CN107344106A - A kind of hydrocracking catalyst and preparation method thereof - Google Patents
A kind of hydrocracking catalyst and preparation method thereof Download PDFInfo
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- CN107344106A CN107344106A CN201610289568.9A CN201610289568A CN107344106A CN 107344106 A CN107344106 A CN 107344106A CN 201610289568 A CN201610289568 A CN 201610289568A CN 107344106 A CN107344106 A CN 107344106A
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- molecular sieve
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 57
- 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 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 14
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 14
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 14
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 105
- 239000002808 molecular sieve Substances 0.000 claims description 104
- 238000000034 method Methods 0.000 claims description 40
- 238000002425 crystallisation Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 27
- 230000008025 crystallization Effects 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 229910019975 (NH4)2SiF6 Inorganic materials 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 17
- 239000011959 amorphous silica alumina Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 238000009415 formwork Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 206010013786 Dry skin Diseases 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 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
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002283 diesel fuel Substances 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 6
- 239000000295 fuel oil Substances 0.000 abstract description 6
- 239000003921 oil Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 16
- 238000001354 calcination Methods 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 239000000446 fuel Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 101100224931 Caenorhabditis elegans dhc-1 gene Proteins 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003317 industrial substance Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001504664 Crossocheilus latius Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of hydrocracking catalyst and preparation method thereof.The hydrocracking catalyst is as follows as predominant cracking component, the property of the Modified Zeolite Y using a kind of Modified Zeolite Y concentrated rich in mesoporous, effective pore sife distribution：Relative crystallinity is 110% ~ 150%, SiO2/Al2O3Mol ratio is 55 ~ 100, and cell parameter is 2.425 ~ 2.435nm, and total pore volume is 0.55 ~ 1.0mL/g, and mesoporous pore volume accounts for more than the 70% of total pore volume.The catalyst is suitable as the hydrocracking catalyst for flexibly producing high-quality heavy naphtha, jet fuel and diesel oil, has higher activity and selectivity.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, particularly a kind of flexibly production heavy naphtha,
Hydrocracking catalyst of jet fuel and diesel oil and preparation method thereof.
Background technology
Hydrocracking technology be mainly characterized by adaptability to raw material is strong, products scheme flexibly, purpose product selectivity is high, production
Quality is good and added value height etc., can directly produce a variety of high-quality oil products（Such as gasoline, jet fuel, diesel oil, oil base is lubricated
Plinth oil etc.）With high-quality industrial chemicals（Such as raw materials for production of benzene,toluene,xylene, ethene）.Therefore, with crude quality by
The sustainable growth and new environmental regulation of year variation, market to high quality oil product and high-quality chemical industry raw materials requirement amount it is successive
Put into effect, the importance day aobvious protrusion of hydrocracking technology, application is also increasingly extensive, it has also become is rationally provided using limited oil
Source, to greatest extent production cleaning oil product and the optimum oil Refining Technologies of high-quality industrial chemicals, it is modern oil refining and oil
Oil, change, the fine core combined in work enterprise.
For hydrocracking catalyst, while catalyst activity is paid attention to, it is necessary to consider the selectivity of purpose product,
Therefore a relatively reasonable balance must be found in active this contradiction with the selectivity of purpose product of catalyst, with more
The performance of catalyst is played well.
The method of industrial production Y type molecular sieve is essentially all in the Hes of USP 3639099 using GRACE companies of the U.S. at present
The directing agent method proposed in USP 4166099, the orifice diameter in the Y type molecular sieve original powder duct of synthesis for 0.74nm ×
0.74nm, its micropore pore volume account for more than the 95% of total pore volume.Polycyclic restructuring fractionated molecule in wax oil hydrogenation cracked stock is straight
Footpath generally in more than 1nm, the cracking reaction for heavy constituent macromolecular, is adapted to the preferable duct aperture that it reacts and product spreads
Scope is 2nm ~ 10nm macropore range, can be exposed by more accessible acid centre, while is also divided greatly beneficial to raw material
The absorption of son and the desorption and diffusion of reaction and purpose product, improve molecular sieve cracking selectivity.It is situated between to improve Y type molecular sieve
The low situation for being unfavorable for wax oil macromolecular reaction of hole pore volume content, is generally modified processing to Y type molecular sieve original powder, can obtain
To the Modified Zeolite Y of different pore passage structures and acid distribution.
US4036739 discloses a kind of method of cracking hydrocarbons raw material production low boiling point hydrocarbon, wherein Y type molecular sieve used
Preparation method, when one section is handled at a temperature of 315 ~ 899 DEG C, and under conditions of being contacted with least 0.5Psi vapor
Between, the cell parameter for making Y type molecular sieve after processing is 2.440 ~ 2.464nm；Molecular sieve after processing is subjected to ammonium exchange, obtained
Sodium oxide content is less than 1wt% product；Then it is calcined again once at 315 ~ 899 DEG C, obtains cell parameter and be less than 2.440nm
Y type molecular sieve.The acid site of the Y type molecular sieve obtained using the above method is reduced, and crystallinity declines, and contains in molecular sieve
Substantial amounts of non-framework aluminum, so that the activity of the hydrocracking catalyst containing this Y type molecular sieve is not high.
US6174429 discloses a kind of hydrocracking catalyst, the catalyst contain at least one acidifying containing aluminium without fixed
Shape matrix, a kind of cell parameter are 2.438nm, SiO2/Al2O3Mol ratio is about 8, SiO2/Al2O3Framework mole ratio is about 20
Y type molecular sieve, at least one metal component of group VIII, at least one metal component of group VIB, auxiliary agent and the VIIth A of at least one
Race's element.The catalyst has preferably activity and stability, but jet fuel and diesel yield be not high.
CN201510147788.3 discloses Y molecular sieve that a kind of silica alumina ratio is high and second hole is abundant and preparation method thereof.
