, specific surface 775m2/ g, total pore volume 0.46ml/g, silica alumina ratio 13.6, Na2O=
0.09w%, meleic acid amount 1.05mmol/g.
Comparative example 4
Modified Y molecular sieve C1 is prepared by the Chinese patent 90102645.X methods recorded.It is as follows to measure C1 properties：Relative crystallinity
97%, lattice constant 2.450nm, specific surface 775m2/ g, total pore volume 0.38ml/g, silica alumina ratio 10.7, Na2O=0.03w% is red
Outer acid amount 1.12mmol/g.
Embodiment 10
Take it is commercially available use triblock copolymer P123 as template, using positive esters of silicon acis as silicon source, under acid condition hydro-thermal close
The mesopore molecular sieve D1 used into pure silicon mesoporous molecular sieve SBA-15 original powder 300g out as the present invention.Measure its property
(being detected after roasting removed template method) is as follows：Aperture 11.2nm, pore volume >=0.82ml/g, specific surface 783m2/g。
Embodiment 11
Catalyst presses Y:SBA-15:MoO3:NiO:Adhesive=0.591:0.009:0.2:0.05:It is prepared by 0.15 proportioning.
The mesopore molecular sieve D1 that 295.5 grams of modified Y molecular sieve A1 (butt 80wt%) that embodiment 8 obtains, embodiment 10 are obtained
3.6 grams of mixing add in 80 grams of molybdenum oxide, 77.8 grams of nickel nitrate, adhesive (butt 30wt%, mole of nitric acid and small porous aluminum oxide
Than being placed in mixed grind in roller for 0.3) 200 grams, be pressed into paste, extruded moulding, and 110 DEG C it is dry 4 it is small when, then 550
When DEG C roasting 4 is small, the catalyst CA1 containing composite molecular screen of the present invention is obtained, physico-chemical property is shown in Table 5.
Embodiment 12
Catalyst presses Y:SBA-15:MoO3:NiO:Adhesive=0.545:0.005:0.2:0.05:0.15 proportioning system
It is standby.The mesopore molecular sieve that 272.5 grams of modified Y molecular sieve B1 (butt 80wt%) that embodiment 9 obtains, embodiment 10 are obtained
2 grams of mixing of D1, add in 80 grams of molybdenum oxide, 77.8 grams of nickel nitrate, (butt 30wt%, nitric acid rub adhesive with small porous aluminum oxide
Your ratio is 0.3) to be placed in mixed grind in roller for 267 grams, is pressed into paste, extruded moulding, and when 110 DEG C of dryings 4 are small, Ran Hou
When 550 DEG C of roastings 4 are small, the catalyst CB1 containing composite molecular screen of the present invention is obtained, physico-chemical property is shown in Table 5.
Comparative example 5
39 grams of 40 grams of 128 grams of modified Y molecular sieve C (butt 80wt%), molybdenum oxide, nickel nitrate, the adhesive that comparative example 4 is obtained
(butt 30wt%, the molar ratio of nitric acid and small porous aluminum oxide are placed in mixed grind in roller for 0.3) 133 grams, are pressed into paste, extrusion
Shaping, and when 110 DEG C of dryings 4 are small, then when 550 DEG C of roastings 4 are small, reference catalyst CD1 is obtained, physico-chemical property is shown in Table
5。
Comparative example 6
Reference catalyst CE1 is prepared by the method for CN101450320A embodiments 4, physico-chemical property is shown in Table 5.
The physico-chemical property of 5 catalyst of table
Embodiment 13
The catalyst containing composite molecular screen and the Activity evaluation of reference catalyst that the present embodiment introduction is prepared by the present invention.
It is vacuum distillate (GVO) to evaluate the raw material used, and property is listed in table 6.Evaluation is on the fixed bed hydrogenation cracking unit of 200ml
It carries out, evaluation condition is：React stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1500:1, volume space velocity 1.67h-1.Evaluation result is listed in
Table 7.
6 vacuum distillate of table (VGO) main character
7 COMPARATIVE CATALYST's evaluation result of table
* engler is fractionated result
From evaluation result as can be seen that the catalyst of the invention containing composite molecular screen is evaporated applied to the decompression that processing height inferior is done
Divide oily (VGO), under identical process conditions, the catalyst of the invention containing composite molecular screen is high compared with reference agent lytic activity, stone
Naphtha yield is high, and liquid product yield is high.
