CN116060111B - Hydrocracking catalyst for producing middle distillate oil, and preparation method and application thereof - Google Patents
Hydrocracking catalyst for producing middle distillate oil, and preparation method and application thereof Download PDFInfo
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- CN116060111B CN116060111B CN202111269658.9A CN202111269658A CN116060111B CN 116060111 B CN116060111 B CN 116060111B CN 202111269658 A CN202111269658 A CN 202111269658A CN 116060111 B CN116060111 B CN 116060111B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002808 molecular sieve Substances 0.000 claims abstract description 197
- 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 197
- 239000002131 composite material Substances 0.000 claims abstract description 86
- 239000011258 core-shell material Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000003921 oil Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 17
- 239000000295 fuel oil Substances 0.000 claims abstract description 15
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 99
- 239000007791 liquid phase Substances 0.000 claims description 69
- 239000011148 porous material Substances 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 56
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 47
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 44
- 229910052710 silicon Inorganic materials 0.000 claims description 43
- 239000010703 silicon Substances 0.000 claims description 43
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- 239000001257 hydrogen Substances 0.000 claims description 42
- 229910052593 corundum Inorganic materials 0.000 claims description 33
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 29
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- 239000007790 solid phase Substances 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- -1 hydrogen ions Chemical class 0.000 claims description 22
- 239000000413 hydrolysate Substances 0.000 claims description 22
- 238000000926 separation method Methods 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- IWICDTXLJDCAMR-UHFFFAOYSA-N trihydroxy(propan-2-yloxy)silane Chemical compound CC(C)O[Si](O)(O)O IWICDTXLJDCAMR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 16
- 239000000243 solution Substances 0.000 description 38
- 238000003756 stirring Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 238000001914 filtration Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 239000011257 shell material Substances 0.000 description 10
- 239000011162 core material Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 2
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 2
- 229910018512 Al—OH Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 2
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 2
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 2
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 108091006231 SLC7A2 Proteins 0.000 description 2
- 108091006230 SLC7A3 Proteins 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000010724 circulating oil Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- 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
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—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
- 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
- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof 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
- B01J29/16—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
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- 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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a hydrocracking catalyst for producing middle distillate, a preparation method and application thereof. The catalyst comprises the following components by taking the weight of the catalyst as a reference: the content of the active metal is 4 to 40 weight percent of oxide; the content of the carrier is 60-96 wt%; wherein, the carrier, based on the total mass of the carrier, comprises: 10 to 15 weight percent of Al-SBA-15/beta core-shell composite molecular sieve, 5 to 15 weight percent of Y molecular sieve, 20 to 60 weight percent of amorphous silica-alumina and 15 to 50 weight percent of adhesive component. The catalyst is suitable for heavy oil hydrocracking reaction, and has the characteristics of high activity, high medium oil selectivity and good product property.
Description
Technical Field
The invention relates to a hydrocracking catalyst for producing middle distillate, a preparation method and application thereof.
Background
Because of the problems of shortage of petroleum resources, increasingly strict environmental protection requirements, inadaptation of petroleum product structures to market demands and the like, the hydrocracking technology becomes an effective technical measure for improving the quality of petroleum products, reducing environmental pollution and increasing market strain capacity, and becomes the most important process technology of modern refineries. Meanwhile, the increasingly strict motor fuel emission standard makes the problem of directly producing high-quality clean fuel by processing inferior heavy oil increasingly prominent, and the hydrocracking technology for producing middle distillate oil in maximum quantity and the development of a middle oil type catalyst matched with the hydrocracking technology are also more active.
The core of the hydrocracking technology is a hydrocracking catalyst, the technological progress of which depends on the improvement of the catalyst level, and a molecular sieve is used as a main acidic component of the hydrocracking catalyst and plays a decisive role in the activity, the selectivity and the product quality of the catalyst. In the traditional hydrocracking catalyst, though Y and beta molecular sieves are subjected to different modification treatments, the pore distribution is improved, and the silicon-aluminum ratio is improved, when heavy oil products with high sulfur content, nitrogen content, complex molecular structure and high carbon number are treated, the heavy oil products are limited by the properties of the molecular sieves, the diffusion resistance of the polycyclic aromatic hydrocarbon with larger kinetic size is larger, the inside of an access hole is influenced to contact with the richer inner surface of an acid center, and the advantage of preferential competitive adsorption of the polycyclic aromatic hydrocarbon is difficult to play; some medium molecules have small kinetic size and small diffusion resistance, and easily enter the micropores of the catalyst to generate secondary cracking reaction, so that the selectivity of middle distillate of the reaction is reduced, and the selectivity of medium oil and the quality of products are not ideal.
The successful synthesis of mesoporous materials not only expands the size range of the molecular sieve from micropores to mesopores in the traditional sense, but also establishes a bridge between the microporous materials and the mesoporous materials. Compared with other micro-mesoporous composite materials, the core-shell type composite mode can fully exert the respective advantages of the micro-mesoporous materials, thereby achieving the aim of effectively treating macromolecular reactants. The SBA-15/beta core-shell type composite molecular sieve hierarchical pore structure utilizes the characteristics of large pore diameter and weak acidity of a shell material to perform a macromolecular raw material presplitting reaction, and chain scission is performed on a side chain with weak macromolecular bond energy, so that macromolecules can easily enter a core material with a small pore canal, and then the cracking reaction is performed by virtue of the strong acidity advantage of the core material, so that the gradual reaction of hydrocracking is realized. Can solve the problem of petrochemical industry development caused by the increasing strictness of petrochemical product upgrading and updating and environmental protection regulations.
CN201010228038.6 describes a method for preparing a mesoporous-microporous core-shell composite molecular sieve catalyst, wherein microporous zeolite is used as a core, and mesoporous silica or mesoporous silica containing aluminum is used as a shell. The obtained composite molecular sieve has a reserved zeolite micropore framework and an ordered two-dimensional hexagonal mesoporous structure, mesoporous pore channels are vertical to the surfaces of zeolite particles, the pore channel openness is high, the thickness of mesoporous shell layers is adjustable, and after the mesoporous shell layers are wrapped, the high smoothness between the mesoporous and micropores can be maintained. The mesoporous shell pore size of the shell-core composite zeolite molecular sieve is generally smaller than 3nm, and is smaller for complex heavy oil and residual oil molecules.
US5536687 describes a catalyst comprising a beta molecular sieve and a Y molecular sieve. When the catalyst is used for producing middle distillate, the composition is as follows: y molecular sieve (1 wt% -15 wt%) and beta molecular sieve (1-15 wt%) and dispersed silicon-aluminum, aluminium oxide, metal W and Ni. The catalyst has low reactivity and low medium oil selectivity, and is difficult to meet the requirement of further increasing the yield of the middle distillate.
The catalyst is used in the reaction of producing middle distillate oil by heavy oil catalytic cracking, and has the problems of low middle distillate oil selectivity, poor activity and poor product quality in different degrees. In particular to a composite molecular sieve with a core-shell structure, which is inevitably easy to cause the separation of a shell and a core or the damage of a framework caused by the influence of external environment, thereby affecting the application of the composite molecular sieve in hydrocracking. Therefore, the further research of the catalyst suitable for the heavy oil hydrocracking reaction to produce high-quality middle oil fraction has great significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a hydrocracking catalyst for producing middle distillate, a preparation method and application thereof. The catalyst is suitable for heavy oil hydrocracking reaction, especially in one-stage serial hydrocracking process, and has the features of high activity, high medium oil selectivity and good product quality.
The first aspect of the invention provides a hydrocracking catalyst for producing middle distillate, which comprises the following components by weight of the catalyst: the content of the active metal is 4 to 40 weight percent of oxide; the content of the carrier is 60-96 wt%; wherein, the carrier, based on the total mass of the carrier, comprises: 10 to 15 weight percent of Al-SBA-15/beta core-shell composite molecular sieve, 5 to 15 weight percent of Y molecular sieve, 20 to 60 weight percent of amorphous silica-alumina and 15 to 50 weight percent of adhesive component.