This method includes：Y type molecular sieve is handled into 1 ~ 5h at 300 DEG C ~ 600 DEG C, dry Y type molecular sieve is obtained, is cooled to 200 ~ 600
℃；In dried over anhydrous environment, it is passed through into dry Y type molecular sieve by the dry gas of dealumination complement silicon agent saturation, reaction
0.5h ~ 7h, or in dried over anhydrous environment, lead to while temperature to be at the uniform velocity warming up to 500 ~ 700 DEG C into dry y-type zeolite
Enter by the dry gas of dealumination complement silicon agent saturation, react 0.5h ~ 7h, obtain crude product；By crude product at 30 ~ 100 DEG C at alkali
10min ~ 5h is managed, the solid-liquid mass ratio of alkali process is 1 ~ 50：1, obtain the Y molecular sieve that silica alumina ratio is high and second hole is abundant.
From the molecular sieve with cracking function from the point of view of the application during Industrial Catalysis, its performance depends primarily on following
Two aspects：Selective absorption and reaction.When reactant molecule size is less than molecular sieve aperture and overcomes molecular sieve crystal surface
It energy barrier, can just diffuse into molecular sieve pore passage, specific catalytic reaction occurs, at this moment be adsorbed molecule and pass through molecular sieve crystal
Hole and cage diffusion serve it is conclusive.Molecular sieve total pore volume and mesoporous pore volume prepared by conventional method of modifying
It is less than normal, it is unfavorable for the conversion of raw material macromolecular, therefore the modification point that pore structure is open, mesoporous content is high and acid site exposure is more
Son sieve can handle the raw material that molecule is bigger, oil product is heavier, improve macromolecular conversion probability etc. show it is more superior
Performance, so as to lift the level of hydrocracking catalyst.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of hydrocracking catalyst and its preparation side
Method.The hydrocracking catalyst is using a kind of Modified Zeolite Y conduct more concentrated rich in meso-hole structure, effective pore sife distribution
Predominant cracking component, for flexibly producing high-quality heavy naphtha, jet fuel and diesel oil, there is good activity and selectivity.
The hydrocracking catalyst of the present invention, including hydrogenation active metal component and carrier, carrier include modified Y type molecules
Sieve, amorphous silica-alumina and aluminum oxide, wherein described Modified Zeolite Y, its property is as follows：Relative crystallinity be 110% ~
150%, SiO2/Al2O3Mol ratio is 55 ~ 100, and cell parameter is 2.425 ~ 2.435nm, and total pore volume is 0.55 ~ 1.0mL/g,
Preferably 0.6 ~ 1.0mL/g, mesoporous pore volume account for more than the 70% of total pore volume, preferably 80% ~ 95%.
The grain size of described Modified Zeolite Y is 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm.
In described Modified Zeolite Y, mesoporous bore dia is 2 ~ 10nm.
The specific surface area of described Modified Zeolite Y is 650 ~ 1000m2/ g, preferably 750 ~ 1000m2/g。
The infrared total acid content of described Modified Zeolite Y is 0.1 ~ 0.5mmol/g.
In described Modified Zeolite Y, Na2O weight content is below 0.15wt%.
In described hydrocracking catalyst, described carrier, on the basis of the weight of carrier, Modified Zeolite Y
Content is 10% ~ 50%, preferably 15% ~ 45%, and the content of amorphous silica-alumina is 5% ~ 30%, preferably 10% ~ 25%, and aluminum oxide contains
Measure as 20% ~ 85%, preferably 30% ~ 75%.
For described hydrogenation active metals typically using vib and the metal of group VIII, vib metals are preferably molybdenum
And/or tungsten, group VIII metal are preferably cobalt and/or nickel.In hydrocracking catalyst catalyst of the present invention, with the weight of catalyst
On the basis of amount, vib metals（In terms of oxide）Content be 10.0% ~ 30.0%, group VIII metal（In terms of oxide）
Content be 4.0% ~ 8.0%, the content of carrier is 62.0% ~ 86.0%.
The property of hydrocracking catalyst of the present invention is as follows：Specific surface area is 250 ~ 450m2/ g, pore volume be 0.30 ~
0.50mL/g。
The preparation method of hydrocracking catalyst of the present invention, include preparation and the load hydrogenation active metal component of carrier,
The preparation process of wherein carrier is as follows：By Modified Zeolite Y, amorphous silica-alumina, aluminum oxide mix, shaping, then dry and
Roasting, is made the preparation method of catalyst carrier, wherein Modified Zeolite Y, comprises the following steps：
（1）NaY types molecular sieve with（NH4）2SiF6Aqueous solution contact is reacted, through filtering and drying after reaction；
（2）To step（1）Gained Y type molecular sieve carries out hydro-thermal process；Hydrothermal conditions：Gauge pressure is 0.20 ~ 0.40MPa, temperature
Spend for 600 ~ 800 DEG C, processing time is 0.5 ~ 5.0 hour；
（3）By step（2）Gained Y type molecular sieve carries out hydrothermal crystallizing processing, Ran Houjing under the conditions of existing for organic formwork agent
Filter and dry；
（4）By step（3）The Y type molecular sieve of gained is calcined under low temperature oxygen-enriched atmosphere, and the modification Y type molecules of the present invention are made
Sieve.
The inventive method step（1）In, the property of NaY type molecular sieves is as follows：
SiO2/Al2O3Mol ratio be 3 ~ 6, preferably 4.5 ~ 5.5, grain size be 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm, relatively
Crystallinity is 80% ~ 110%, and cell parameter is 2.465 ~ 2.470nm, Na2O weight content is 6.0wt% ~ 8.0wt%, compares surface
Product is 600 ~ 900m2/ g, total pore volume are 0.3 ~ 0.4 mL/g, and micropore pore volume accounts for more than the 75% of total pore volume.
