CN108067290B - Carrier and catalyst containing bimolecular sieve, and preparation method and application thereof - Google Patents
Carrier and catalyst containing bimolecular sieve, and preparation method and application thereof Download PDFInfo
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- CN108067290B CN108067290B CN201611011394.6A CN201611011394A CN108067290B CN 108067290 B CN108067290 B CN 108067290B CN 201611011394 A CN201611011394 A CN 201611011394A CN 108067290 B CN108067290 B CN 108067290B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 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 116
- 239000002808 molecular sieve Substances 0.000 claims abstract description 115
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000011148 porous material Substances 0.000 claims description 46
- 238000010335 hydrothermal treatment Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 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 12
- 239000012065 filter cake Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- 229920000428 triblock copolymer Polymers 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 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
- 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
- 238000004517 catalytic hydrocracking Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 13
- 238000004523 catalytic cracking Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 16
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 238000005336 cracking Methods 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 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
- 239000011959 amorphous silica alumina Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000002739 metals Chemical class 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
- 238000000967 suction filtration Methods 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
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000000203 mixture Substances 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
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- -1 ammonium hexafluorosilicate Chemical compound 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
- 239000007853 buffer solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000010771 distillate fuel oil Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 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
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000013598 vector 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
Abstract
The invention provides a carrier containing a bimolecular sieve, a catalyst, a preparation method and application thereof. The carrier is characterized in that the carrier is composed of 48.5wt% -89.9 wt% of modified Y molecular sieve, 0.1wt% -1.5 wt% of SBA-15 molecular sieve and 10wt% -50 wt% of alumina. The catalyst is characterized in that the modified Y molecular sieve accounts for 28.5-74.9 wt% of the weight of the catalyst, and the SBA-15 mesoporous molecular sieve accounts for 0.1-1.5 wt%; the VIB group metal accounts for 10.0-25.0 wt% of the oxide, the VIII group metal accounts for 3.0-8.0 wt% of the oxide, and the alumina accounts for 10-30 wt%. The carrier is particularly suitable for preparing light oil type hydrocracking catalysts, and has high catalytic cracking activity and high target product selectivity.
Description
Technical Field
The invention relates to a carrier and a catalyst containing a bimolecular sieve, and a preparation method and application thereof, in particular to a carrier and a catalyst containing a bimolecular sieve, a preparation method thereof, and application thereof in producing light distillate oil.
Technical Field
Along with the gradual realization of Chinese dream, the living quality of people is higher and higher, and the requirement on light fuel oil is increased day by day and the requirement on clean fuel oil is also more and more strict. The quantity and quality of primary processing of petroleum can not meet the requirements of people, the heavy distillate oil is converted into high-quality light fuel through secondary processing of a hydrocracking process, limited petroleum resources are fully utilized, the market demand of the light distillate oil is relieved, and the product quality is high and environment-friendly. The key point of the hydrocracking technology is the hydrocracking catalyst, and the quality of the catalyst carrier determines the activity of the catalyst, the selectivity of a target product and the quality of the product.
The carrier is a dispersed place for loading the acidic cracking component and providing the hydrogenation active component for the hydrocracking catalyst, and is a reaction platform for triggering a cracking reaction by connecting reactants and active sites and carrying out hydrogenation saturation on the products in a hydrogenation center.
CN101618347A discloses a hydrocracking catalyst carrier containing Y molecular sieve. The carrier consists of a modified Y molecular sieve and alumina. The Y-type molecular sieve is obtained by treating a mixed aqueous solution of aluminum salt and acid with a hydrothermal treatment, and has the following properties: specific surface area is 750-850 m2The total pore volume is 0.35-0.48 ml/g, the relative crystallinity is 90-130%, the unit cell constant is 2.437-2.445 nm, the molar ratio of silicon to aluminum is 15-70, the infrared acid content is 0.5-1.0 mmol/g, the B acid/L acid content is more than 7.0, and the sodium oxide content is less than or equal to 0.05 wt%. The catalyst carrier contains 30-70% of modified molecular sieve and 30-70% of alumina (based on the weight of the carrier); large pore volume and high specific surface area. The carrier used for preparing the hydrocracking catalyst has the characteristics of good catalytic activity, high heavy naphtha selectivity, high heavy naphtha aromatic hydrocarbon potential content and the like, but can discharge fluorine-containing byproducts when the modified Y molecular sieve is prepared, is not environment-friendly, and C5 +The liquid yield is not high.
US4,672,048 describes a light oil hydrocracking catalyst using a molecular sieve of LZ-210, the SiO of which2/Al2O3The molar ratio is preferably 11-15, and the preparation method comprises the following steps: treatment of NH in acidic buffer solution with ammonium hexafluorosilicate4The NaY molecular sieve, fluorine-containing by-product enters into liquid phase, sodium in the product LZ-210 and solution reach balance, so the content of LZ-210 sodium is higher, generally about 0.5w%, if low sodium content is obtained, further ammonium exchange is needed. The catalyst has high light oil selectivity and nitrogen resistance, but the activity of the catalyst is not very high.