According to the invention, the active metal comprises at least one of a group VIB metal and a group VIII metal.
According to the invention, the content of group VIB metals is preferably between 10 wt.% and 30 wt.% calculated as oxides, based on the weight of the catalyst.
According to the present invention, preferably, the group VIII metal is contained in an amount of 4 to 12wt% in terms of oxide based on the weight of the catalyst.
According to the invention, the group VIB metal comprises W and/or Mo; the group VIII metal comprises Co and/or Ni.
According to the invention, the specific surface area of the catalyst is 280-600 m 2/g; the pore volume is 0.3-0.7 mL/g.
According to the present invention, the composite molecular sieve comprises: al-SBA-15 is taken as a shell, and beta-type molecular sieve is taken as a core; the mass ratio of the shell to the core is 20:80-30:70; the SiO 2/Al2O3 molar ratio of the composite molecular sieve is 40-60.
According to the invention, the mass ratio of framework aluminum to non-framework aluminum in the composite molecular sieve is 95:5-99:1.
According to the invention, the SiO 2 content in the amorphous silica-alumina is 20-60 wt%, preferably 25-35 wt%; the pore volume is 0.6-1.1 mL/g, preferably 0.8-1.0 mL/g; the specific surface area is 300 to 500m 2/g, preferably 350 to 500m 2/g. The amorphous silica-alumina may be prepared by conventional methods, preferably by coprecipitation or graft copolymerization.
According to the invention, the Y molecular sieve has the following properties: the specific surface area is 700-1000 m 2/g, the total pore volume is 0.40-1.0 mL/g, the relative crystallinity is 95-130%, the SiO 2/Al2O3 molar ratio is 35-60, the unit cell parameter is 2.428-2.432 nm, and the infrared total acid amount is 0.2-0.4 mmol/g. The Y-type molecular sieve can be prepared by a conventional method in the prior art.
The second aspect of the present invention provides a method for preparing the hydrocracking catalyst, comprising the steps of: mixing Al-SBA-15/beta core-shell composite molecular sieve, Y molecular sieve, amorphous silica-alumina and adhesive, molding, drying and roasting to obtain a catalyst carrier; and loading active metal on the carrier to obtain the catalyst.
According to the invention, the Al-SBA-15/beta core-shell composite molecular sieve is prepared according to the following preparation method, which comprises the following steps:
(1) Adding a silicon source into the acid solution, uniformly mixing, standing and aging to obtain a silicon source hydrolysate;
(2) Uniformly mixing part of the silicon source hydrolysate in the step (1), the first beta molecular sieve and the first template agent, performing a first reaction, and performing first solid-liquid separation to obtain a first solid-phase product and a first liquid-phase product;
Controlling the solid content of the first liquid phase product to be 0.1-8wt%, preferably 0.5-2wt%, and more preferably 0.8-1.5wt%;
(3) Uniformly mixing part of the silicon source hydrolysate in the step (1), the second beta molecular sieve, part of the first liquid phase product obtained in the step (2) and the second template agent, and performing a second reaction and second solid-liquid separation to obtain a second solid phase product and a second liquid phase product;
Controlling the solid content of the second liquid phase product to be 0.1-8wt%, preferably 0.5-2wt%, and more preferably 0.8-1.5wt%;
(4) And taking the mixture of the first solid-phase product and the second solid-phase product and the first liquid-phase product and/or the second liquid-phase product as raw materials, carrying out hydrothermal crystallization, washing, drying and roasting to obtain the Al-SBA-15/beta core-shell composite molecular sieve.
According to the preparation method of the core-shell composite molecular sieve, the silicon source in the step (1) is one or more of methyl orthosilicate, ethyl orthosilicate TEOS, propyl orthosilicate, isopropyl orthosilicate and butyl orthosilicate. The acid is one or more of hydrochloric acid, sulfuric acid and phosphoric acid. The pH of the acid solution is 2 to 5, preferably 2.5 to 4.0.
According to the preparation method of the core-shell composite molecular sieve, in the step (1), the mechanical stirring mode is adopted for mixing, and the stirring time is 1-12 hours, preferably 4-8 hours; the standing aging time is 4 to 120 hours, preferably 24 to 96 hours.
According to the preparation method of the core-shell composite molecular sieve, in the step (2), the first template agent is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, which is abbreviated as P123; preferably, the template P123 is first dissolved in an acid solution and then mixed with the other raw materials. The acid is one or more of hydrochloric acid, sulfuric acid and phosphoric acid. The molar concentration of hydrogen ions in the acid solution is 0.2 to 0.7mol/L, preferably 0.3 to 0.5mol/L.
According to the preparation method of the core-shell composite molecular sieve, the molar concentration of hydrogen ions in the mixed material obtained in the step (2) is 0.2-0.7 mol/L, preferably 0.3-0.5 mol/L; the mass content of the first template agent in the system is 0.3-3%, preferably 0.5-2%; the mass content of the silicon source in the system is 1% -7%, preferably 2% -6%; the mass content of the first beta molecular sieve in the system is 0.5-12%, preferably 1.0-8%.
According to the preparation method of the core-shell composite molecular sieve, the conditions of the first reaction in the step (2) are as follows: the reaction temperature is 30-60 ℃, preferably 35-50 ℃, and the reaction time is 2-12 h, preferably 4-8 h.
According to the preparation method of the core-shell composite molecular sieve, in the step (2), one or more of centrifugal separation and filtering separation are adopted for the first solid-liquid separation; the first solid-liquid separation is not as aimed at as conventional separation, and this separation requires the retention of a suitable solid content in the liquid phase.
According to the preparation method of the core-shell composite molecular sieve, the first beta molecular sieve in the step (2) is a hydrogen beta molecular sieve.
According to the preparation method of the core-shell composite molecular sieve, in the step (2), the weight content of the Na 2 O of the first beta molecular sieve is less than 0.3 percent; the molar ratio SiO 2/Al2O3 of silicon to aluminum is 30-45; the specific surface area is 400-700 m 2/g; the pore volume is 0.3-0.6 mL/g; the grain diameter is 500-1000 nm.
According to the preparation method of the core-shell composite molecular sieve, the second beta molecular sieve in the step (3) is a hydrogen beta molecular sieve.
According to the preparation method of the core-shell composite molecular sieve, in the step (3), the weight content of the Na 2 O of the second beta molecular sieve is less than 0.3%; the molar ratio SiO 2/Al2O3 of silicon to aluminum is 30-45; the specific surface area is 400-700 m 2/g; the pore volume is 0.3-0.6 mL/g, and the grain diameter is 500-1000 nm.
According to the preparation method of the core-shell composite molecular sieve, in the step (3), the second template agent is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, which is abbreviated as P123; preferably, the template P123 is first dissolved in an acid solution and then mixed with the other raw materials. The acid is one or more of hydrochloric acid, sulfuric acid and phosphoric acid. The molar concentration of hydrogen ions of the acid solution is 0.1 to 0.6mol/L, preferably 0.3 to 0.5mol/L.
According to the preparation method of the core-shell composite molecular sieve, the molar concentration of hydrogen ions in the mixed material obtained in the step (3) is 0.2-0.7 mol/L, preferably 0.3-0.5 mol/L. The mass content of the added second template agent in the system is 0.3-3%, preferably 0.2-2%; the mass content of the added silicon source in the system is 1-7%, preferably 2-6%; the mass content of the added second beta molecular sieve in the system is 0.5-12%, preferably 1.0-8%. The addition amount of the first liquid phase product accounts for 60-80% of the mass fraction of the mixed material system in the step (3), and preferably 60-75%.
According to the preparation method of the core-shell composite molecular sieve, the conditions of the second reaction in the step (3) are as follows: the reaction temperature is 30-60 ℃, preferably 35-50 ℃, and the reaction time is 2-12 h, preferably 4-8 h.
According to the preparation method of the core-shell composite molecular sieve, in the step (3), one or more of centrifugal separation and filtering separation are adopted for the second solid-liquid separation.