The inventive method step（1）In,（NH4）2SiF6Addition for NaY type molecular sieve butt weight 5wt% ~
20wt%。
The inventive method step（1）In,（NH4）2SiF6The mass concentration of the aqueous solution is 50 ~ 100g/L.NaY type molecular sieves
With（NH4）2SiF6The reaction condition that aqueous solution contact is reacted：Temperature is 80 ~ 150 DEG C, preferably 90 ~ 120 DEG C, during reaction
Between be 0.1 ~ 5.0 hour, preferably 1.0 ~ 3.0 hours.
The inventive method step（1）In, NaY types molecular sieve with（NH4）2SiF6After aqueous solution contact is reacted, separation point
Son sieve and accessory substance, can wash, refilter, dry, preferably dry after gained Y type molecular sieve butt for 60wt% ~
80wt%.Dry condition is usually to be dried 0.5 ~ 5.0 hour at 50 ~ 95 DEG C.
The inventive method step（2）In, hydro-thermal process is to use saturated steam processing step（1）In obtained molecular sieve,
Treatment conditions：0.20 ~ 0.40MPa of gauge pressure, preferably 0.25 ~ 0.40MPa, preferably 600 ~ 800 DEG C of temperature, 610 ~ 750 DEG C, place
Manage 0.5 ~ 5.0 hour time, preferably 1.0 ~ 3.0 hours.
The inventive method step（3）In, organic formwork agent is tetraethyl ammonium hydroxide, TMAH, tetrapropyl
The one or more of ammonium hydroxide.Wherein, by step（2）In after obtained Y type molecular sieve uniformly mixes with organic formwork agent, enter
Water-filling thermal crystallisation, process are as follows：By step（2）In obtained Y type molecular sieve be beaten in the organic formwork agent aqueous solution, liquid weighs admittedly
Amount is than being 3：1~8：1, temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 5.0 hour, the mass concentration of the organic formwork agent aqueous solution for 3% ~
10%, mixed material is then placed in crystallization in crystallizing kettle, crystallization temperature is 80 ~ 120 DEG C, and crystallization time is 4 ~ 10h, and gauge pressure is
0.1~0.2MPa.After crystallization, filtered and drying can use conventional method to carry out, and typically dry condition is as follows：50 ~
1 ~ 10h is dried at 110 DEG C.
In the inventive method, step（4）It is by step（3）Obtained Y type molecular sieve be calcined under low temperature oxygen-enriched atmosphere,
Wherein oxygen-enriched atmosphere refers to that oxygen content is more than 50v%, and sintering temperature is 300 ~ 450 DEG C, and roasting time is 5 ~ 10h.Roasting is general
Using the method being calcined under temperature programming again constant temperature, heating rate is preferably 1 ~ 2 DEG C/min.
Y type molecular sieve in hydrocracking catalyst of the present invention is to use（NH4）2SiF6Place is modified to NaY molecular sieve
Reason, while modulation molecular sieve silica alumina ratio is realized, can deviate from the sodium ion in NaY molecular sieve together, then in organic mould
Hydrothermal crystallizing is carried out to the molecular sieve after hydro-thermal process in the presence of plate agent, can so make part silicon atom and aluminium atom in organic mould
Plate agent effect enters framework of molecular sieve structure down, while further stablizing and improving the skeleton structure of modified molecular screen, disappears
Except caused non-skeleton structure, unimpeded pore passage structure, part organic formwork agent can also enter in zeolite-water heat treatment process
Into the duct of molecular sieve, coordinate follow-up oxygen-enriched low-temperature treatment, can by the organic formwork agent in molecular sieve it is controllable in order removing,
So as to produce a large amount of ordered mesopore structures, and pore size distribution is more concentrated.
Y type molecular sieve in hydrocracking catalyst of the present invention, acidity is suitable, crystallinity is high, mesoporous proportion is high, hole
Footpath distribution is more concentrated, suitably as Cracking Component.Because the Y type molecular sieve has bigger pore volume and mesopore volume, more
More acid centres are exposed, and are advantageous to raw material heavy oil macromolecular and are cracked, but also with more preferably pore-size distribution model
Enclose, the cracking degree of reactant can be efficiently controlled, and be advantageous to product and be diffused in duct, so in cracking reaction
In, can relative increase activated centre, and can make heavy oil macromolecular carry out suitable degree cracking reaction, both improved splitting for heavy oil
Change ability, while coke yield is reduced, catalyst can show good cracking activity and product selectivity.
Hydrocracking catalyst of the present invention is hydrocracked flexibly production industrial chemicals and traffic especially suitable for heavy wax oil
Transport fuel.
Brief description of the drawings
Fig. 1 is the SEM electromicroscopic photographs of the gained Modified Zeolite Y of embodiment 1；
Fig. 2 is the SEM electromicroscopic photographs of the gained Modified Zeolite Y of comparative example 1；
Fig. 3 is the XRD diffraction patterns of the gained Modified Zeolite Y of embodiment 1.
Embodiment
Aluminum oxide can use oxygen used in conventional hydrocracking catalyst in carrier of hydrocracking catalyst of the present invention
Change aluminium, such as macroporous aluminium oxide and small porous aluminum oxide, the mass ratio of general macroporous aluminium oxide and small porous aluminum oxide is 1：8~8：1.Institute
The property for the macroporous aluminium oxide stated is as follows：Pore volume is 0.6 ~ 1.3mL/g, and specific surface area is 300 ~ 450m2/g。
Adhesive therefor of the present invention is made up of small porous aluminum oxide and inorganic acid and/or organic acid.Aperture oxidation used
Aluminium pore volume is 0.3 ~ 0.5mL/g, and specific surface area is 200 ~ 400m2/g。
Amorphous silica-alumina used can be prepared by coprecipitation or grafting copolymerization process in catalyst carrier of the present invention, by document
It is prepared by middle conventional method.In obtained amorphous silica-alumina, SiO2Weight content be 10% ~ 60%, preferably 20% ~ 55%,
The pore volume of amorphous silica-alumina is 0.6 ~ 1.1mL/g, preferably 0.8 ~ 1.0mL/g, and specific surface area is 300 ~ 500m2/ g, preferably
For 350 ~ 500m2/g。
Detailed process prepared by catalyst carrier for hydrgenating of the present invention is as follows：By Modified Zeolite Y, amorphous silica-alumina, oxygen
Change aluminium mixing, shaping, then dry and be calcined, be prepared into carrier；It is small that drying can dry 3 ~ 6 at a temperature of 80 DEG C ~ 150 DEG C
When, roasting is calcined 2.5 ~ 6.0 hours at 500 DEG C ~ 600 DEG C.