CN101269343A discloses a composite mesoporous molecular sieve hydrocracking catalyst. The catalyst consists of 20-50% of amorphous silica-alumina, 5-30% of alumina, 10-20% of an adhesive, 10-40% of VIB group metal (Mo and/or W) oxide, 1-20% of VIII group metal (Co and/or Ni) oxide, 0.1-10% of VA group nonmetal (P) oxide and 1-40% of a composite mesoporous molecular sieve; the composite mesoporous molecular sieve is a mesoporous molecular sieve AlSBA-15 and/or AlSBA-15/Y composite molecular sieve. Because the AlSBA-15/Y composite molecular sieve is formed by modifying SBA-15 by using a mixed solution of aluminum isopropoxide and hydrochloric acid and then mixing NH4Preparing the Y molecular sieve. SBA-15 is weak in acidity after being modified by mixed solution of aluminum isopropoxide and hydrochloric acid, and prepared NH4The Y molecular sieve has high sodium oxide content, low acidity and poor thermal stability; the AlSBA-15/Y composite molecular sieve is used as an acid cracking component of a hydrocracking catalyst, so that the cracking activity of the catalyst is poor, and the thermal and hydrothermal stability of the catalyst is poor.
CN101590424A introduces a distillate oil hydrogenation catalyst and a preparation method thereof. The distillate oil hydrogenation catalyst comprises the following components in percentage by weight: the catalyst does not contain an acidic cracking component and is a hydrofining catalyst.
CN103769194A discloses a hydrogenation dearomatization catalyst and a preparation method thereof. The catalyst comprises a main active component of Pt, an auxiliary component of Pd, a carrier of amorphous silica-alumina and an SBA-15/Y composite molecular sieve, wherein the catalyst is based on the weight, the content of Pt is 0.1-0.5 wt%, the content of Pd is 0.3-0.8 wt%, the content of amorphous silica-alumina is 50-90 wt%, the content of SBA-15/Y composite molecular sieve is 5-20 wt%, and the content of an adhesive is 9-30 wt%; the weight content of the Y-type molecular sieve in the SBA-15/Y composite molecular sieve is 50-90 wt%; the properties of the SBA-15/Y composite molecular sieve used are as follows: SiO 22/A12O3The molar ratio is 40-85, and the specific surface area is 400m2/g～1000m2Per g, pore volume of 0.5cm3/g～2.0cm3The infrared acidity is 0.3-0.6 mmol/g. The preparation process of the catalyst is as follows: mixing, kneading, molding, drying and roasting the SBA-15/Y composite molecular sieve, amorphous silica-alumina and an adhesive to obtain a catalyst carrier; pd and Pt are loaded on a catalyst carrier by an impregnation method, and then the hydrogenation dearomatization catalyst is obtained by drying and roasting. The SBA-15/Y composite molecular sieve is prepared by the following method, (a) adding a silicon source into an acid solution, and stirring until the silicon source is changed into a transparent solution; (b) dissolving a cationic surfactant in water and uniformly stirring; (c) y type is divided intoCarrying out hydrothermal treatment on the sub-sieve, wherein the hydrothermal treatment temperature is 350-650 ℃, the pressure is 0.5-3.0 MPa, and the reaction time is 1-6 hours; and (d) adding the solution obtained in the step (a) into the mixed solution containing the cationic surfactant obtained in the step (b), stirring, adding the molecular sieve obtained in the step (c), uniformly mixing, performing hydrothermal treatment at 70-150 ℃ for 24-72 hours, filtering, washing, and drying to obtain the mesoporous-microporous composite molecular sieve. Although the SBA-15/Y composite molecular sieve has a mesoporous structure as a whole, the matching degree between the mesoporous SBA-15-micropore Y of different pore channels in the composite molecular sieve is poor, the material transmission is not facilitated, the pore channels of the SBA-15/Y composite molecular sieve and amorphous silicon-aluminum cannot be connected, the channel function cannot be really realized, and in addition, the problems of complex preparation process, high cost and the like exist.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a carrier and a catalyst containing a bimolecular sieve, and a preparation method and application thereof. The carrier is particularly suitable for preparing light oil type hydrocracking catalysts, and has high catalytic cracking activity and high target product selectivity.