According to the preparation method of the core-shell composite molecular sieve, in the step (4), the liquid-solid mass ratio of the mixed raw materials is controlled to be 1:1-10:1, preferably 1:1-8:1, and more preferably 1:1-5:1 by adjusting the addition amount of the first liquid-phase product and/or the second liquid-phase product. The first liquid phase product and/or the second liquid phase product are/is used for hydrothermal crystallization to synthesize the raw materials of the molecular sieve, and the rest part can be recycled.
According to the preparation method of the core-shell composite molecular sieve, ammonia water is added into the mixed material until the pH value is 3-7, preferably 4-5, before the hydrothermal crystallization in the step (4).
According to the preparation method of the core-shell composite molecular sieve, the hydrothermal crystallization condition in the step (4) is as follows: the crystallization temperature is 80-140 ℃, preferably 100-120 ℃; the crystallization time is 4 to 48 hours, preferably 24 to 30 hours. The drying temperature is 100-120 ℃, and the drying time is 6-10 h. The roasting temperature is 500-550 ℃ and the roasting time is 4-6 h.
According to the preparation method of the core-shell composite molecular sieve, the ratio of the SiO 2/Al2O3 mol ratio in the raw material of the step (4) to the SiO 2/Al2O3 mol ratio of the composite molecular sieve in the step (4) is 97-100%.
According to the present invention, in the preparation method of the hydrocracking catalyst, the binder may be a binder commonly used in the art, preferably small pore alumina; the pore volume of the small pore alumina is 0.3-0.5 mL/g, and the specific surface area is 200-400 m 2/g.
In the method for producing a hydrocracking catalyst according to the present invention, the molding may be selected as usual as required. The shape can be cylindrical strips, clover, etc. In the process of forming the catalyst, forming aids such as peptizing acid, extrusion aids and the like can be added, and the peptizing agent can generally adopt inorganic acid and/or organic acid, and the extrusion aids such as sesbania powder. The drying is carried out for 3-10 hours at the temperature of 80-150 ℃. The roasting is carried out for 3-12 hours at 400-800 ℃.
In the preparation method of the hydrocracking catalyst according to the present invention, the method of loading the active metal may employ a conventional loading method, preferably an impregnation method, and may be saturated impregnation, excessive impregnation or complex impregnation. Further, the impregnation method is to impregnate the carrier with a solution containing active metal, dry and bake the carrier to obtain the catalyst. The drying is carried out for 1-12 hours at 100-150 ℃. The roasting is carried out for 3-12 hours at 400-750 ℃.
The third aspect of the invention provides the use of the hydrocracking catalyst described above in heavy oil hydrocracking reactions.
According to the invention, the method used is a series hydrocracking process for producing middle distillates.
According to the present invention, the heavy oil includes one or more of various hydrocarbon oils such as vacuum gas oil, coker gas oil, deasphalted oil, thermally cracked gas oil, catalytically cracked circulating oil, and the like. The heavy oil is typically a hydrocarbon containing a distillation range of 300 to 600 c, and the nitrogen content is typically 50 to 2500 μg/g.
According to the invention, the hydrocracking conditions in the one-stage tandem hydrocracking process are as follows: the reaction temperature is 350-420 ℃, preferably 360-390 ℃; the reaction pressure is 6-20 MPa, preferably 9-16 MPa; the volume ratio of hydrogen to oil is 500-2000:1, preferably 800-1500: 1, a step of; the liquid hourly space velocity is 0.5-1.8 h -1, preferably 0.8-1.5 h -1.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) In the present invention, the catalyst comprises, based on the weight of the catalyst: the content of the active metal is 4 to 40 weight percent of oxide; the content of the carrier is 60-96 wt%; wherein, the carrier, based on the total mass of the carrier, comprises: 10 to 15 weight percent of Al-SBA-15/beta core-shell composite molecular sieve, 5 to 15 weight percent of Y molecular sieve, 20 to 60 weight percent of amorphous silica-alumina and 15 to 50 weight percent of adhesive component. The special Al-SBA-15/beta core-shell type composite molecular sieve is selected in the catalyst composition, the morphology of the composite molecular sieve is more uniform, and the 'core-shell' structure is more complete. The Al-SBA-15/beta molecular sieve and the Y molecular sieve are used as cracking centers together, the pore volume, the specific surface area, the gradient acid distribution and pore distribution pore channels consisting of mesopores and micropores are larger, and the size of the macromolecular material can be reduced and the capability of treating the macromolecular material of the microporous molecular sieve can be enhanced through the pre-cracking of the shell Al-SBA-15 weak acid site; and secondly, the free and smooth gradient pore canal is beneficial to the rapid escape of the reaction molecules from the catalytic surface, so that the reaction molecules are prevented from being excessively reacted. The beta molecular sieve has good isomerization effect on long side chains on alkane or arene, can effectively reduce the condensation point of the product, and meanwhile, the Y-type molecular sieve has high ring opening selectivity on arene, so that the product property of the product is improved. Therefore, the catalyst of the invention is used for producing middle distillate in the hydrocracking process, has the characteristics of higher middle oil selectivity, and has good product quality, in particular to aviation kerosene smoke point and diesel oil with higher cetane number.
(2) In the method, in particular to the preparation step of the Al-SBA-15/beta core-shell type composite molecular sieve, the solid content of a liquid phase product is controlled, and the shell type molecular sieve is introduced in a plurality of steps, so that the phase separation of the phase separation SBA-15 material and the beta molecular sieve is restrained, the morphology of the formed composite molecular sieve is more uniform, and the 'core-shell' structure is more complete. In the method, the silicon source is hydrolyzed in advance, and the method maintains the complete structure and higher crystallinity of the beta molecular sieve. In the method, SBA-15 is synthesized in an acidic system, the characteristic that beta molecular sieve is dealuminated in specific acid concentration is utilized, non-framework aluminum formed by dealumination is released from pore channels of a microporous molecular sieve in the system to serve as an aluminum source for synthesizing a mesoporous molecular sieve, the synthesis of the composite molecular sieve fully utilizes the non-framework aluminum released by the microporous molecular sieve, an aluminum source externally added in the conventional preparation of the SBA-15 molecular sieve is omitted, and the released Al 3+ is hydrolyzed to form Al-OH through the adjustment of the pH value of the system, and the Al-OH and silicon hydroxyl Si-OH are mutually polymerized to enter the framework of the SBA-15. Meanwhile, the in-situ aluminum supplementing of SBA-15 and the acidic dealumination modification of the beta molecular sieve are completed. Meanwhile, the silicon-aluminum ratio of the beta molecular sieve is improved, and the structure and crystallinity of the beta molecular sieve are well maintained. The Al-SBA-15/beta molecular sieve prepared by the method has larger pore volume, specific surface area, and gradient acid distribution and pore distribution pore canal composed of mesopores and micropores, and is suitable for the field of macromolecular catalysis. In particular to the heavy oil hydrocracking reaction, the catalyst prepared by the method has higher activity and middle distillate selectivity, and the product quality is good, in particular to aviation kerosene smoke point and diesel oil cetane number are higher.
(3) In the invention, the catalyst is suitable for heavy oil hydrocracking reaction, and is preferably applied to heavy oil hydrocracking in a one-stage serial hydrocracking process to produce middle distillate. The catalyst has the advantages of high medium oil selectivity, high activity, good product quality, and high cetane number of aviation kerosene smoke point and diesel oil. Under the condition of 63 percent conversion, the selectivity of oil in the catalyst can reach 88.4 percent, the smoke point of jet fuel can reach 29mm, and the cetane number of diesel oil can reach 73.