Carrier of hydrocracking catalyst of the present invention loads hydrogenation active metal component by conventional methods（Vib and
Group VIII metal component such as Co, Ni, Mo, W etc.）, it is prepared into hydrocracking catalyst.Using load side conventional in the prior art
Method, preferably infusion process, can be saturation leaching, excessive leaching or complexing leaching, i.e., with the solution impregnation catalyst containing required active component
Agent carrier, carrier after dipping are then small in 450 DEG C ~ 550 DEG C roastings 2.5 ~ 6.0 in 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour
When, final catalyst is made.
The following examples are used to technical scheme be described in more detail, but the scope of the present invention is not limited solely to this
The scope of a little embodiments.In the present invention, wt% is mass fraction.
Analysis method of the present invention：Specific surface area, pore volume, mesoporous pore volume use low temperature liquid nitrogen determination of adsorption method, relatively
Crystallinity and cell parameter use x-ray diffraction method, and silica alumina ratio uses XRF methods（X ray fluorescence spectrometry）Measure, molecular sieve
Grain size use SEM（SEM）Mode determine.Meleic acid amount uses Pyridine adsorption IR spectra method, sodium
Content uses plasma emission spectrometry.
NaY molecular sieve original powder employed in the embodiment of the present invention and comparative example is industrially prepared, and property is as follows：SiO2/
Al2O3Mol ratio is 5.1, and grain size is ~ 1.7 μm, relative crystallinity 95%, cell parameter 2.468nm, Na2O weight content
For 6.5wt%, specific surface area 856m2/ g, total pore volume 0.32mL/g, micropore pore volume account for the 81.3% of total pore volume, butt
72.0wt%。
Embodiment 1
Take NaY original powder 278g to be put into 800mL water purification, be warming up to 95 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6
The aqueous solution, it is 72g/L's that 307mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature stirs after completion of dropwise addition
2 hours, constant temperature was filtered and dried after terminating, and the butt of molecular sieve is 65.3wt% after drying；By above-mentioned dried molecule
Sieve is added in hydrothermal treatment device, in gauge pressure 0.25MPa, 610 DEG C of temperature, under the conditions of 1.0 hours processing times molecular sieve is entered
Water-filling is heat-treated；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetraethyl ammonium hydroxide that 520mL mass concentrations are 5.3%
In the aqueous solution, constant temperature is stirred 4 hours under the conditions of 80 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydrothermal crystallizing,
90 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization time 10 hours, crystallization is filtered after terminating and drying process；Hydro-thermal is brilliant
To change obtained drying sample to be calcined under oxygen-enriched state, oxygen content is 70v% in calcination atmosphere, and heating rate is 1 DEG C/min,
Constant temperature calcining temperature is 420 DEG C, and the constant temperature calcining time is 6 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-1, molecular sieve
Property is listed in table 1.
Embodiment 2
Take NaY original powder 278g to be put into 800mL water purification, be warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 55g/L's that 182mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature after completion of dropwise addition
Stirring 2 hours, constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 68.0wt% after drying；Will be above-mentioned dried
Molecular sieve is added in hydrothermal treatment device, gauge pressure 0.30MPa, 670 DEG C of temperature, under the conditions of 2.0 hours processing times to point
Son sieve carries out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetrapropyl hydrogen that 910mL mass concentrations are 7.5%
Aoxidize in aqueous ammonium, constant temperature is stirred 4 hours under the conditions of 90 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal
Crystallization, 110 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization time 10 hours, crystallization is filtered after terminating and drying process；Will
The drying sample that hydrothermal crystallizing obtains is calcined under oxygen-enriched state, and oxygen content is 65v% in calcination atmosphere, heating rate 1
DEG C/min, constant temperature calcining temperature is 360 DEG C, and the constant temperature calcining time is 10 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-
2, molecular sieve property is listed in table 1.
Embodiment 3
Take NaY original powder 278g to be put into 1000mL water purification, be warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 85g/L's that 417mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature after completion of dropwise addition
Stirring 3 hours, constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 67.2wt% after drying；Will be above-mentioned dried
Molecular sieve is added in hydrothermal treatment device, gauge pressure 0.35MPa, 700 DEG C of temperature, under the conditions of 3.0 hours processing times to molecule
Sieve carries out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetraethyl hydrogen-oxygen that 1040mL mass concentrations are 3.5%
Change in aqueous ammonium, constant temperature is stirred 3 hours under the conditions of 85 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal crystalline substance
Change, 80 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization time 5 hours, crystallization is filtered after terminating and drying process；By hydro-thermal
The drying sample that crystallization obtains is calcined under oxygen-enriched state, and oxygen content is 75v% in calcination atmosphere, and heating rate is 1 DEG C/
Min, constant temperature calcining temperature are 320 DEG C, and the constant temperature calcining time is 8 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-3, point
Son sieve property is listed in table 1.