The carrier containing the double molecular sieve comprises 48.5-89.9 wt% of modified Y molecular sieve, 0.1-1.5 wt% of SBA-15 molecular sieve, 10-50 wt% of alumina and 280-480 m of specific surface area of the carrier containing the double molecular sieve2The specific molecular weight of the modified Y molecular sieve is as follows: relative crystallinity of 90-110%, unit cell constant of 2.435-2.446 nm, and specific surface area of 750-850 m2The total pore volume is 0.40-0.50 ml/g, the molar ratio of silicon to aluminum is 8-20, and the infrared acid content is 0.8-1.2 mmol/g; the properties of the SBA-15 molecular sieve are as follows: the pore diameter is 4.6-30 nm, preferably 6-20 nm, the pore volume is more than or equal to 0.75ml/g, preferably more than or equal to 0.8ml/g, and the specific surface is 600-900 m2Preferably 650 to 850 m/g2/g。
A catalyst containing bimolecular sieve is composed of modified Y molecular sieve, SBA-15 molecular sieve, alumina and hydrogenation active metal, wherein the hydrogenation active component is VIB familyThe catalyst comprises metals and VIII family metals, wherein the VIB family metals are molybdenum and/or tungsten, the VIII family metals are cobalt and/or nickel, and based on the weight of the catalyst, the modified Y molecular sieve accounts for 28.5-74.9 wt%, and the SBA-15 mesoporous molecular sieve accounts for 0.1-1.5 wt%; the VIB group metal accounts for 10.0-25.0 wt% of the oxide, the VIII group metal accounts for 3.0-8.0 wt% of the oxide, the alumina accounts for 10-30 wt%, and the BET specific surface area of the catalyst is 260-450 m2The pore volume is 0.25-0.50 ml/g, and the modified Y molecular sieve has the following properties: relative crystallinity of 90-110%, unit cell constant of 2.435-2.446 nm, and specific surface area of 750-850 m2The total pore volume is 0.40-0.50 ml/g, the molar ratio of silicon to aluminum is 8-20, and the infrared acid content is 0.8-1.2 mmol/g; the properties of the SBA-15 molecular sieve are as follows: the pore diameter is 4.6-30 nm, preferably 6-20 nm, the pore volume is more than or equal to 0.75ml/g, preferably more than or equal to 0.8ml/g, and the specific surface is 600-900 m2Preferably 650 to 850 m/g2/g。
In the invention, the modified Y molecular sieve is NH4The NaY molecular sieve is prepared by taking a raw material through hydrothermal dealumination and chemical dealumination modification processes. The SBA-15 molecular sieve is a pure silicon mesoporous molecular sieve which is hydrothermally synthesized by taking a triblock copolymer P123 as a template agent and taking orthosilicate as a silicon source under an acidic condition
The preparation method of the carrier containing the bimolecular sieve comprises the following steps: mechanically mixing, rolling and forming the modified Y molecular sieve, the SBA-15 molecular sieve of the unfired template agent and an adhesive prepared by peptizing alumina by dilute nitric acid solution, and then drying and roasting to obtain the carrier containing the double molecular sieve.
The preparation method of the catalyst containing the bimolecular sieve comprises the following steps: mechanically mixing, rolling, extruding, forming, drying and roasting the modified Y molecular sieve, the SBA-15 mesoporous molecular sieve of the unfired template agent, the hydrogenation active metal and the adhesive prepared by peptizing alumina with dilute nitric acid solution to obtain the catalyst containing the double molecular sieve.
In the invention, the preparation of the modified Y molecular sieve comprises the following steps:
(1) adding commercially available NH4NaY molecular sieve (the relative crystallinity is more than or equal to 90 percent, the unit cell constant is 2.466-2.470 nm, SiO)2/Al2O3≥5.0，Na2O is less than or equal to 2.5w%, and the dry basis is 75-90%), placing the raw materials in a hydrothermal treatment furnace, and raising the hydrothermal treatment temperature to 500-750 ℃, preferably 550-700 ℃; controlling the system pressure (partial pressure of water vapour P)H2OAnd partial pressure P of ammoniaNH3Sum) of 0.01 to 0.3MPa, preferably 0.05 to 0.15MPa, PNH3/(PNH3+PH2O) Not less than 0.1, preferably PNH3/(PNH3+PH2O) = 0.2-0.5; carrying out hydrothermal dealumination for 0.5-5 hours, preferably 1-3 hours;
(2) h is used for the material obtained in the step (1)+And NH4 +The mixed solution is subjected to chemical dealumination, and the dealumination conditions are as follows: h+And NH4 +The weight ratio of the mixed solution to the material obtained in the step (1) is 5: 1-15: 1, and H is+The concentration of (A) is 0.1-1 mol/L, NH4 +The concentration of (A) is 0.2-2 mol/L; the temperature is 60-130 ℃, and preferably 80-100 ℃; the time is 0.2 to 5 hours, preferably 0.5 to 2 hours; and then filtering, washing until the pH value is more than or equal to 6.5, and drying a filter cake at 100-120 ℃ until the dry basis is more than or equal to 80% to obtain the modified Y molecular sieve.
The catalyst containing the double molecular sieve is used for processing and treating high-dry-point inferior distillate oil, and can obtain high catalytic cracking activity and high target product selectivity.