Drawings
FIG. 1 is a small angle XRD spectrum of an example molecular sieve;
wherein: line 1 is the composite molecular sieve Al-SBA-15/beta-1 of example 1, line 2 is the composite molecular sieve Al-SBA-15/beta-2 of example 2, and line 3 is the composite molecular sieve Al-SBA-15/beta-3 of example 3;
FIG. 2 is a small angle XRD spectrum of the molecular sieves of the examples and comparative examples;
Wherein: line 1 is the composite molecular sieve Al-SBA-15/beta-3-1 of comparative example 1, line 2 is the composite molecular sieve Al-SBA-15/beta-3 of example 3, line 3 is the composite molecular sieve Al-SBA-15/beta-3-2 of comparative example 2, and line 4 is the composite molecular sieve Al-SBA-15/beta-3-3 of comparative example 3;
FIG. 3 is a high angle XRD spectrum of the molecular sieves of the examples and comparative examples;
Wherein: line 1 is molecular sieve beta-1, line 2 is composite molecular sieve Al-SBA-15/beta-1 of example 1, line 3 is composite molecular sieve Al-SBA-15/beta-2 of example 2, and line 4 is composite molecular sieve Al-SBA-15/beta-3 of example 3;
FIG. 4 is XRD spectra of molecular sieves of examples and comparative examples;
Wherein: line 1 is molecular sieve beta-1, line 2 is comparative example 4 molecular sieve beta-2, line 3 is comparative example 5 molecular sieve beta-3, and line 4 is comparative example 1 composite molecular sieve Al-SBA-15/beta-3-1; line 5 is the composite molecular sieve Al-SBA-15/beta-3-2 of comparative example 2, and line 6 is the composite molecular sieve Al-SBA-15/beta-3-3 of comparative example 3;
FIG. 5 is a TEM image of the composite molecular sieve Al-SBA-15/beta-3 prepared in example 3;
FIG. 6 is a TEM image of the composite molecular sieve Al-SBA-15/beta-3-1 prepared in comparative example 1.
Detailed Description
In the invention, the specific surface area and pore volume of the product are measured by adopting ASAP2405 and a low-temperature liquid nitrogen adsorption method.
In the invention, the acid amount is measured by an infrared spectrometer, and the adsorbent used is pyridine.
In the present invention, TEM analysis was performed on a JEM-2100 high resolution transmission electron microscopy device.
In the present invention, the relative crystallinity is measured by XRD. The relative crystallinity of the beta molecular sieve is based on the hydrogen form of the beta molecular sieve in step (2) of example 1. The relative crystallinity of the Y molecular sieve is based on the starting Y molecular sieve in example 1. The molar ratio of silicon to aluminum is determined by a chemical method.
In the invention, 27 Al MAS NMR characterization of skeleton aluminum and non-skeleton aluminum adopts a Bruker AV-500 type nuclear magnetic resonance instrument in Switzerland.
In the invention,% is mass fraction unless otherwise specified.
The solid content of the liquid phase in the process according to the invention is defined as the ratio of the weight of the solid after evaporation of the water removed to the total mass of the liquid phase.
Example 1:
(1) Under stirring, 10.0g of TEOS was added to 25.0g of HCl solution with ph=2.7, and after stirring at room temperature for 4 hours, the solution was changed from a turbid solution to a clear solution, and was left to stand for 24 hours, to obtain a silicon source hydrolysate.
(2) 1.2G of P123 are dissolved in 120g of 0.50mol/L hydrochloric acid solution; 5.8g of hydrogen beta molecular sieve, named beta-1 (specific surface area 685m 2/g, pore volume 0.52mL/g, particle size 800nm, siO 2/Al2O3 mol ratio 37, na 2 O weight content 0.1%, relative crystallinity 100%) was mixed with 40g of water, added to the above-mentioned mixed solution of hydrochloric acid and P123, stirred for 5min, then added with 1/2 of the silicon source hydrolysate obtained in step (1) and mixed uniformly. The molar concentration of hydrogen ions in the mixed material is 0.45mol/L; stirring at constant temperature of 45 ℃ for 4h. And then centrifugal separation is carried out to obtain a solid-phase product and a liquid-phase product. The solid content of the liquid phase product was controlled to be 0.8wt%.
(3) And (2) dissolving P123 in 0.50mol/L hydrochloric acid solution, adding 2/3 of the liquid phase product obtained in the step (2), adding hydrogen beta molecular sieve with the same property as the beta-1 molecular sieve in the step (2), and mixing the rest silicon source hydrolysate uniformly. The molar concentration of hydrogen ions in the mixed material is 0.45mol/L, and the mass content of the added P123 in the system is 0.73%; the mass content of the added silicon source TEOS in the system is 5%; the mass content of the added hydrogen type beta molecular sieve in the system is 1.8 percent. The added amount of the liquid phase product in the step (2) accounts for 65% of the mass fraction of the mixed material system in the step (3). Stirring at constant temperature of 45 ℃ for 4h. And then filtering and separating to obtain a solid-phase product and a liquid-phase product. The solid content of the liquid phase product was controlled to be 0.8wt%.
(4) And (3) hydrothermal crystallization: mixing the solid-phase products obtained in the step (2) and the step (3) to obtain a solid-phase raw material of the step (4); mixing the liquid-phase product remained in the step (2) with the liquid-phase product obtained in the step (3) to obtain a liquid-phase raw material of the step (4); and feeding according to the metering ratio, and controlling the liquid-solid mass ratio of the mixed materials to be 2:1. Stirring uniformly, adding ammonia water to regulate pH to 4.0, crystallizing at 100deg.C for 24 hr, filtering, washing, drying at 100deg.C for 6 hr, and calcining at 550deg.C for 4 hr to obtain core-shell composite molecular sieve, which is designated as Al-SBA-15/beta-1. The ratio of SiO 2/Al2O3 mol ratio in the raw material of the step (4) to SiO 2/Al2O3 mol ratio of the composite molecular sieve is 99%. The physical parameters of the composite molecular sieve are shown in Table 1.XRD patterns are shown in fig. 1 and 3.
A binder composed of 20.1 g of the Al-SBA-15/beta-1 molecular sieve of example 1, 11.5 g of the Y molecular sieve (specific surface area: 807m 2/g, total pore volume: 0.58mL/g, relative crystallinity: 100%, siO 2/Al2O3 molar ratio: 48, unit cell parameter: 2.430nm, total infrared acid content: 0.273 mmol/g), 93 g of amorphous silica alumina (pore volume: 1.0mL/g, specific surface area: 380m 2/g, silica weight content: 31%), and 35 g of small-pore alumina (pore volume: 0.35mL/g, specific surface area: 330m 2/g) and 40g of 10wt% dilute nitric acid was put into a roll mill, water was added, rolled into paste, extruded bars, the extruded bars were dried at 110℃for 4 hours, and then calcined at 550℃for 4 hours to obtain a carrier TCAT-1.
The carrier is immersed in immersion liquid containing tungsten and nickel for 2 hours at room temperature, dried for 4 hours at 120 ℃, and baked for 4 hours at a temperature of 500 ℃ by programming, thus obtaining the catalyst CAT-1, and the properties of the catalyst are shown in Table 2.
The catalyst CAT-1 was subjected to an activity evaluation test. The tests were carried out on a 200mL small hydrogenation unit using a one-stage serial hydrocracking process with the properties of the feedstock oil as shown in table 3. The hydrocracking operating conditions were as follows: the reaction pressure is 15.7MPa, and the hydrogen-oil volume ratio is 1200:1, liquid hourly space velocity 1.0h -1, catalyst evaluation results after 300 hours of operation are shown in Table 4.
Example 2:
(1) Under stirring, 10.0g of teos was added to 25.0gpH =2.8 of HCl solution, and after stirring at room temperature for 4 hours, the solution was changed from a turbid solution to a clear solution, and was left to stand for 24 hours, to obtain a silicon source hydrolysate.
(2) 1.4G of P123 are dissolved in 120g of 0.48mol/L hydrochloric acid solution; 6.5g of hydrogen beta molecular sieve (the specific surface area is 608m 2/g, the pore volume is 0.47mL/g, the particle size is 800nm, the SiO 2/Al2O3 mol ratio is 31, the Na 2 O weight content is 0.1%, the relative crystallinity is 101%) and 40g of water are mixed, then added into the mixed solution of hydrochloric acid and P123, stirred for 5min, and then 1/2 of the silicon source hydrolysate obtained in the step (1) is added and mixed uniformly. The molar concentration of hydrogen ions in the mixed material is 0.43mol/L; stirring at 48 ℃ for 4 hours at constant temperature. And then centrifugal separation is carried out to obtain a solid-phase product and a liquid-phase product. The solid content of the liquid phase product was controlled to be 1.0wt%.