Embodiment 4
Take NaY original powder 278g to be put into 1400mL water purification, be warming up to 95 DEG C, start to be added dropwise into molecular sieve pulp（NH4）2SiF6The aqueous solution, it is 60g/L's that 200mL solution concentrations were uniformly added dropwise at 60 minutes（NH4）2SiF6Solution, constant temperature after completion of dropwise addition
Stirring 2 hours, constant temperature is filtered and dried after terminating, and the butt of molecular sieve is 68.1wt% after drying；Will be above-mentioned dried
Molecular sieve is added in hydrothermal treatment device, gauge pressure 0.30MPa, 750 DEG C of temperature, under the conditions of 2.0 hours processing times to point
Son sieve carries out hydro-thermal process；The molecular sieve after 130g hydro-thermal process is taken to be put into the tetrapropyl hydrogen that 520mL mass concentrations are 6.8%
Aoxidize in aqueous ammonium, constant temperature is stirred 3 hours under the conditions of 90 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal
Crystallization, 95 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization time 8 hours, crystallization is filtered after terminating and drying process；By water
The drying sample that thermal crystallisation obtains is calcined under oxygen-enriched state, and oxygen content is 70v% in calcination atmosphere, and heating rate is 1 DEG C/
Min, constant temperature calcining temperature are 380 DEG C, and the constant temperature calcining time is 10 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-4,
Molecular sieve property is listed in table 1.
Comparative example 1
Take NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concns are 1.5mol/L, be warming up to 95 DEG C, constant temperature stirring
2 hours, constant temperature was filtered, washed and dried after terminating, and the butt of molecular sieve is 63.8wt% after drying；Temperature programming will divide
Son sieve is calcined 3 hours at 600 DEG C；Then repeat an ammonium to exchange, and filter and dry；After taking second of ammonium of 100g to exchange
Molecular sieve be put into 650mL mass concentrations be 7.5% the tetraethyl ammonium hydroxide aqueous solution in, constant temperature stirs under the conditions of 80 DEG C
Mix 2 hours, then mixed material is transferred in crystallizing kettle and carries out crystallization, 100 DEG C, gauge pressure 0.1MPa of crystallization temperature, crystallization
8 hours time, crystallization is filtered after terminating and drying process；The drying sample that crystallization obtains is calcined under oxygen-enriched state,
Oxygen content is 60v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 360 DEG C, and the constant temperature calcining time is
8 hours, obtain molecular sieve.Sample number into spectrum LDAY-1, molecular sieve property are listed in table 1.
Comparative example 2
Take NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concns are 1.5mol/L, be warming up to 95 DEG C, constant temperature stirring
2 hours, constant temperature divides after terminating to be filtered, washed and dried, and the butt of molecular sieve is 63.8wt% after drying；Temperature programming will
Molecular sieve is calcined 3 hours at 600 DEG C；Then repeat an ammonium to exchange, and filter and dry；Second of ammonium of 100g is taken to exchange
Molecular sieve afterwards is put into the dust technology that 800mL concentration is 0.3mol/L, and constant temperature stirs 2 hours under the conditions of 80 DEG C, constant temperature
Filtered after end and drying process；Above-mentioned dried molecular sieve is added in hydrothermal treatment device, in gauge pressure
0.30MPa, 670 DEG C of temperature, molecular sieve is obtained to molecular sieve progress hydro-thermal process under the conditions of 2.0 hours processing times；Sample is compiled
Number LDAY-2, molecular sieve property are listed in table 1.
Comparative example 3
Molecular sieve, sample number into spectrum LDAY-3, molecular sieve property row are prepared using the method for embodiment in CN201510147788.3 1
In table 1.
The property of the Y type molecular sieve of table 1
| Production code member | LAY-1 | LAY-2 | LAY-3 | LAY-4 |
| Specific surface area, m2/g | 912 | 887 | 941 | 923 |
| Pore volume, cm3/g | 0.74 | 0.69 | 0.88 | 0.72 |
| Lattice constant, nm | 2.433 | 2.431 | 2.428 | 2.426 |
| Relative crystallinity, % | 131 | 119 | 140 | 132 |
| Average crystallite size, μm | 1.7 | 1.7 | 1.7 | 1.7 |
| SiO2/Al2O3Mol ratio | 73.6.3 | 62.3 | 81.9 | 65.8 |
| Mesoporous pore volume（Bore dia 2nm ~ 10nm）Account for total pore volume ratio, % | 86 | 83 | 91 | 87 |
| Infrared total acid content, mmol/g | 0.45 | 0.33 | 0.30 | 0.21 |
| Na2O, wt% | 0.05 | 0.06 | 0.03 | 0.07 |
Continued 1
| Production code member | LDAY-1 | LDAY-2 | LDAY-3 |
| Specific surface area, m2/g | 633 | 703 | 603 |
| Pore volume, cm3/g | 0.44 | 0.37 | 0.38 |
| Lattice constant, nm | 2.439 | 2.433 | 2.449 |
| Relative crystallinity, % | 98 | 103 | 86 |
| Average crystallite size, μm | 1.7 | 1.7 | 1.7 |
| SiO2/Al2O3Mol ratio | 7.5 | 33.5 | 8.6 |
| Mesoporous pore volume（Bore dia 2nm ~ 10nm）Account for total pore volume ratio, % | 47 | 31 | 37 |
| Infrared total acid content, mmol/g | 0.77 | 0.35 | 0.71 |
| Na2O, wt% | 0.21 | 0.19 | 0.45 |
Embodiment 5
By 100 grams of LAY-1 molecular sieves（Butt 90wt%）, 64.3 grams of amorphous silica-aluminas（SiO2Content 25wt%, pore volume
0.85mL/g, specific surface area 370m2/ g, butt 70wt%）, 150 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area
400m2/ g, butt 70wt%）, 200 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）It is put into stone roller
Mixed grind in press, adds water, is rolled into paste, extrusion, and extrusion bar is dried 4 hours at 110 DEG C, is then calcined 4 hours at 550 DEG C,
Obtain carrier ZS-1.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst HC-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 6
By 50 grams of LAY-1 molecular sieves（Butt 90wt%）, 50 grams of amorphous silica-aluminas（SiO2Content 25wt%, pore volume 0.85mL/g,
Specific surface area 370m2/ g, butt 70wt%）, 214.3 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, do
Base 70wt%）, 200 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）It is put into roller and mixes
Grind, add water, be rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, is then calcined 4 hours at 550 DEG C, obtains carrier ZS-
2。
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst HC-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 7 ~ 8
As described in Example 5, change LAY-1 into LAY-2, LAY-3 respectively, carrier ZS-3, ZS-4 and catalyst HC- is made
3 and HC-4, carrier and catalyst composition are shown in Table 2.