The modified Y molecular sieve adopted by the invention is NH4The method comprises the following steps of (1) properly dealuminizing a NaY molecular sieve serving as a raw material through hydrothermal dealumination and chemical dealumination modification processes, and adjusting the acid center concentration and the acid strength of the molecular sieve and the distribution of B acid and L acid; the framework Si/Al of the molecular sieve is improved, so that unit cells shrink, and the stability of the molecular sieve is improved; meanwhile, abundant secondary mesopores are generated, so that the adsorption and desorption performances of the molecular sieve are improved, the diffusion resistance of reactants and products is reduced, and the reaction rate is increased; thereby having higher catalytic cracking performance. The SBA-15 molecular sieve adopted by the invention is a pure silicon mesoporous molecular sieve synthesized by hydrothermal reaction under an acidic condition by using a triblock copolymer P123 as a template agent and using orthosilicate as a silicon source. Adding a small amount of SBA-15 molecular sieve raw powder which does not provide catalytic activity into the catalyst, and enabling the components in the catalyst to be mixed on the premise of not influencing the activity of the catalystThe pore channels are effectively connected, the template agent in the pore channels of the SBA-15 molecular sieve is removed by roasting at the end of the catalyst preparation process, so that the pore channels become smooth, a plurality of micropores with the size of 1-3 nm are generated on the pore walls of the SBA-15 and can be well matched with the pore channels of the modified Y molecular sieve, and the diffusion resistance of reactants and products is favorably reduced. SBA-15 is equivalent to 'paving and bridging' in a catalytic material body phase, the probability and the speed of contacting macromolecular reactants with an active site of a catalytic material through a large pore channel of an SBA-15 molecular sieve are greatly improved, and the reaction activity of the catalytic material is improved; in addition, the product generated by the reaction can be quickly diffused away through a road bridge, so that excessive reaction is avoided, and the liquid yield of the product is improved.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the present invention, and the following examples and comparative examples are given by mass% unless otherwise specified.
Example 1
Taking commercially available NH4NaY molecular sieve (relative crystallinity 92%, unit cell constant 2.469nm, SiO)2/Al2O3=5.1，Na2O =2.5w%, dry basis is 80%), 300g is put into a hydrothermal treatment furnace, the temperature is raised by electricity, the hydrothermal treatment temperature is raised to 580 ℃, and the system pressure (partial pressure P of water vapor) is controlledH2OAnd partial pressure P of ammoniaNH3Sum) of 0.1MPa, PNH3/(PNH3+PH2O) = 0.25; the hydrothermal treatment was carried out for 2.5 hours. Taking 100g of molecular sieve sample after hydrothermal treatment by using 0.3M nitric acid and 1.8M NH4NO3And (3) carrying out chemical dealumination reaction on 0.8L of the mixed solution at the temperature of 95 ℃ for 1.5 hours, carrying out suction filtration, repeatedly carrying out reaction once under the same condition, washing a filter cake until the pH of the filtrate is =6.8, and drying the filter cake at the temperature of 120 ℃ until the dry basis is =80% to obtain the modified Y molecular sieve A. The A properties were measured as follows: relative crystallinity of 97%, unit cell constant of 2.441nm, specific surface 786m2Per g, total pore volume 0.44ml/g, Si/Al molar ratio 12.7, Na2O =0.11w%, infrared acid amount 1.09 mmol/g.
Example 2
Taking commercially available NH4NaY molecular sieve (relative crystallinity 92%, unit cell constant 2.469nm, SiO)2/Al2O3=5.1，Na2O =2.5w%, 80% dry basis) 600g was placed in a hydrothermal treatment furnace, the temperature was raised by supplying electricity, the hydrothermal treatment temperature was raised to 630 ℃, and the system pressure (partial pressure P of water vapor) was controlledH2OAnd partial pressure P of ammoniaNH3Sum) of 0.08MPa, PNH3/(PNH3+PH2O) = 0.3; the hydrothermal treatment was carried out for 2.0 hours. 200g of the molecular sieve sample after hydrothermal treatment was treated with 0.1M nitric acid and 2.0M NH4NO3And (3) carrying out chemical dealumination reaction on 2L of the mixed solution at 90 ℃ for 1.0 hour, carrying out suction filtration, repeating the reaction twice under the same condition, washing a filter cake until the pH of the filtrate is =6.5, and drying the filter cake at 120 ℃ until the dry basis is =80% to obtain the modified Y molecular sieve B. The B properties were measured as follows: relative crystallinity 95%, unit cell constant 2.439nm, specific surface 775m2Per g, total pore volume 0.46ml/g, Si/Al molar ratio 13.6, Na2O =0.09w%, infrared acid amount 1.05 mmol/g.
Comparative example 1
The modified Y molecular sieve C is prepared according to the method described in Chinese patent 90102645. X. The C properties were measured as follows: relative crystallinity of 97%, unit cell constant of 2.450nm, specific surface 775m2Per g, total pore volume 0.38ml/g, Si/Al molar ratio 10.7, Na2O =0.03w%, infrared acid amount 1.12 mmol/g.