(3) And (2) dissolving P123 in 0.48mol/L hydrochloric acid solution, adding 2/3 of the liquid phase product obtained in the step (2), adding hydrogen beta molecular sieve with the same molecular sieve property as that in the step (2), and mixing the rest silicon source hydrolysate uniformly. The molar concentration of hydrogen ions in the mixed material is 0.43mol/L, and the mass content of the added P123 in the system is 0.80 percent; the mass content of the added silicon source TEOS in the system is 4.6%; the mass content of the added hydrogen type beta molecular sieve in the system is 2.6 percent. The added amount of the liquid phase product in the step (2) accounts for 62% of the mass fraction of the mixed material system in the step (3). Stirring at constant temperature of 45 ℃ for 4h. And then filtering and separating to obtain a solid-phase product and a liquid-phase product. The solid content of the liquid phase was controlled to be 1.0wt%.
(4) And (3) hydrothermal crystallization: mixing the solid-phase products obtained in the step (2) and the step (3) to obtain a solid-phase raw material of the step (4); mixing the liquid-phase product remained in the step (2) with the liquid-phase product obtained in the step (3) to obtain a liquid-phase raw material of the step (4); and feeding according to the metering ratio, and controlling the liquid-solid mass ratio of the mixed materials to be 2:1. Stirring uniformly, adding ammonia water to regulate pH to 4.5, crystallizing at 100deg.C for 24 hr, filtering, washing, drying at 100deg.C for 6 hr, and calcining at 550deg.C for 4 hr to obtain core-shell composite molecular sieve, which is designated as Al-SBA-15/beta-2. The ratio of SiO 2/Al2O3 mol ratio in the raw material of the step (4) to the mol ratio of the composite molecular sieve SiO 2/Al2O3 is 98%. The physical parameters of the composite molecular sieve are shown in Table 1.XRD patterns are shown in fig. 1 and 3.
18.3 G of the Al-SBA-15/beta-2 molecular sieve of this example, 12.5 g of Y molecular sieve (specific surface area 798m 2/g, total pore volume 0.56mL/g, relative crystallinity 107%, siO 2/Al2O3 molar ratio 45, unit cell parameter 2.430nm, total infrared acid content 0.279 mmol/g), 93 g of amorphous silica alumina (pore volume 1.0mL/g, specific surface area 380m 2/g, silica weight content 31%), and 32 g of small pore alumina (pore volume 0.32mL/g, specific surface area 310m 2/g) were mixed with 37 g of 10wt% dilute nitric acid, put into a rolling machine, added with water, rolled into paste, extruded into bars, dried at 110℃for 4 hours, and then calcined at 550℃for 4 hours to obtain the carrier TCAT-2.
The carrier is immersed in immersion liquid containing tungsten and nickel for 2 hours at room temperature, dried for 4 hours at 120 ℃, and baked for 4 hours at a temperature of 500 ℃ by programming, thus obtaining the catalyst CAT-2, and the properties of the catalyst are shown in Table 2.
The catalyst CAT-2 was subjected to an activity evaluation test. The tests were carried out on a 200mL small hydrogenation unit using a one-stage serial hydrocracking process with the properties of the feedstock oil as shown in table 3. The hydrocracking operating conditions were as follows: the reaction pressure is 15.7MPa, and the hydrogen-oil volume ratio is 1200:1, liquid hourly space velocity 1.0h -1, catalyst evaluation results after 300 hours of operation are shown in Table 4.
Example 3:
(1) 10.0g of TEOS was added to 25.0g of HCl solution with pH=2.9 under stirring, and after stirring at room temperature for 4 hours, the solution was changed from turbid solution to clear solution, and left to stand for 24 hours to obtain silicon source hydrolysate.
(2) 1.6G of P123 are dissolved in 120g of 0.45mol/L hydrochloric acid solution; 7.5g of hydrogen beta molecular sieve (specific surface area 541m 2/g, pore volume 0.40mL/g, particle size 800nm, siO 2/Al2O3 mol ratio 41, na 2 O weight content 0.1%, relative crystallinity 101%) and 40g of water are mixed, added into the mixed solution of hydrochloric acid and P123, stirred for 5min, and then added into 1/2 of the silicon source hydrolysate obtained in the step (1) to be mixed uniformly. The molar concentration of hydrogen ions in the mixed material is 0.40mol/L; stirring at 48 ℃ for 4 hours at constant temperature. And then centrifugal separation is carried out to obtain a solid-phase product and a liquid-phase product. The solid content of the liquid phase product was controlled to be 1.2wt%.
(3) And (2) dissolving P123 in 0.45mol/L hydrochloric acid solution, adding 2/3 of the liquid phase product obtained in the step (2), adding hydrogen beta molecular sieve with the same property as the beta molecular sieve in the step (2), and mixing the rest silicon source hydrolysate uniformly. The molar concentration of hydrogen ions in the mixed material is 0.42mol/L, and the mass content of the added P123 in the system is 0.78%; the mass content of the added silicon source TEOS in the system is 4%; the mass content of the added beta molecular sieve in the system is 3.5 percent. The added amount of the liquid phase product in the step (2) accounts for 64% of the mass fraction of the mixed material system in the step (3). Stirring at 48 ℃ for 4 hours at constant temperature. And then filtering and separating to obtain a solid-phase product and a liquid-phase product. The solid content of the liquid phase was controlled to be 1.2wt%.
(4) And (3) hydrothermal crystallization: mixing the solid-phase products obtained in the step (2) and the step (3) to obtain a solid-phase raw material of the step (4); mixing the liquid-phase product remained in the step (2) with the liquid-phase product obtained in the step (3) to obtain a liquid-phase raw material of the step (4); and feeding according to the metering ratio, and controlling the liquid-solid mass ratio of the mixed materials to be 3:1. Stirring uniformly, adding ammonia water to regulate pH to 4.8, crystallizing at 100deg.C for 24 hr, filtering, washing, drying at 100deg.C for 6 hr, and calcining at 550deg.C for 4 hr to obtain core-shell composite molecular sieve, which is designated as Al-SBA-15/beta-3. The ratio of SiO 2/Al2O3 mol ratio in the raw material of the step (4) to SiO 2/Al2O3 mol ratio of the composite molecular sieve is 99%. The physical parameters of the composite molecular sieve are shown in Table 1.XRD patterns are shown in fig. 1 and 3. The TEM image is shown in FIG. 5.
23.9 G of the Al-SBA-15/beta-3 molecular sieve of this example, 10.6 g of Y molecular sieve (specific surface area 760m 2/g, total pore volume 0.55mL/g, relative crystallinity 118%, siO 2/Al2O3 molar ratio 42, unit cell parameter 2.430nm, total infrared acid content 0.295 mmol/g), 100 g of amorphous silica alumina (pore volume 0.9mL/g, specific surface area 350m 2/g, silica weight content 30%), and 35 g of small pore alumina (pore volume 0.38mL/g, specific surface area 360m 2/g) were mixed with 40 g of 10wt% dilute nitric acid, put into a rolling machine, added with water, rolled into paste, extruded into bars, dried at 110℃for 4 hours, and then calcined at 550℃for 4 hours to obtain the carrier TCAT-3.
The carrier is immersed in immersion liquid containing tungsten and nickel for 2 hours at room temperature, dried for 4 hours at 120 ℃, and baked for 4 hours at a temperature of 500 ℃ by programming, thus obtaining the catalyst CAT-3, and the properties of the catalyst are shown in Table 2.
The catalyst CAT-3 was subjected to an activity evaluation test. The tests were carried out on a 200mL small hydrogenation unit using a one-stage serial hydrocracking process with the properties of the feedstock oil as shown in table 3. The operating conditions were as follows: the reaction pressure is 15.7MPa, and the hydrogen-oil volume ratio is 1200:1, liquid hourly space velocity 1.0h -1, catalyst evaluation results after 300 hours of operation are shown in Table 4.