Comparative example 4 ~ 6
As described in Example 5, change LAY-1 into LDAY-1, LDAY-2, LDAY-2 respectively, be made carrier DZS-1, DZS-2,
DZS-3 and catalyst DHC-1, DHC-2 and DHC-3, carrier and catalyst composition are shown in Table 3.
Embodiment 9 ~ 12
This embodiment describes catalyst HC-1, HC-2, HC-3 and HC-4 Activity evaluation of the present invention.Tried in fixed bed hydrogenation
Evaluated on experiment device, appreciation condition is：React stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity 1.30h during liquid-1, using vacuum distillate as feedstock oil, feedstock property is listed in table 3, and evaluation result is listed in table 4.
Comparative example 7 ~ 9
This comparative example describes comparative example catalyst DHC-1, DHC-2 and DHC-3 Activity evaluation of the present invention.In fixed bed plus
Evaluated on hydrogen experimental rig, appreciation condition is：React stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity during liquid
1.30h-1, using vacuum distillate as feedstock oil, feedstock property is listed in table 3, and evaluation result is listed in table 4.
The composition and physico-chemical property of the catalyst carrier of table 2 and catalyst
| Carrier forms and property | ||||
| Numbering | ZS-1 | ZS-2 | ZS-3 | ZS-4 |
| Composition | ||||
| Modified Zeolite Y, wt% | 30.0 | 15.0 | 30.0 | 30.0 |
| Amorphous silica-alumina, wt% | 15.0 | 15.0 | 15.0 | 15.0 |
| Macroporous aluminium oxide, wt% | 35.0 | 50.0 | 35.0 | 35.0 |
| Adhesive, wt% | Surplus | Surplus | Surplus | Surplus |
| Property | ||||
| Pore volume, mL/g | 0.65 | 0.70 | 0.67 | 0.69 |
| Specific surface area, m2/g | 529 | 445 | 538 | 521 |
| Catalyst forms and property | ||||
| Numbering | HC-1 | HC-2 | HC-3 | HC-4 |
| WO3, wt% | 22.52 | 23.52 | 21.94 | 23.15 |
| NiO, wt% | 5.71 | 5.98 | 5.84 | 5.83 |
| Pore volume, mL/g | 0.42 | 0.45 | 0.41 | 0.44 |
| Specific surface area, m2/g | 429 | 386 | 425 | 433 |
Continued 2
| Carrier forms and property | |||
| Numbering | DZS-1 | DZS-2 | DZS-3 |
| Composition | |||
| Modified Zeolite Y, wt% | 30.0 | 30.0 | 30.0 |
| Amorphous silica-alumina, wt% | 15.0 | 15.0 | 15.0 |
| Macroporous aluminium oxide, wt% | 35.0 | 35.0 | 35.0 |
| Adhesive, wt% | Surplus | Surplus | Surplus |
| Property | |||
| Pore volume, mL/g | 0.51 | 0.50 | 0.54 |
| Specific surface area, m2/g | 422 | 433 | 428 |
| Catalyst forms and property | |||
| Numbering | DHC-1 | DHC-2 | DHC-3 |
| WO3, wt% | 22.49 | 22.50 | 22.56 |
| NiO, wt% | 5.81 | 5.78 | 5.89 |
| Pore volume, mL/g | 0.30 | 0.30 | 0.27 |
| Specific surface area, m2/g | 322 | 335 | 305 |
The feedstock oil main character of table 3
| Feedstock oil | Vacuum distillate |
| Density（20℃）, kg/m3 | 920.6 |
| Boiling range, DEG C | |
| IBP/10% | 328/413 |
| 30%/50% | 450/471 |
| 70%/90% | 493/522 |
| 95%/EBP | 534/545 |
| Nitrogen, μ g/g | 1575 |
| Carbon, wt% | 85.25 |
| Hydrogen, wt% | 11.96 |
| Carbon residue, wt% | 0.35 |
The comparative evaluation's result of table 4
| Catalyst | HC-1 | HC-2 | HC-3 | HC-4 |
| Feedstock oil | Vacuum distillate | Vacuum distillate | Vacuum distillate | Vacuum distillate |
| Operating condition | ||||
| Volume space velocity during liquid, h-1 | 1.30 | 1.30 | 1.30 | 1.30 |
| Hydrogen to oil volume ratio | 1200:1 | 1200:1 | 1200:1 | 1200:1 |
| React stagnation pressure, MPa | 14.7 | 14.7 | 14.7 | 14.7 |
| Reaction temperature, DEG C | 371 | 372 | 369 | 363 |
| Product yield and property | ||||
| Heavy naphtha | ||||
| Yield, wt% | 23.1 | 24.6 | 23.0 | 24.3 |
| Virtue is latent, wt% | 61.5 | 60.6 | 62.9 | 63.1 |
| Jet fuel | ||||
| Yield, wt% | 21.2 | 20.6 | 20.7 | 21.5 |
| Smoke point, mm | 28 | 29 | 28 | 28 |
| Aromatic hydrocarbons, v% | 6.2 | 5.7 | 6.3 | 6.1 |
| Diesel oil | ||||
| Yield, wt% | 19.4 | 19.9 | 20.5 | 18.6 |
| Cetane number | 60.9 | 62.5 | 60.6 | 61.9 |
| Tail oil | ||||
| Yield, wt% | 29.1 | 29.0 | 29.9 | 29.5 |
| BMCI values | 8.9 | 9.1 | 8.2 | 9.8 |
| Chemical hydrogen consumption, wt% | 2.25 | 2.26 | 2.21 | 2.11 |
| Liquid is received, wt% | 96.7 | 96.5 | 97.3 | 97.5 |
Continued 4
| Catalyst | DHC-1 | DHC-2 | DHC-3 |
| Feedstock oil | Vacuum distillate | Vacuum distillate | Vacuum distillate |
| Operating condition | |||
| Volume space velocity during liquid, h-1 | 1.30 | 1.30 | 1.30 |
| Hydrogen to oil volume ratio | 1200:1 | 1200:1 | 1200:1 |
| React stagnation pressure, MPa | 14.7 | 14.7 | 14.7 |
| Reaction temperature, DEG C | 375 | 379 | 385 |
| Product yield and property | |||
| Heavy naphtha | |||
| Yield, wt% | 22.3 | 22.5 | 21.5 |
| Virtue is latent, wt% | 60.0 | 55.1 | 52.3 |
| Jet fuel | |||
| Yield, wt% | 21.2 | 21.2 | 21.5 |
| Smoke point, mm | 26 | 24 | 23 |
| Aromatic hydrocarbons, v% | 7.7 | 8.9 | 10.3 |
| Diesel oil | |||
| Yield, wt% | 17.6 | 19.4 | 18.5 |
| Cetane number | 59.1 | 58.1 | 59.3 |
| Tail oil | |||
| Yield, wt% | 29.6 | 28.4 | 28.5 |
| BMCI values | 12.0 | 11.3 | 10.6 |
| Chemical hydrogen consumption, wt% | 2.34 | 2.48 | 2.51 |
| Liquid is received, wt% | 95.8 | 95.1 | 94.6 |
When it can be seen from the evaluation result of table 4 using hydrocracking catalyst of the present invention, heavy naphtha, jet fuel and bavin
The yield and quality of oil are superior to reference catalyst.