Example 3
300g of pure silicon mesoporous molecular sieve SBA-15 raw powder which is prepared by hydrothermal synthesis under acidic conditions by using a commercially available triblock copolymer P123 as a template agent and using orthosilicate as a silicon source is taken as the mesoporous molecular sieve D used by the invention. The properties (measured after the template agent is removed by roasting) were measured as follows: the pore diameter is 11.2nm, the pore volume is more than or equal to 0.82ml/g, and the specific surface is 783m2/g。
Example 4
74.1 g (dry basis 80wt%) of the modified Y molecular sieve A obtained in example 1, 0.9 g of the unfired mesoporous molecular sieve D obtained in example 3 and 66 g of a binder (dry basis 30wt%, molar ratio of nitric acid to small-pore alumina is 0.3) are mixed and ground in a rolling machine, pressed into a paste, extruded into strips, dried at 110 ℃ for 4 hours and then calcined at 560 ℃ for 4 hours to obtain a catalyst carrier ZA, and the physicochemical properties of the catalyst carrier ZA are shown in Table 1.
Example 5
207 g of the modified Y molecular sieve B obtained in example 2 (dry basis: 80wt%), 0.5 g of the mesoporous molecular sieve D obtained in example 3 and 100g of a binder (dry basis: 30wt%, molar ratio of nitric acid to small-pore alumina: 0.3) were mixed and milled in a roll mill, pressed into a paste, extruded into a strip, and dried at 110 ℃ for 4 hours, and then calcined at 560 ℃ for 4 hours to obtain a catalyst carrier ZB, the physicochemical properties of which are shown in Table 1.
Comparative example 2
97.5 g (dry basis 80wt%) of the modified Y molecular sieve C obtained in comparative example 1 and 66 g of a binder (dry basis 30wt%, molar ratio of nitric acid to the small-pore alumina is 0.3) were mixed and milled in a roll mill, pressed into a paste, extruded into strips, dried at 110 ℃ for 4 hours, and then calcined at 550 ℃ for 4 hours to obtain a catalyst carrier ZC, the physicochemical properties of which are shown in Table 1.
Comparative example 3
The physical and chemical properties of catalyst support ZD prepared according to CN101618347A in example 4 are shown in Table 1.
TABLE 1 physicochemical Properties of the vectors
Example 6
Respectively using a catalyst containing WO345.82g/100ml, NiO 11.49g/100ml ammonium metatungstate, nickel nitrate mixed solution impregnation of the carrier ZA obtained in example 4, the carrier ZB obtained in example 5, the carrier ZC obtained in comparative example 2 and the carrier ZD obtained in comparative example 3, the volume ratio of the impregnation solution to the carrier being 2:1, filtering off the excessive impregnation solution, drying at 105 ℃, and calcining at 500 ℃ to obtain the corresponding catalysts CA, CB, CC and CD. The physicochemical properties are shown in Table 2.
TABLE 2 physicochemical Properties of the catalyst
Example 7
This example presents the results of activity evaluation of a catalyst prepared by impregnating a hydrogenation metal component with a support according to the invention. The feedstock used was evaluated as vacuum distillate (GVO) and the properties are given in Table 3. The evaluation was carried out on a 200ml fixed bed hydrocracking unit under the following conditions: the total reaction pressure is 14.7MPa, the volume ratio of hydrogen to oil is 1500:1, and the volume space velocity is 1.67h-1. The evaluation results are shown in Table 4.
TABLE 3 Main Properties of vacuum distillates (VGO)
TABLE 4 comparative evaluation results of catalysts
Results of the enrichments fractionation
From the evaluation results, the catalyst is used for treating the poor-quality high-dry-point Vacuum Gas Oil (VGO), and under the same process conditions, the catalyst obtained by impregnating hydrogenation metal with the carrier has high activity and high liquid yield. Therefore, the carrier of the invention is suitable for being used as a light oil type hydrocracking catalyst, and can obtain higher cracking activity and higher liquid yield.
Example 8
Taking commercially available NH4NaY molecular sieve (relative crystallinity 92%, unit cell constant 2.469nm, SiO)2/Al2O3=5.1，Na2O =2.5w%, dry basis is 80%), 300g is put into a hydrothermal treatment furnace, the temperature is raised by electricity, the hydrothermal treatment temperature is raised to 580 ℃, and the system pressure (partial pressure P of water vapor) is controlledH2OAnd partial pressure P of ammoniaNH3Sum) of 0.1MPa, PNH3/(PNH3+PH2O) = 0.25; the hydrothermal treatment was carried out for 2.5 hours. Taking 100g of molecular sieve sample after hydrothermal treatment by using 0.3M nitric acid and 1.8M NH4NO30.8L of mixed solution is subjected to chemical dealuminization reaction for 1.5 hours at the temperature of 95 ℃, suction filtration is carried out, and the reaction is repeated under the same conditionsOnce, the filter cake was washed to filtrate pH =6.8 and the filter cake was dried at 120 ℃ to dry basis =80% yielding modified Y molecular sieve a1 of the present invention. The a1 properties were measured as follows: relative crystallinity of 97%, unit cell constant of 2.441nm, specific surface 786m2Per g, total pore volume 0.44ml/g, Si/Al molar ratio 12.7, Na2O =0.11w%, infrared acid amount 1.09 mmol/g.