Comparative example 1:
(1) 5.0g of TEOS was added to 12.5g of HCl solution with pH=2.9 under stirring, and after stirring at room temperature for 4 hours, the solution was changed from turbid solution to clear solution, and left to stand for 24 hours to obtain silicon source hydrolysate.
(2) 1.6G of P123 are dissolved in 120g of a 0.45mol/L hydrochloric acid solution; 7.5g of hydrogen beta molecular sieve (raw material hydrogen beta molecular sieve in the step (2) in the example 3) and 40g of water are mixed, added into the mixed solution of hydrochloric acid and P123, stirred for 5min, and then added into the silicon source hydrolysate obtained in the step (1) to be uniformly mixed. The molar concentration of hydrogen ions in the mixed material is 0.40mol/L; stirring at constant temperature of 50 ℃ for 4 hours.
(3) And (3) hydrothermal crystallization: adding ammonia water into the product of the step (2) to adjust the pH of the system to 4.8, crystallizing at 100 ℃ for 24 hours, filtering, washing, drying at 100 ℃ for 6 hours, and roasting at 550 ℃ for 4 hours to obtain the core-shell composite molecular sieve, which is denoted as Al-SBA-15/beta-3-1. The ratio of SiO 2/Al2O3 mol ratio in the raw material to the composite molecular sieve SiO 2/Al2O3 mol ratio is 92%. The physical parameters of the composite molecular sieve are shown in Table 1.XRD patterns are shown in FIG. 2 and FIG. 4, and TEM patterns are shown in FIG. 6.
23.9 G of the Al-SBA-15/beta-3-1 molecular sieve of this example, 10.6 g of Y molecular sieve (specific surface area 760m 2/g, total pore volume 0.55mL/g, relative crystallinity 118%, siO 2/Al2O3 molar ratio 42, unit cell parameter 2.430nm, total infrared acid content 0.295 mmol/g), 100 g of amorphous silica alumina (pore volume 0.9mL/g, specific surface area 350m 2/g, silica weight content 30%), and 35 g of small pore alumina (pore volume 0.38mL/g, specific surface area 360m 2/g) were mixed with 40 g of 10wt% dilute nitric acid, put into a rolling machine, added with water, rolled into paste, extruded into bars, dried at 110℃for 4 hours, and then calcined at 550℃for 4 hours to obtain the carrier TCAT-3-1.
The carrier is immersed in the immersion liquid containing tungsten and nickel for 2 hours at room temperature, dried for 4 hours at 120 ℃, and baked for 4 hours at the temperature of 500 ℃ by programming, thus obtaining the catalyst CCAT-3-1, and the catalyst properties are shown in Table 2.
The catalyst CCAT-3-1 was subjected to an activity evaluation test. The tests were carried out on a 200mL small hydrogenation unit using a one-stage serial hydrocracking process with the properties of the feedstock oil as shown in table 3. The operating conditions were as follows: the reaction pressure is 15.7MPa, and the hydrogen-oil volume ratio is 1200:1, liquid hourly space velocity 1.0h -1, catalyst evaluation results after 300 hours of operation are shown in Table 4.
Comparative example 2:
(1) 1.6g of P123 are dissolved in 120g of 0.45mol/L hydrochloric acid solution; 7.5g of hydrogen form beta molecular sieve (raw material hydrogen form beta molecular sieve in the same way as in the step (2) of the example 3) and 40g of water are mixed and added into the mixed solution of the hydrochloric acid and the P123, and the mixture is stirred for 5min, and then 5g of TEOS is slowly added dropwise by a pipette. The molar concentration of hydrogen ions in the mixture is 0.40mol/L, and the mixture is stirred for 30 hours at a constant temperature of 50 ℃.
(2) And (3) hydrothermal crystallization: adding ammonia water to regulate pH to 4.8, crystallizing at 100deg.C for 24 hr, filtering, washing, drying at 100deg.C for 6 hr, and calcining at 550deg.C for 4 hr to obtain core-shell composite molecular sieve, which is designated as Al-SBA-15/beta-3-2. The ratio of SiO 2/Al2O3 mol ratio in the raw material to the composite molecular sieve SiO 2/Al2O3 mol ratio is 70%. The physical parameters of the composite molecular sieve are shown in Table 1.XRD patterns are shown in fig. 2 and 4.
23.9 G of the Al-SBA-15/beta-3-2 molecular sieve of this example, 10.6 g of Y molecular sieve (specific surface area 760m 2/g, total pore volume 0.55mL/g, relative crystallinity 118%, siO 2/Al2O3 molar ratio 42, unit cell parameter 2.430nm, total infrared acid content 0.295 mmol/g), 100 g of amorphous silica alumina (pore volume 0.9mL/g, specific surface area 350m 2/g, silica weight content 30%), and 35 g of small pore alumina (pore volume 0.38mL/g, specific surface area 360m 2/g) were mixed with 40 g of 10wt% dilute nitric acid, put into a rolling machine, added with water, rolled into paste, extruded into bars, dried at 110℃for 4 hours, and then calcined at 550℃for 4 hours to obtain the carrier TCAT-3-2.
The carrier is immersed in the immersion liquid containing tungsten and nickel for 2 hours at room temperature, dried for 4 hours at 120 ℃, and baked for 4 hours at the temperature of 500 ℃ by programming, thus obtaining the catalyst CCAT-3-2, and the catalyst properties are shown in Table 2.
The catalyst CCAT-3-2 was subjected to an activity evaluation test. The tests were carried out on a 200mL small hydrogenation unit using a one-stage serial hydrocracking process with the properties of the feedstock oil as shown in table 3. The operating conditions were as follows: the reaction pressure is 15.7MPa, and the hydrogen-oil volume ratio is 1200:1, liquid hourly space velocity 1.0h -1, catalyst evaluation results after 300 hours of operation are shown in Table 4.
Comparative example 3:
(1) Under stirring, 10.0g of teos was added to 25.0gpH =2.9 of HCl solution, and after stirring at room temperature for 4 hours, the solution was changed from a turbid solution to a clear solution, and was left to stand for 24 hours, to obtain a silicon source hydrolysate.
(2) 1.6G of P123 are dissolved in 120g of 0.45mol/L hydrochloric acid solution; 7.5g of hydrogen beta molecular sieve (raw material hydrogen beta molecular sieve in the step (2) in the example 3) and 20g of water are mixed, added into the mixed solution of hydrochloric acid and P123, stirred for 5min, and then added into the silicon source hydrolysate obtained in the step (1) in the 1/2 step, and the mixture is uniformly mixed. The molar concentration of hydrogen ions in the mixed material is 0.40mol/L; stirring at constant temperature of 50 ℃ for 4 hours.
(3) And (3) hydrothermal crystallization: crystallizing the product in the step (2) for 24 hours at 100 ℃, filtering, washing, drying for 6 hours at 100 ℃, and roasting for 4 hours at 550 ℃ to obtain the core-shell structure Al-SBA-15/beta-3-3 material. The ratio of SiO 2/Al2O3 mol ratio in the raw material to SiO 2/Al2O3 mol ratio of the composite molecular sieve is 57%. The physical parameters of the composite molecular sieve are shown in Table 1.XRD patterns are shown in fig. 2 and 4.
23.9 G of the Al-SBA-15/beta-3-3 molecular sieve of this example, 10.6 g of Y molecular sieve (specific surface area 760m 2/g, total pore volume 0.55mL/g, relative crystallinity 118%, siO 2/Al2O3 molar ratio 42, unit cell parameter 2.430nm, total infrared acid content 0.295 mmol/g), 100 g of amorphous silica alumina (pore volume 0.9mL/g, specific surface area 350m 2/g, silica weight content 30%), and 35 g of small pore alumina (pore volume 0.38mL/g, specific surface area 360m 2/g) were mixed with 40 g of 10wt% dilute nitric acid, put into a rolling machine, added with water, rolled into paste, extruded into bars, dried at 110℃for 4 hours, and then calcined at 550℃for 4 hours to obtain the carrier TCAT-3-3.