Claims (17)
1. a kind of carrier of the sieve containing bimolecular, it is characterised in that：The carrier is by modified Y molecular sieve, SBA-15 molecular sieves and oxygen
Change aluminium composition, in terms of the vehicle weight sieved containing bimolecular, modified Y molecular sieve accounts for 48.5wt% ~ 89.9wt%, and SBA-15 molecular sieves account for
0.1wt% ~ 1.5wt%, aluminium oxide account for 10wt% ~ 50wt%, and the specific surface area of the carrier of the sieve containing bimolecular is 280 ~ 480m2/
G, pore volume are 0.32 ~ 0.52ml/g, and the property of the modified Y molecular sieve is as follows：Relative crystallinity 90 ~ 110%, lattice constant
2.435 ~ 2.446nm, 750 ~ 850m of specific surface2/ g, 0.40 ~ 0.50ml/g of total pore volume, silica alumina ratio 8 ~ 20, meleic acid amount
0.8~1.2mmol/g；The property of the SBA-15 molecular sieves is as follows：4.6 ~ 30nm of aperture, pore volume >=0.75ml/g, specific surface area
600~900m2/g。
2. carrier according to claim 1, it is characterised in that：The property of the SBA-15 molecular sieves is as follows：Aperture 6 ~
20nm, pore volume >=0.8ml/g, specific surface area are 650 ~ 850m2/g。
3. a kind of catalyst of the sieve containing bimolecular, it is characterised in that：The catalyst by modified Y molecular sieve, SBA-15 molecular sieves,
Aluminium oxide and hydrogenation active metals composition, the hydrogenation active component are group VIB metal and group VIII metal, and group VIB is golden
Belong to for molybdenum and/or tungsten, group VIII metal is cobalt and/or nickel, in terms of the weight of catalyst, modified Y molecular sieve account for 28.5wt% ~
74.9wt%, SBA-15 mesopore molecular sieve account for 0.1wt% ~ 1.5wt%；Group VIB metal accounts for 10.0 ~ 25.0wt% based on oxide,
Group VIII metal accounts for 3.0 ~ 8.0wt% based on oxide, and aluminium oxide meter accounts for 10 ~ 30wt%, and the specific surface area of catalyst is 260 ~
450m2/ g, pore volume are 0.25 ~ 0.50ml/g, and the property of the modified Y molecular sieve is as follows：Relative crystallinity 90 ~ 110%, structure cell
2.435 ~ 2.446nm of constant, 750 ~ 850m of specific surface2/ g, 0.40 ~ 0.50ml/g of total pore volume, silica alumina ratio 8 ~ 20, meleic acid
Measure 0.8 ~ 1.2mmol/g；The property of the SBA-15 molecular sieves is as follows：4.6 ~ 30nm of aperture, pore volume >=0.75ml/g, specific surface
600 ~ 900m of product2/g。
4. catalyst according to claim 3, it is characterised in that：The property of the SBA-15 molecular sieves is as follows：Aperture 6 ~
20nm, pore volume >=0.8ml/g, specific surface area are 650 ~ 850m2/g。
5. the preparation method of the sieve carrier containing bimolecular described in claim 1, it is characterised in that：Including following content：It will be Y points modified
Son sieve, do not burn made from the SBA-15 molecular sieves of template and dilute nitric acid solution peptized alumina adhesive carry out mechanical mixture,
It rolls, be molded, then dry, roasting obtains the carrier of the sieve containing bimolecular.
6. preparation method according to claim 5, it is characterised in that：The modified Y molecular sieve is with NH4NaY molecular sieve is
Raw material is made via hydrothermal dealumination and chemical dealuminization modifying process.
7. preparation method according to claim 5, it is characterised in that：SBA-15 molecular sieves use triblock copolymer
P123 is template, using positive esters of silicon acis as silicon source, the SBA-15 for not roasting template of hydrothermal synthesis out under acid condition
Molecular sieve.
