CN105817259A - Productive naphtha type hydrocracking catalyst and preparation method thereof - Google Patents
Productive naphtha type hydrocracking catalyst and preparation method thereof Download PDFInfo
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- CN105817259A CN105817259A CN201610236230.7A CN201610236230A CN105817259A CN 105817259 A CN105817259 A CN 105817259A CN 201610236230 A CN201610236230 A CN 201610236230A CN 105817259 A CN105817259 A CN 105817259A
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- acid
- molecular sieve
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- preparation
- hydrocracking catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 36
- 239000002808 molecular sieve Substances 0.000 claims abstract description 63
- 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 63
- 239000002253 acid Substances 0.000 claims abstract description 35
- 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 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 6
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000005470 impregnation Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 235000015165 citric acid Nutrition 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 230000036541 health Effects 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000005453 pelletization Methods 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 238000002161 passivation Methods 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005987 sulfurization reaction Methods 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- 235000011054 acetic acid Nutrition 0.000 claims 1
- 210000004556 brain Anatomy 0.000 claims 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 238000005336 cracking Methods 0.000 abstract description 9
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000010792 warming Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 238000002803 maceration Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 101100224931 Caenorhabditis elegans dhc-1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical group [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 1
- TYOIKSXJQXGLFR-UHFFFAOYSA-N niobium nitric acid Chemical compound [Nb].[N+](=O)(O)[O-] TYOIKSXJQXGLFR-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001179 sorption measurement 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
- B01J29/08—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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (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 productive naphtha type hydrocracking catalyst and a preparation method thereof. The hydrocracking catalyst is prepared from hydrogenation active metal and a carrier containing a modified Y molecular sieve, amorphous silica-alumina and alumina powder, wherein the physicochemical properties of the modified Y molecular sieve are as follows: the average diameter of crystalline grains is 150-650nm, the molar ratio of skeleton SiO2/Al2O3 is 10.0-25.0, the content of sodium oxide is less than 0.05wt%, the cell parameter is 2.434-2.445nm, the relative crystallinity is 95-125%,the pyridine-infrared acid content is 0.60-1.2mmol/g, the content of a medium-strong acid B is 75-85% of total acid content, the specific surface area is 550-580m<2>/g, and the pore volume is 0.40-0.85mL/g. A technique for coupling ammonium salt inorganic salt-rare earth organic acid and modified Y molecular sieve and an active metal positioning, regulating and controlling technique are adopted for the productive naphtha type hydrocracking catalyst and the preparation method thereof, the cracking activity and a hydrogenation activity center are synthetically matched, and the convertibility of a catalyst to medium-molecular and macromolecular components in a raw material and the selectivity of naphtha are improved.
Description
Technical field
The present invention relates to catalyst technical field, relate to a kind of hydrocracking catalyst and preparation method thereof, especially
Relate to containing modified Y molecular sieve and the voluminous hydrocracking catalyst for naphtha of amorphous silica-alumina, preparation side
Method and application thereof.
Background technology
In the face of the heaviness increasingly of boundary's petroleum resources, in poor quality, the high quality increasingly of petroleum fuel products, cleaning
Change, thus the head that development heavy crude Efficient Conversion and clear gusoline production technology become current petrochemical processing industry bends
Weight.Hydrocracking technology has been that heavy oil lighting combines in one with production clear gusoline, solution industrial chemicals demand
The comprehensive processing technology of body.The speedup of current domestic aromatic hydrocarbons market development, Petroleum latent to high virtue is former as reforming
The demand of material constantly increases.Solve this problem it is critical only that high activity and selective hydrogenation Cracking catalyst
Development.
Chinese invention patent CN103191775A discloses the preparation method of a kind of hydrocracking catalyst.Should
Method is that first low-temperature hydrothermal processes aluminum oxide dry glue powder, then soaks with the solution containing hydrogenation active metals component
Stain, through dried, together with molecular sieve under the effect of peptizer or binding agent, through fully rolling, becoming
Type, be dried and roasting and obtain catalyst.The method can improve the pore structure of catalyst, has big specific surface
Long-pending and pore volume, beneficially hydrogenation component coordinate with the optimization of Cracking Component, have the highest catalysis activity, suitableeer
Together in processing, height is done, being hydrocracked of vacuum distillate inferior raises productivity and improves the quality heavy naphtha and improve tail oil product
The catalytic process of quality.