Example 9
Taking commercially available NH4NaY molecular sieve (relative crystallinity 92%, unit cell constant 2.469nm, SiO)2/Al2O3=5.1，Na2O =2.5w%, 80% dry basis) 600g was placed in a hydrothermal treatment furnace, the temperature was raised by supplying electricity, the hydrothermal treatment temperature was raised to 630 ℃, and the system pressure (partial pressure P of water vapor) was controlledH2OAnd partial pressure P of ammoniaNH3Sum) of 0.08MPa, PNH3/(PNH3+PH2O) = 0.3; the hydrothermal treatment was carried out for 2.0 hours. 200g of the molecular sieve sample after hydrothermal treatment was treated with 0.1M nitric acid and 2.0M NH4NO3And (3) carrying out chemical dealumination reaction on 2L of the mixed solution at 90 ℃ for 1.0 hour, carrying out suction filtration, repeating the reaction twice under the same condition, washing a filter cake until the pH of the filtrate is =6.5, and drying the filter cake at 120 ℃ until the dry basis is 80% to obtain the modified Y molecular sieve B1. The B1 properties were measured as follows: relative crystallinity 95%, unit cell constant 2.439nm, specific surface 775m2Per g, total pore volume 0.46ml/g, Si/Al molar ratio 13.6, Na2O =0.09w%, infrared acid amount 1.05 mmol/g.
Comparative example 4
The modified Y molecular sieve C1 was prepared according to the method described in Chinese patent No. 90102645. X. The C1 properties were measured as follows: relative crystallinity of 97%, unit cell constant of 2.450nm, specific surface 775m2Per g, total pore volume 0.38ml/g, Si/Al molar ratio 10.7, Na2O =0.03w%, infrared acid amount 1.12 mmol/g.
Example 10
300g of pure silicon mesoporous molecular sieve SBA-15 raw powder which is prepared by hydrothermal synthesis under acidic conditions by using a commercially available triblock copolymer P123 as a template agent and using orthosilicate as a silicon source is taken as the mesoporous molecular sieve D1 used by the invention. The properties (measured after the template agent is removed by roasting) were measured as follows: the pore diameter is 11.2nm, the pore volume is more than or equal to 0.82ml/g, and the specific surface is 783m2/g。
Example 11
The catalyst is based on Y: SBA-15: MoO3NiO is prepared according to the proportion of adhesive =0.591:0.009:0.2:0.05: 0.15. 1295.5 g (dry basis 80wt%) of the modified Y molecular sieve A obtained in example 8 and 13.6 g of the mesoporous molecular sieve D obtained in example 10 are mixed, 80 g of molybdenum oxide, 77.8 g of nickel nitrate and 200g of a binder (dry basis 30wt%, molar ratio of nitric acid to small-pore alumina is 0.3) are added and mixed in a rolling machine, and the mixture is pressed into paste, extruded into strips and molded, dried at 110 ℃ for 4 hours and then roasted at 550 ℃ for 4 hours to obtain the catalyst CA1 containing the composite molecular sieve, wherein the physicochemical properties of the catalyst CA1 are shown in Table 5.
Example 12
The catalyst is based on Y: SBA-15: MoO3NiO is prepared according to the proportion of 0.545:0.005:0.2:0.05: 0.15 of a binder. 1272.5 g of the modified Y molecular sieve B obtained in example 9 (80 wt% on a dry basis) and 12 g of the mesoporous molecular sieve D obtained in example 10 were mixed, 80 g of molybdenum oxide, 77.8 g of nickel nitrate and 267 g of a binder (30 wt% on a dry basis, the molar ratio of nitric acid to small-pore alumina is 0.3) were added, the mixture was mixed and milled in a mill, the mixture was pressed into a paste, and the paste was extruded into a bar and molded, and dried at 110 ℃ for 4 hours, and then calcined at 550 ℃ for 4 hours, so that the composite molecular sieve-containing catalyst CB1 of the present invention was obtained, and the physicochemical properties thereof are shown in Table 5.
Comparative example 5
128 g (dry basis 80wt%) of the modified Y molecular sieve C obtained in comparative example 4, 40 g of molybdenum oxide, 39 g of nickel nitrate and 133 g of a binder (dry basis 30wt% and molar ratio of nitric acid to small-pore alumina is 0.3) are mixed and ground in a rolling machine, pressed into a paste, extruded into strips, dried at 110 ℃ for 4 hours and then calcined at 550 ℃ for 4 hours to obtain a reference catalyst CD1, and the physicochemical properties of the reference catalyst CD1 are shown in Table 5.