8. preparation method according to claim 6, it is characterised in that：The preparation of the modified Y molecular sieve includes as follows
Step：
（1）Commercially available NH4NaY molecular sieve raw material is placed in hydro-thermal process stove, and hydro-thermal process temperature is risen to 500 ~ 750 DEG C；
Control system pressure is in 0.01 ~ 0.3MPa, PNH3/(PNH3+PH2O)≥0.1；When progress hydrothermal dealumination 0.5 ~ 5 is small；
（2）To step（1）Obtained material is used containing H+And NH4 +Mixed solution carry out chemical dealuminization, dealuminzation condition is：H+And NH4 +Mixed solution and step（1）The weight ratio of obtained material is 5:1~15:1, H+Concentration be 0.1 ~ 1mol/L, NH4 +Concentration
For 0.2 ~ 2mol/L；60 ~ 130 DEG C of temperature；When time 0.2 ~ 5 is small；Then filter, wash to pH >=6.5, filter cake is 100 ~ 120
It is DEG C dry to butt >=80%, obtain modified Y molecular sieve.
9. preparation method according to claim 8, it is characterised in that：Step（1）It is middle commercially available NH4NaY molecular sieve raw material
It is placed in hydro-thermal process stove, hydro-thermal process temperature is risen to 550 ~ 700 DEG C；Control system pressure 0.05 ~ 0.15MPa, PNH3/
(PNH3+PH2O)=0.2~0.5；When progress hydrothermal dealumination 1 ~ 3 is small.
10. preparation method according to claim 8, it is characterised in that：Step（2）In to step（1）Obtained material is used
Containing H+And NH4 +Mixed solution carry out chemical dealuminization, dealuminzation condition is：80 ~ 100 DEG C of temperature；When time 0.5 ~ 2 is small.
11. the preparation method of the sieve catalyst containing bimolecular described in claim 3, it is characterised in that：Including following content：It will be modified
Made from Y molecular sieve, the SBA-15 mesopore molecular sieves for not burning template, hydrogenation active metals and dilute nitric acid solution peptized alumina
Adhesive carries out mechanical mixture, rolls, extruded moulding, and then dry, roasting obtains the catalyst of the sieve containing bimolecular.
12. preparation method according to claim 11, it is characterised in that：The modified Y molecular sieve is with NH4NaY molecular sieve
It is made for raw material via hydrothermal dealumination and chemical dealuminization modifying process.
13. preparation method according to claim 11, it is characterised in that：SBA-15 molecular sieves use triblock copolymer
P123 is template, using positive esters of silicon acis as silicon source, the SBA-15 for not roasting template of hydrothermal synthesis out under acid condition
Molecular sieve.
14. preparation method according to claim 11, it is characterised in that：The preparation of the modified Y molecular sieve is included such as
Lower step：
（1）Commercially available NH4NaY molecular sieve raw material is placed in hydro-thermal process stove, and hydro-thermal process temperature is risen to 500 ~ 750 DEG C；
Control system pressure is in 0.01 ~ 0.3MPa, PNH3/(PNH3+PH2O)≥0.1；When progress hydrothermal dealumination 0.5 ~ 5 is small；
（2）To step（1）Obtained material is used containing H+And NH4 +Mixed solution carry out chemical dealuminization, dealuminzation condition is：H+And NH4 +Mixed solution and step（1）The weight ratio of obtained material is 5:1~15:1, H+Concentration be 0.1 ~ 1mol/L, NH4 +Concentration
For 0.2 ~ 2mol/L；60 ~ 130 DEG C of temperature；When time 0.2 ~ 5 is small；Then filter, wash to pH >=6.5, filter cake is 100 ~ 120
It is DEG C dry to butt >=80%, obtain modified Y molecular sieve.
15. preparation method according to claim 14, it is characterised in that：Step（1）It is middle commercially available NH4NaY molecular sieve is former
Material is placed in hydro-thermal process stove, and hydro-thermal process temperature is risen to 550 ~ 700 DEG C；Control system pressure 0.05 ~ 0.15MPa, PNH3/
(PNH3+PH2O)=0.2~0.5；When progress hydrothermal dealumination 1 ~ 3 is small.
16. preparation method according to claim 14, it is characterised in that：Step（2）In to step（1）Obtained material is used
Containing H+And NH4 +Mixed solution carry out chemical dealuminization, dealuminzation condition is：80 ~ 100 DEG C of temperature；When time 0.5 ~ 2 is small.
17. catalyst described in claim 3 does inferior distillate oil for working process height.
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