Chinese invention patent CN102049280A discloses a kind of hydrocracking catalyst and preparation method thereof.
This catalyst includes hydrogenation active metals component and small-grain Y molecular sieve, amorphous silica-alumina and aluminium oxide composition
Carrier, wherein said small crystal grain Y-shaped molecular sieve is to use the small crystal grain Y-shaped molecular sieve after hydrothermal treatment consists.
By hydrocracking catalyst of the present invention, there is high catalysis activity, good purpose product selectivity, production chains
The feature such as big, can produce heavy naphtha, the boat product such as coal and diesel oil, and yield is high, good product quality.
Chinese invention patent CN103406143A discloses a kind of light oil type hydrogen cracking catalyst and preparation thereof
Method.This invention is hydrocracked agent carrier and contains the high modified Y molecular sieve of lytic activity and isomery performance simultaneously
Excellent modified ZSM-5-23 molecular sieve so that the catalytic performance of carrier is more comprehensively.Y molecular sieve is modified dealuminzation,
Improving its skeleton Si/Al causes structure cell contraction, the reduction of surface acid center concentration, acid site intensity to increase, simultaneously
Produce abundant secondary mesopore, be conducive to improving the adsorption and desorption performance of molecular sieve, reduce reactant, generation
The diffusional resistance of thing, improves reaction rate, so that catalyst obtains higher catalytic pyrolysis performance, fecund is light
Matter distillate.Modified ZSM-23 molecular screen duct is unobstructed, and acid site number is few, and isomery performance highlights,
Light naphthar component isomery is conducive to make its octane number improve.
Chinese invention patent CN104588123A discloses the preparation method of a kind of carrier of hydrocracking catalyst.
The method includes: by small crystal grain Y-shaped molecular sieve, amorphous silica-alumina and the binding agent mixing made with aluminium oxide,
Extruded moulding, then drying and roasting, make carrier.This carrier of hydrocracking catalyst adds for light oil type
During hydrogen Cracking catalyst, catalyst can be made to have good activity, heavy naphtha selectivity and the product of excellence
Matter.
In a word, for activity and the selectivity of hydrocracking catalyst, although existing many is studied round Y
Other sieve technology aspects molecular sieve modified and compounding realize hydrogenation cracking activity, and existing open method is respectively arranged with
Excellence, the main distinction one of different technologies is the compound skill of modification technology and the acidic components being Y molecular sieve
Art aspect, but explore the hydrocracking catalyst that a kind of activity is higher, selectivity is more excellent, obtaining more Gao Fang
While latent Petroleum, and the stability solving catalyst is the mesh that petroleum refining field is pursued with the life-span all the time
Mark.
Summary of the invention
For deficiency of the prior art, the present invention provides a kind of ammonium salt mineral acid-rare earth organic acid coupling modification
Small-grain Y molecular sieve and amorphous silica-alumina, collectively as acidic components, are prepared as tooth ball type carrier, with non-noble
Metal is hydrogenation sites, by active metal positioning load and control technique, have matched the cracking of catalyst
Active center and hydrogenation sites, preparation fecund petroleum naphtha hydrogenation Cracking catalyst.