Comparative example 6
Reference catalyst CE1 was prepared according to CN101450320A, example 4, and its physico-chemical properties are shown in Table 5.
TABLE 5 physicochemical Properties of the catalyst
Example 13
This example presents the results of activity evaluation of a composite molecular sieve containing catalyst prepared according to the present invention and a reference catalyst. The feedstock used was evaluated as vacuum distillate (GVO) and the properties are given in Table 6. The evaluation was carried out on a 200ml fixed bed hydrocracking unit under the following conditions: the total reaction pressure is 14.7MPa, the volume ratio of hydrogen to oil is 1500:1, and the volume space velocity is 1.67h-1. The evaluation results are shown in Table 7.
TABLE 6 Main Properties of vacuum distillates (VGO)
TABLE 7 comparative evaluation results of catalysts
Results of the enrichments fractionation
The evaluation results show that the catalyst containing the composite molecular sieve is applied to treating the poor vacuum distillate oil (VGO) with high dry point, and under the same process conditions, the catalyst containing the composite molecular sieve has high cracking activity, high naphtha yield and high liquid product yield compared with a reference agent.
Claims (17)
1. A carrier containing a bimolecular sieve is characterized in that: the carrier consists of a modified Y molecular sieve, an SBA-15 molecular sieve and alumina, wherein the modified Y molecular sieve accounts for 48.5-89.9 wt%, the SBA-15 molecular sieve accounts for 0.1-1.5 wt%, the alumina accounts for 10-50 wt%, and the specific surface area of the carrier containing the bimolecular sieve is 280-480 m2The specific molecular weight of the modified Y molecular sieve is as follows, wherein the pore volume is 0.32-0.52 mL/g: relative crystallinity of 90-110%, unit cell constant of 2.435-2.446 nm, and specific surface area of 750-850 m2The total pore volume is 0.40-0.50 mL/g, the molar ratio of silicon to aluminum is 8-20, and the infrared acid content is 0.8-1.2 mmol/g; the properties of the SBA-15 molecular sieve are as follows: the pore diameter is 4.6-30 nm, the pore volume is more than or equal to 0.75mL/g, and the specific surface area is 600-900 m2/g；
Wherein, the carrier is prepared by adopting an SBA-15 molecular sieve of an unfired template agent.
2. The carrier of claim 1, wherein: the properties of the SBA-15 molecular sieve are as follows: the pore diameter is 6-20 nm, the pore volume is more than or equal to 0.8mL/g, and the specific surface area is 650-850 m2/g。
3. A catalyst containing a bimolecular sieve is characterized in that: the catalyst consists of a modified Y molecular sieve, an SBA-15 molecular sieve, alumina and hydrogenation active metal, wherein the hydrogenation active components are VIB group metal and VIII group metal, the VIB group metal is molybdenum and/or tungsten, the VIII group metal is cobalt and/or nickel, based on the weight of the catalyst, the modified Y molecular sieve accounts for 28.5wt% -74.9 wt%, and the SBA-15 mesoporous molecular sieve accounts for 0.1wt% -1.5 wt%; the VIB group metal accounts for 10.0-25.0 wt% of the oxide, the VIII group metal accounts for 3.0-8.0 wt% of the oxide, the alumina accounts for 10-30 wt%, and the specific surface area of the catalyst is 260-450 m2The pore volume is 0.25-0.50 mL/g, and the modified Y molecular sieve has the following properties: relative crystallinity of 90-110%, unit cell constant of 2.435-2.446 nm, and specific surface area of 750-850 m2The total pore volume is 0.40-0.50 mL/g, the molar ratio of silicon to aluminum is 8-20, and the infrared acid content is 0.8-1.2 mmol/g; the properties of the SBA-15 molecular sieve are as follows: the pore diameter is 4.6-30 nm, the pore volume is more than or equal to 0.75mL/g, and the specific surface area is 600-900 m2/g；
Wherein, SBA-15 molecular sieve of the unfired template agent is adopted in the preparation of the catalyst.
4. The catalyst of claim 3, wherein: the properties of the SBA-15 molecular sieve are as follows: the pore diameter is 6-20 nm, the pore volume is more than or equal to 0.8mL/g, and the specific surface area is 650-850 m2/g。
5. The method for preparing the carrier containing the bimolecular sieve according to claim 1, which is characterized in that: the method comprises the following steps: mechanically mixing, rolling and forming the modified Y molecular sieve, the SBA-15 molecular sieve of the unfired template agent and an adhesive prepared by peptizing alumina by dilute nitric acid solution, and then drying and roasting to obtain the carrier containing the double molecular sieve.