The carrier is immersed in the immersion liquid containing tungsten and nickel for 2 hours at room temperature, dried for 4 hours at 120 ℃, and baked for 4 hours at a temperature of 500 ℃ by programming, thus obtaining the catalyst CCAT-3-3, and the catalyst properties are shown in Table 2.
The catalyst CCAT-3-3 was subjected to an activity evaluation test. The tests were carried out on a 200mL small hydrogenation unit using a one-stage serial hydrocracking process with the properties of the feedstock oil as shown in table 3. The operating conditions were as follows: the reaction pressure is 15.7MPa, and the hydrogen-oil volume ratio is 1200:1, liquid hourly space velocity 1.0h -1, catalyst evaluation results after 300 hours of operation are shown in Table 4.
Comparative example 4:
10g of hydrogen type beta molecular sieve (the same as the raw material hydrogen type beta molecular sieve in the step (2) of the example 1) is added into hydrochloric acid solution with the molar concentration of hydrogen ions of 0.4mol/L, the liquid-solid mass ratio is controlled to be 10:1, and the mixture is stirred for 4 hours at the constant temperature of 50 ℃. Filtering, washing, drying at 120 ℃ for 6 hours, and roasting at 550 ℃ for 4 hours to obtain the beta-2 material. The physical parameters of the molecular sieve are shown in Table 1. The XRD spectrum is shown in FIG. 4.
Comparative example 5:
10g of hydrogen type beta molecular sieve (the same as the raw material hydrogen type beta molecular sieve in the step (2) of the example 1) is added into a hydrochloric acid solution with the molar concentration of hydrogen ions of 5mol/L, the liquid-solid mass ratio is controlled to be 10:1, and the mixture is stirred for 4 hours at the constant temperature of 50 ℃. Filtering, washing, drying at 120 ℃ for 6 hours, and roasting at 550 ℃ for 4 hours to obtain the beta-3 material. The physical parameters of the molecular sieve are shown in Table 1. The XRD spectrum is shown in FIG. 4.
Table 1 physicochemical properties of molecular sieves
The composite molecular sieve is shown in FIG. 5 as a core-shell Al-SBA-15/beta composite molecular sieve. As can be seen from FIGS. 5 and 6, the Al-SBA-15/beta-3 has less split-phase SBA-15, more uniform morphology and more complete "core-shell" structure than the Al-SBA-15/beta-3-1. As can be seen from Table 1, the molecular sieve prepared by the invention simultaneously completes in-situ aluminum supplementation of SBA-15. Meanwhile, the silicon-aluminum ratio of the beta molecular sieve is improved, and the structure and crystallinity of the beta molecular sieve are well maintained.
TABLE 2 physicochemical Properties of the catalysts
As can be seen from Table 2, compared with the catalyst of comparative example, the catalyst of the present invention has more uniform morphology and more complete core-shell structure, so that the catalyst has more uniform metal dispersion and larger pore volume and specific surface area. The total amount of infrared acids is also increased.
TABLE 3 Properties of raw oil
| Raw oil | Iran VGO |
| Density (20 ℃), g/cm 3 | 0.9081 |
| Distillation range, DEG C | 321～551 |
| Condensation point, DEG C | 32 |
| Carbon residue, wt% | 0.2 |
| S，wt％ | 2.34 |
| N，μg/g | 1502 |
| Aromatic hydrocarbon, wt% | 43.2 |
| BMCI value | 46.9 |
TABLE 4 evaluation results of catalyst Activity
As can be seen from the evaluation results of the catalysts in Table 4, the catalyst prepared by the invention has the characteristics of higher activity and medium oil selectivity, good product properties, especially high aviation kerosene smoke point, diesel oil cetane number, low condensation point and the like under the same operation conditions and with basically the same conversion rate.
Claims (29)
1. A hydrocracking catalyst for producing middle distillates, which is characterized in that the catalyst comprises, based on the weight of the catalyst: the content of the active metal is 4-40 wt% of oxide; the content of the carrier is 60-96 wt%;
Wherein, the carrier, based on the total mass of the carrier, comprises: 10-15 wt% of Al-SBA-15/beta core-shell composite molecular sieve, 5-15 wt% of Y molecular sieve, 20-60 wt% of amorphous silica-alumina, and 15-50 wt% of adhesive component;
The active metal comprises at least one of a group VIB metal and a group VIII metal;
the composite molecular sieve takes Al-SBA-15 as a shell and beta-type molecular sieve as a core; the mass ratio of the shell to the core is 20:80-30:70; the SiO 2/Al2O3 molar ratio of the composite molecular sieve is 40-60;
The preparation method of the hydrocracking catalyst comprises the following steps: mixing Al-SBA-15/beta core-shell composite molecular sieve, Y molecular sieve, amorphous silica-alumina and adhesive, molding, drying and roasting to obtain a catalyst carrier; the catalyst is obtained by loading active metal on the carrier;
The Al-SBA-15/beta core-shell composite molecular sieve is prepared according to the following method, and the method comprises the following steps:
(1) Adding a silicon source into the acid solution, uniformly mixing, standing and aging to obtain a silicon source hydrolysate;
(2) Uniformly mixing part of the silicon source hydrolysate in the step (1), the first beta molecular sieve and the first template agent, performing a first reaction, and performing first solid-liquid separation to obtain a first solid-phase product and a first liquid-phase product;
controlling the solid content of the first liquid phase product to be 0.1-8wt%;
(3) Uniformly mixing part of the silicon source hydrolysate in the step (1), the second beta molecular sieve, part of the first liquid phase product obtained in the step (2) and the second template agent, and performing a second reaction and second solid-liquid separation to obtain a second solid phase product and a second liquid phase product;
controlling the solid content of the second liquid phase product to be 0.1-8wt%;
(4) And taking the mixture of the first solid-phase product and the second solid-phase product and the first liquid-phase product and/or the second liquid-phase product as raw materials, carrying out hydrothermal crystallization, washing, drying and roasting to obtain the Al-SBA-15/beta core-shell composite molecular sieve.
2. The hydrocracking catalyst of claim 1 wherein the group VIB metal comprises W and/or Mo; the group VIII metal comprises Co and/or Ni.
3. The hydrocracking catalyst according to claim 1, wherein the specific surface area of the Y molecular sieve is 700 to 1000 m 2/g; the total pore volume is 0.40-1.0 mL/g; the relative crystallinity is 95% -130%; siO 2/Al2O3 in a molar ratio of 35-60; the unit cell parameters are 2.428-2.432 nm; the total infrared acid amount is 0.2-0.4 mmol/g;
And/or the content of SiO 2 in the amorphous silica-alumina is 20-60 wt%; the pore volume is 0.6-1.1 mL/g; the specific surface area is 300-500 m 2/g.
4. The hydrocracking catalyst according to claim 3, wherein the content of SiO 2 in the amorphous silica-alumina is 25wt% to 35wt%; the pore volume is 0.8-1.0 mL/g; the specific surface area is 350-500 m 2/g.
5. The hydrocracking catalyst according to claim 1, wherein the specific surface area of the catalyst is 280-600 m 2/g; the pore volume is 0.3-0.7 mL/g.
6. The hydrocracking catalyst according to claim 1, wherein the mass ratio of framework aluminum to non-framework aluminum in the composite molecular sieve is 95:5 to 99:1.