A kind of fecund hydrocracking catalyst for naphtha, it is characterised in that:
Described voluminous hydrocracking catalyst for naphtha composition weight content is: modified Y molecular sieve is
20～40wt%, amorphous silica-alumina 10～30wt%, group vib metal be 10～16wt%, group VIII metal be
2～6wt%, auxiliary agent is 0～2wt%, and remaining component is alumina powder；Described auxiliary agent is in F or P
Plant or two kinds；
Described voluminous hydrocracking catalyst for naphtha specific surface area is 320～480m2/ g, pore volume is
0.35～0.55cm3/ g, pyridine meleic acid amount is 0.60～1.00mmol/g, and B-acid/L acid ratio is 0.5～0.8；
Described modified Y molecular sieve, its character is as follows: average grain diameter is 150～650nm, skeleton
SiO2/Al2O3Mol ratio 10.0～25.0, sodium oxide content < 0.05wt%, cell parameter 2.438～2.450nm,
Relative crystallinity 95～125%, pyridine-meleic acid amount 0.60～1.20mmol/g, in strong B-acid content account for total acid
The 75～85% of amount, specific surface area is 550～850m2/ g, pore volume is 0.40～0.85mL/g, rare earth metal oxygen
The weight/mass percentage composition changed is 0.2～1.0wt%；
Its character of described amorphous silica-alumina is as follows: SiO2With Al2O3Mass ratio 0.25～1.0, specific surface area is
350～600m2/ g, pore volume is 0.80～1.40cm3/ g, most probable pore size 10.0～15.0nm, pyridine meleic acid
Amount is 0.40～0.80mmol/g.
Fecund hydrocracking catalyst for naphtha of the present invention, wherein catalyst appearance is preferably tooth ball
Type.
Present invention also offers the preparation method of a kind of fecund hydrocracking catalyst for naphtha, including following step
Rapid:
1) preparation of carrier: modified Y molecular sieve, amorphous silica-alumina, alumina powder are mixed all with extrusion aid
Even, be configured to mix former powder, after adding acid solution kneading become can plasticized body, through be squeezed into bar,
Stretching, pelletizing obtain carrier；
2) preparation of impregnation liquid: organic acid, soluble activating group vib metal will be sequentially added in deionized water
With group VIII slaine and the presoma of auxiliary agent, uniform stirring is heated to dissolving, obtains after constant volume
Stablize impregnation liquid；
3) load of active component: use equi-volume impregnating active metal is loaded to step 2) described in load
On body, then by the carrier after dipping through health preserving, be dried, obtain hydrocracking catalyst after roasting；
The preparation method of wherein said modified Y molecular sieve comprises the following steps:
1) NaY molecular sieve is placed in the solution of ammonium salt-containing and mineral acid, in temperature 80～the temperature of 100 DEG C
Lower exchange 2～12h, exchanges 2～6 times, obtains HY molecular sieve after drying, roasting；
2) HY molecular sieve is first after processing 0.5～8h in 580～800 DEG C of hydro-thermal stoves, then place containing organic acid with
In the dynamic response still of rare earth metal salt solutions, hydrothermal treatment consists 6～48h, drying at a temperature of 80～200 DEG C
After obtain modified Y molecular sieve.
According to preparation method of the present invention, described vib metals is W or Mo, group VIII
Metal is Ni, and wherein W/Ni atomic molar ratio is 0.5～1.5, and Mo/Ni atomic molar ratio is 0.8～2.0.
According to preparation method of the present invention, described modified Y molecular sieve preparation method step 1) described in
Ammonium salt is one or several in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium dihydrogen phosphate, ammonium oxalate, described
Modified Y molecular sieve preparation method step 1) in mineral acid be one or more in nitric acid, sulphuric acid, hydrochloric acid；
Described modified Y molecular sieve preparation method step 2) in organic acid be citric acid, oxalic acid, tartaric acid, second two
One or several in amine tetraacethyl, succinic acid, wherein the molar concentration of organic acid is 0.4～5.0mol/L；
Described rare earth metal is La, Ce and one or more in Nd.
According to preparation method of the present invention, described modified Y molecular sieve preparation method step 1) in liquid-solid
Mass ratio 5:1～20:1.
According to preparation method of the present invention, described modified Y molecular sieve preparation method step 1) in solution
Middle NH4 +The molar concentration of ion is 1.0～4.0mol/L, H+The molar concentration of ion is 0.05～0.80mol/L.