Claims (23)
1. a kind of hydrocracking catalyst, including hydrogenation active metal component and carrier, carrier includes Modified Zeolite Y, nothing
Amorphous silicon-alumina and aluminum oxide, wherein described Modified Zeolite Y, its property is as follows：Relative crystallinity is 110% ~ 150%,
SiO2/Al2O3Mol ratio is 55 ~ 100, and cell parameter is 2.425 ~ 2.435nm, and total pore volume is 0.55 ~ 1.0mL/g, mesoporous hole
Volume accounts for more than the 70% of total pore volume.
2. according to the catalyst described in claim 1, it is characterised in that：The property of the Y type molecular sieve is as follows：Total pore volume is
0.6 ~ 1.0mL/g, mesoporous pore volume account for the 80% ~ 95% of total pore volume.
3. according to the catalyst described in claim 1, it is characterised in that：The grain size of the Y type molecular sieve is 1.0 ~ 2.5 μm,
Preferably 1.2 ~ 1.8 μm.
4. according to the catalyst described in claim 1, it is characterised in that：The mesoporous bore dia of the Y type molecular sieve be 2nm ~
10nm。
5. according to the catalyst described in claim 1, it is characterised in that：The specific surface area of the Y type molecular sieve is 650m2/g~
1000m2/ g, preferably 750m2/g~1000m2/g。
6. according to the catalyst described in claim 1, it is characterised in that：The infrared total acid content of the Y type molecular sieve be 0.1 ~
0.5mmol/g。
7. according to the catalyst described in claim 1, it is characterised in that：In the Y type molecular sieve, Na2O weight content is
Below 0.15wt%.
8. according to the catalyst described in claim 1, it is characterised in that：The property of the hydrocracking catalyst is as follows：Compare table
Area is 250 ~ 450m2/ g, pore volume are 0.30 ~ 0.50mL/g.
9. according to the catalyst described in claim 1, it is characterised in that：Described hydrogenation active metals are vib and the
The metal of VIII, vib metals are molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；With the weight of catalyst
On the basis of, vib metals are using the content that oxide is counted as 10.0% ~ 30.0%, content of the group VIII metal in terms of oxide
For 4.0% ~ 8.0%, the content of carrier is 62.0% ~ 86.0%.
10. according to the catalyst described in claim 1 or 9, it is characterised in that：Described carrier of hydrocracking catalyst, to carry
On the basis of the weight of body, the content of Modified Zeolite Y is 10% ~ 50%, and the content of amorphous silica-alumina is 5% ~ 30%, aluminum oxide
Content is 20% ~ 85%, is preferably as follows：The content of Modified Zeolite Y is 15% ~ 45%, the content of amorphous silica-alumina for 10% ~
25%, the content of aluminum oxide is 30% ~ 75%.
11. according to the catalyst described in claim 1, it is characterised in that：In described amorphous silica-alumina, SiO2Weight content
It is as follows for 10% ~ 60%, preferably 20% ~ 55%, the property of amorphous silica-alumina：Pore volume is 0.6 ~ 1.1mL/g, and specific surface area is
300~500m2/ g, is preferably as follows：Pore volume is 0.8 ~ 1.0mL/g, and specific surface area is 350 ~ 500m2/g。
12. the preparation method of any catalyst of claim 1 ~ 11, include preparation and the load hydrogenation active metals of carrier
The preparation process of component, wherein carrier is as follows：Modified Zeolite Y, amorphous silica-alumina, aluminum oxide are mixed, shaping, Ran Hougan
Dry and roasting, is made the preparation method of catalyst carrier, wherein Modified Zeolite Y, comprises the following steps：
（1）NaY types molecular sieve with（NH4）2SiF6Aqueous solution contact is reacted, through filtering and drying after reaction；
（2）To step（1）Gained Y type molecular sieve carries out hydro-thermal process；Hydrothermal conditions：Gauge pressure is 0.20 ~ 0.40MPa, temperature
Spend for 600 ~ 800 DEG C, processing time is 0.5 ~ 5.0 hour, and preferably hydrothermal conditions are as follows：Gauge pressure is 0.25 ~ 0.40MPa,
Temperature is 610 ~ 750 DEG C, and processing time is 1.0 ~ 3.0 hours；
（3）By step（2）Gained Y type molecular sieve carries out hydrothermal crystallizing processing, Ran Houjing under the conditions of existing for organic formwork agent
Filter and dry；
（4）By step（3）The Y type molecular sieve of gained is calcined under low temperature oxygen-enriched atmosphere, and Modified Zeolite Y is made.