7. A method for preparing a hydrocracking catalyst as claimed in any one of claims 1 to 6, characterized in that the method comprises the steps of:
Mixing Al-SBA-15/beta core-shell composite molecular sieve, Y molecular sieve, amorphous silica-alumina and adhesive, molding, drying and roasting to obtain a catalyst carrier; the catalyst is obtained by loading active metal on the carrier;
The Al-SBA-15/beta core-shell composite molecular sieve is prepared according to the following method, and the method comprises the following steps:
(1) Adding a silicon source into the acid solution, uniformly mixing, standing and aging to obtain a silicon source hydrolysate;
(2) Uniformly mixing part of the silicon source hydrolysate in the step (1), the first beta molecular sieve and the first template agent, performing a first reaction, and performing first solid-liquid separation to obtain a first solid-phase product and a first liquid-phase product;
controlling the solid content of the first liquid phase product to be 0.1-8wt%;
(3) Uniformly mixing part of the silicon source hydrolysate in the step (1), the second beta molecular sieve, part of the first liquid phase product obtained in the step (2) and the second template agent, and performing a second reaction and second solid-liquid separation to obtain a second solid phase product and a second liquid phase product;
controlling the solid content of the second liquid phase product to be 0.1-8wt%;
(4) And taking the mixture of the first solid-phase product and the second solid-phase product and the first liquid-phase product and/or the second liquid-phase product as raw materials, carrying out hydrothermal crystallization, washing, drying and roasting to obtain the Al-SBA-15/beta core-shell composite molecular sieve.
8. The method according to claim 7, wherein the solid content of the first liquid-phase product is controlled to be 0.5wt% to 2wt%.
9. The method according to claim 7, wherein the solid content of the first liquid-phase product is controlled to be 0.8wt% to 1.5wt%.
10. The method according to claim 7, wherein the solid content of the second liquid-phase product is controlled to be 0.5wt% to 2wt%.
11. The method according to claim 7, wherein the solid content of the second liquid-phase product is controlled to be 0.8wt% to 1.5wt%.
12. The preparation method according to claim 7, wherein the molar concentration of hydrogen ions in the mixed material obtained by the mixing in the step (2) is 0.2 to 0.7mol/L; the mass content of the first template agent in the system is 0.3% -3%; the mass content of the silicon source in the system is 1% -7%; the mass content of the first beta molecular sieve in the system is 0.5% -12%;
And/or, in the mixed material obtained by mixing in the step (3), the molar concentration of hydrogen ions is 0.2-0.7 mol/L; the mass content of the added second template agent in the system is 0.3% -3%; the mass content of the added silicon source in the system is 1% -7%; the mass content of the added second beta molecular sieve in the system is 0.5% -12%; the addition amount of the first liquid phase product accounts for 60-80% of the mass fraction of the mixed material system in the step (3).
13. The preparation method according to claim 12, wherein the molar concentration of hydrogen ions in the mixed material obtained by the mixing in the step (2) is 0.3 to 0.5mol/L; the mass content of the first template agent in the system is 0.5% -2%; the mass content of the silicon source in the system is 2% -6%; the mass content of the first beta molecular sieve in the system is 1.0% -8%;
And/or, in the mixed material obtained by mixing in the step (3), the molar concentration of hydrogen ions is 0.3-0.5 mol/L; the mass content of the added second template agent in the system is 0.2% -2%; the mass content of the added silicon source in the system is 2% -6%; the mass content of the added second beta molecular sieve in the system is 1.0% -8%; the addition amount of the first liquid phase product accounts for 60-75% of the mass fraction of the mixed material system in the step (3).
14. The method according to claim 7, wherein the silicon source in the step (1) is one or more of methyl orthosilicate, ethyl orthosilicate TEOS, propyl orthosilicate, isopropyl orthosilicate, butyl orthosilicate; the acid is one or more of hydrochloric acid, sulfuric acid and phosphoric acid; the pH of the acid solution is 2-5;
and/or, in the step (2), the first template agent is P123;
And/or, in the step (2), the first beta molecular sieve is a hydrogen beta molecular sieve;
and/or, in the step (3), the second beta molecular sieve is a hydrogen beta molecular sieve.
15. The method according to claim 14, wherein in the step (1), the pH of the acid solution is 2.5 to 4.0.
16. The method of claim 14, wherein the first beta molecular sieve Na 2 O in step (2) is less than 0.3% by weight; the molar ratio SiO 2/Al2O3 of silicon to aluminum is 30-45; the specific surface area is 400-700 m 2/g; the pore volume is 0.3-0.6 mL/g; the grain diameter is 500-1000 nm;
And/or, the second beta molecular sieve Na 2 O weight content in step (3) is less than 0.3%; the molar ratio SiO 2/Al2O3 of silicon to aluminum is 30-45; the specific surface area is 400-700 m 2/g; the pore volume is 0.3-0.6 mL/g, and the particle size is 500-1000 nm.
17. The method according to claim 7, wherein the conditions of the first reaction in step (2) are: the reaction temperature is 30-60 ℃ and the reaction time is 2-12 h;
And/or, the conditions of the second reaction in step (3) are: the reaction temperature is 30-60 ℃ and the reaction time is 2-12 h.
18. The method of claim 17, wherein the conditions of the first reaction in step (2) are: the reaction temperature is 35-50 ℃ and the reaction time is 4-8 hours;
And/or, the conditions of the second reaction in step (3) are: the reaction temperature is 35-50 ℃ and the reaction time is 4-8 h.
19. The method according to claim 7, wherein the ratio of the SiO 2/Al2O3 molar ratio in the raw material of the step (4) to the SiO 2/Al2O3 molar ratio of the composite molecular sieve in the step (4) is 97% -100%.
20. The preparation method of claim 7, wherein in the step (4), the liquid-solid mass ratio of the mixed raw materials is controlled to be 1:1-10:1 by adjusting the addition amount of the first liquid-phase product and/or the second liquid-phase product.
21. The preparation method of claim 20, wherein in the step (4), the liquid-solid mass ratio of the mixed raw materials is controlled to be 1:1-8:1 by adjusting the addition amount of the first liquid-phase product and/or the second liquid-phase product.
22. The preparation method of claim 20, wherein in the step (4), the liquid-solid mass ratio of the mixed raw materials is controlled to be 1:1-5:1 by adjusting the addition amount of the first liquid-phase product and/or the second liquid-phase product.
23. The method according to claim 7, wherein the hydrothermal crystallization conditions in the step (4) are: the crystallization temperature is 80-140 ℃, and the crystallization time is 4-48 h;
and/or the drying temperature is 100-120 ℃, and the drying time is 6-10 hours;
And/or the roasting temperature is 500-550 ℃ and the roasting time is 4-6 h.
24. The method according to claim 23, wherein the hydrothermal crystallization conditions in step (4) are: the crystallization temperature is 100-120 ℃; the crystallization time is 24-30 h.
25. The method according to claim 7, wherein the drying is for 3 to 10 hours at a temperature of 80 to 150 ℃; the roasting is carried out for 3 to 12 hours at the temperature of 400 to 800 ℃;
And/or the method for loading the active metal is an impregnation method.
26. The method according to claim 25, wherein the impregnation method is a method of impregnating a carrier with a solution containing an active metal, drying, and calcining; the drying is 100-150 ℃ drying for l-12 hours; the roasting is carried out for 3-12 hours at 400-750 ℃.
27. Use of the catalyst of any one of claims 1 to 6 or the catalyst prepared by the preparation method of any one of claims 7 to 26 in heavy oil hydrocracking reactions; the method is a series hydrocracking process and is used for producing middle distillate.
28. The use according to claim 27, wherein the hydrocracking conditions in the one-stage tandem hydrocracking process are: the reaction temperature is 350-420 ℃; the reaction pressure is 6-20 MPa; hydrogen oil volume ratio is 500-2000:1: 1, a step of; the liquid hourly space velocity is 0.5-1.8 h -1.
29. The use according to claim 28, wherein the hydrocracking conditions in the one-stage tandem hydrocracking process are: the reaction temperature is 360-390 ℃; the reaction pressure is 9-16 MPa; hydrogen oil volume ratio 800-1500: 1, a step of; the liquid hourly space velocity is 0.8-1.5 h -1.
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| CN106140280A (en) * | 2015-03-27 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation method thereof |
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| CN113019422B (en) * | 2019-12-25 | 2022-09-09 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier, hydrocracking catalyst and preparation method thereof |
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| CN106140280A (en) * | 2015-03-27 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation method thereof |
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