6. The method of claim 5, wherein: the modified Y molecular sieve is NH4The NaY molecular sieve is prepared by taking a raw material through hydrothermal dealumination and chemical dealumination modification processes.
7. The method of claim 5, wherein: the SBA-15 molecular sieve adopts triblock copolymer P123 as a template agent, takes orthosilicate as a silicon source, and is hydrothermally synthesized under an acidic condition to obtain the SBA-15 molecular sieve of the unfired template agent.
8. The method of claim 6, wherein: the preparation of the modified Y molecular sieve comprises the following steps:
(1) adding commercially available NH4Placing a NaY molecular sieve raw material in a hydrothermal treatment furnace, and raising the hydrothermal treatment temperature to 500-750 ℃; the pressure of the system is controlled to be 0.01-0.3 MPa, PNH3/(PNH3+PH2O) Not less than 0.1; carrying out hydrothermal dealumination for 0.5-5 hours;
(2) h is used for the material obtained in the step (1)+And NH4 +The mixed solution is subjected to chemical dealumination, and the dealumination conditions are as follows: h+And NH4 +The weight ratio of the mixed solution to the material obtained in the step (1) is 5: 1-15: 1, and H is+The concentration of (A) is 0.1-1 mol/L, NH4 +The concentration of (A) is 0.2-2 mol/L; the temperature is 60-130 ℃; the time is 0.2-5 hours; and then filtering, washing until the pH value is more than or equal to 6.5, and drying a filter cake at 100-120 ℃ until the dry basis is more than or equal to 80% to obtain the modified Y molecular sieve.
9. The method of claim 8, wherein: step (1) of adding commercially available NH4Placing a NaY molecular sieve raw material in a hydrothermal treatment furnace, and raising the hydrothermal treatment temperature to 550-700 ℃; the pressure of the control system is 0.05-0.15 MPa, PNH3/(PNH3+PH2O) = 0.2-0.5; performing hydrothermal dealumination for 1-3 hours.
10. The method of claim 8, wherein: in the step (2), the material obtained in the step (1) contains H+And NH4 +The mixed solution is subjected to chemical dealumination, and the dealumination conditions are as follows: the temperature is 80-100 ℃; the time is 0.5 to 2 hours.
11. The method for preparing the catalyst containing the bimolecular sieve of claim 3, which is characterized in that: the method comprises the following steps: mechanically mixing, rolling, extruding, forming, drying and roasting the modified Y molecular sieve, the SBA-15 mesoporous molecular sieve of the unfired template agent, the hydrogenation active metal and the adhesive prepared by peptizing alumina with dilute nitric acid solution to obtain the catalyst containing the double molecular sieve.
12. The method of claim 11, wherein: the modified Y molecular sieve is NH4The NaY molecular sieve is prepared by taking a raw material through hydrothermal dealumination and chemical dealumination modification processes.
13. The method of claim 11, wherein: the SBA-15 molecular sieve adopts triblock copolymer P123 as a template agent, takes orthosilicate as a silicon source, and is hydrothermally synthesized under an acidic condition to obtain the SBA-15 molecular sieve of the unfired template agent.
14. The method of claim 11, wherein: the preparation of the modified Y molecular sieve comprises the following steps:
(1) adding commercially available NH4Placing a NaY molecular sieve raw material in a hydrothermal treatment furnace, and raising the hydrothermal treatment temperature to 500-750 ℃; the pressure of the system is controlled to be 0.01-0.3 MPa, PNH3/(PNH3+PH2O) Not less than 0.1; carrying out hydrothermal dealumination for 0.5-5 hours;
(2) h is used for the material obtained in the step (1)+And NH4 +Mixed solution of (2)Carrying out chemical dealumination on the solution, wherein the dealumination conditions are as follows: h+And NH4 +The weight ratio of the mixed solution to the material obtained in the step (1) is 5: 1-15: 1, and H is+The concentration of (A) is 0.1-1 mol/L, NH4 +The concentration of (A) is 0.2-2 mol/L; the temperature is 60-130 ℃; the time is 0.2-5 hours; and then filtering, washing until the pH value is more than or equal to 6.5, and drying a filter cake at 100-120 ℃ until the dry basis is more than or equal to 80% to obtain the modified Y molecular sieve.
15. The method of claim 14, wherein: step (1) of adding commercially available NH4Placing a NaY molecular sieve raw material in a hydrothermal treatment furnace, and raising the hydrothermal treatment temperature to 550-700 ℃; the pressure of the control system is 0.05-0.15 MPa, PNH3/(PNH3+PH2O) = 0.2-0.5; performing hydrothermal dealumination for 1-3 hours.
16. The method of claim 14, wherein: in the step (2), the material obtained in the step (1) contains H+And NH4 +The mixed solution is subjected to chemical dealumination, and the dealumination conditions are as follows: the temperature is 80-100 ℃; the time is 0.5 to 2 hours.
17. The catalyst of claim 3 is used for processing and treating high dry point inferior distillate oil.
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