13. in accordance with the method for claim 12, it is characterised in that：Step（1）In, the property of NaY type molecular sieves is as follows：
SiO2/Al2O3Mol ratio be 3 ~ 6, grain size be 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm, relative crystallinity be 80% ~
110%, cell parameter is 2.465 ~ 2.470nm, Na2O weight content is 6.0wt% ~ 8.0wt%, specific surface area is 600 ~
900m2/ g, total pore volume are 0.3 ~ 0.4mL/g, and micropore pore volume accounts for more than the 75% of total pore volume.
14. in accordance with the method for claim 12, it is characterised in that：Step（1）In,（NH4）2SiF6Addition be NaY types
5wt% ~ 20wt% of molecular sieve butt weight.
15. in accordance with the method for claim 12, it is characterised in that：Step（1）In,（NH4）2SiF6The quality of the aqueous solution is dense
Spend for 50 ~ 100g/L.
16. in accordance with the method for claim 12, it is characterised in that：Step（1）In, NaY types molecular sieve with（NH4）2SiF6Water
The reaction condition that solution contact is reacted：Temperature is 80 ~ 150 DEG C, and the reaction time is 0.1 ~ 5.0 hour, preferred reaction conditions
It is as follows：Temperature is 90 ~ 120 DEG C, and the reaction time is 1.0 ~ 3.0 hours.
17. in accordance with the method for claim 12, it is characterised in that：Step（1）In, dry condition is at 50 ~ 95 DEG C
Dry 0.5 ~ 5.0 hour, the butt of the Y type molecular sieve of gained is 60wt% ~ 80wt% after drying.
18. in accordance with the method for claim 12, it is characterised in that：Step（3）In, organic formwork agent is tetraethyl hydroxide
One or more in ammonium, TMAH, TPAOH.
19. in accordance with the method for claim 12, it is characterised in that：By step（2）In obtained Y type molecular sieve and organic mould
Plate agent uniformly after mixing, carries out hydrothermal crystallizing, and process is as follows：By step（2）In obtained Y type molecular sieve in organic formwork agent water
It is beaten in solution, solvent and solute weight ratio 3：1~8：1, temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 5.0 hour, and organic formwork agent is water-soluble
The mass concentration of liquid is 3% ~ 10%, and mixed material then is placed in into crystallization in crystallizing kettle, and crystallization temperature is 80 ~ 120 DEG C, during crystallization
Between be 4 ~ 10h, gauge pressure is 0.1 ~ 0.2MPa.
20. in accordance with the method for claim 12, it is characterised in that：Step（4）It is by step（3）Obtained Y type molecular sieve
Be calcined under low temperature oxygen-enriched atmosphere, wherein oxygen-enriched atmosphere refers to that oxygen content is more than 50v%, and sintering temperature is 300 ~ 450 DEG C,
Roasting time is 5 ~ 10h.
21. in accordance with the method for claim 12, it is characterised in that：Described aluminum oxide includes macroporous aluminium oxide and aperture oxygen
The mass ratio of change aluminium, macroporous aluminium oxide and small porous aluminum oxide is 1：8~8：1；The property of described macroporous aluminium oxide is as follows：Hole body
Product is 0.6 ~ 1.3mL/g, and specific surface area is 300 ~ 450m2/g；The property of described small porous aluminum oxide is as follows：Pore volume be 0.3 ~
0.5mL/g, specific surface area are 200 ~ 400m2/g。
22. in accordance with the method for claim 12, it is characterised in that：Process prepared by the carrier of hydrocracking catalyst
For：
Modified Zeolite Y, amorphous silica-alumina, aluminum oxide are mixed, shaping, is then dried and is calcined, be prepared into carrier,
Described drying is dried 3 ~ 6 hours at a temperature of 80 DEG C ~ 150 DEG C, and roasting is calcined 2.5 ~ 6.0 hours at 500 DEG C ~ 600 DEG C.
23. in accordance with the method for claim 12, it is characterised in that：In the hydrocracking catalyst, active metal is born
Load uses infusion process, i.e., with the solution impregnated catalyst carrier containing active metal component, in 100 DEG C ~ 150 DEG C dryings after dipping
1 ~ 12 hour, then it is calcined 2.5 ~ 6.0 hours at 450 DEG C ~ 550 DEG C, hydrocracking catalyst is made.
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| WO2018205839A1 (en) * | 2017-05-08 | 2018-11-15 | 武汉凯迪工程技术研究总院有限公司 | Hydrocracking catalyst for production of diesel and jet fuel, and preparation method therefor |
| CN111977667A (en) * | 2020-08-11 | 2020-11-24 | 海南泽能科技有限公司 | High-heteroatom-content hierarchical pore MFI type molecular sieve, and preparation method and application thereof |
| CN116060122A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method and application thereof |
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|---|---|---|---|---|
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN104843736A (en) * | 2015-03-31 | 2015-08-19 | 中国石油天然气集团公司 | Y molecular sieve high in silica alumina ratio and abundant in secondary holes and preparation method therefor |
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2016
- 2016-05-05 CN CN201610289568.9A patent/CN107344106B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN104843736A (en) * | 2015-03-31 | 2015-08-19 | 中国石油天然气集团公司 | Y molecular sieve high in silica alumina ratio and abundant in secondary holes and preparation method therefor |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018205839A1 (en) * | 2017-05-08 | 2018-11-15 | 武汉凯迪工程技术研究总院有限公司 | Hydrocracking catalyst for production of diesel and jet fuel, and preparation method therefor |
| CN111977667A (en) * | 2020-08-11 | 2020-11-24 | 海南泽能科技有限公司 | High-heteroatom-content hierarchical pore MFI type molecular sieve, and preparation method and application thereof |
| CN116060122A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method and application thereof |
| CN116060122B (en) * | 2021-10-29 | 2024-05-03 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method and application thereof |
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