According to preparation method of the present invention, described modified Y molecular sieve preparation method step 1) in be dried
Temperature is 100～150 DEG C, and sintering temperature is 480～600 DEG C；Step 2) in baking temperature be 120～180
℃。
According to preparation method of the present invention, described method for preparing catalyst step 2) in organic acid be second
Acid, tartaric acid, citric acid, malic acid, aminotriacetic acid, oxalic acid, maleic acid, CDTA
In one or more, it is preferably one or more in citric acid, tartaric acid, aminotriacetic acid.
According to preparation method of the present invention, described catalyst preparation step 3) in baking temperature be 80～200
DEG C, sintering temperature is 280～580 DEG C, and its preferred baking temperature is 110～150 DEG C, and sintering temperature is 420～520
℃。
The present invention still further provides a kind of fecund hydrocracking catalyst for naphtha in producing Petroleum
Application, it is high that wherein said voluminous hydrocracking catalyst for naphtha is applied to wax oil after sulfuration, passivation
Pressure is hydrocracked in production Petroleum.
Detailed description of the invention
Further illustrate one fecund naphtha type of the present invention below in conjunction with embodiment and comparative example to be hydrocracked
Catalyst and preparation method thereof.
Embodiment-1
The 400g NaY molecular sieve that average crystal grain size is 280nm is put into 3000g NH Han 1.8mol/L4 +
Ion and 0.10mol/L H+In the mixed solution of ion, stirring 4h under 95 DEG C of constant temperatures, sucking filtration,
Deionized water is washed till neutrality, 120 DEG C of dry 8h, 520 DEG C of roasting 3h, repeated exchanged three times, obtains HY
Molecular sieve；HY molecular sieve is placed in hydrothermal aging stove, under 560 DEG C of pressure 0.2MP of temperature at hydro-thermal
Reason 3h；160g powder after hydrothermal treatment consists is loaded in there-necked flask, adds 800mL containing 0.2mol/L
Citric acid and the cerous nitrate solution of 0.006mol/L, at a temperature of 90 DEG C after mechanical agitation backflow 4h, will mix
Close in turbid liquid loading autoclave and after Dynamic Hydrothermal process 12h, carry out sucking filtration separation at a temperature of 160 DEG C,
It is washed to neutrality, in 120 DEG C of dry 8h, i.e. obtains modified Y molecular sieve.Gained modified Y molecular sieve mark
Being designated as GY-1, its physico-chemical property is as shown in Table-1.
Embodiment-2
The 400g NaY molecular sieve that average crystal grain size is 360nm is put into 4000g NH Han 2.0mol/L4 +
Ion and 0.18mol/L H+In the mixed solution of ion, stirring 6h under 90 DEG C of constant temperatures, sucking filtration,
Deionized water is washed till neutrality, 120 DEG C of dry 6h, 540 DEG C of roasting 2h, repeated exchanged three times, obtains HY
Molecular sieve；HY molecular sieve is placed in hydrothermal aging stove, under 600 DEG C of pressure 0.2MP of temperature at hydro-thermal
Reason 3h；150g powder after hydrothermal treatment consists is loaded in there-necked flask, adds 1000mL containing 0.24mol/L
Oxalic acid and the lanthanum nitrate hexahydrate of 0.004mol/L, at a temperature of 90 DEG C after mechanical agitation backflow 4h, will mix
After Dynamic Hydrothermal processes 16h at a temperature of 160 DEG C in turbid liquid loading autoclave, carry out sucking filtration separation,
It is washed to neutrality, in 120 DEG C of dry 8h, i.e. obtains modified Y molecular sieve.Gained modified Y molecular sieve mark
Being designated as GY-2, its physico-chemical property is as shown in Table-1.
Embodiment-3
The 400g NaY molecular sieve that average crystal grain size is 450nm is put into 4500g NH Han 3.0mol/L4 +
Ion and 0.27mol/L H+In the mixed solution of ion, stirring 6h under 90 DEG C of constant temperatures, sucking filtration,
Deionized water is washed till neutrality, 120 DEG C of dry 6h, 540 DEG C of roasting 2h, repeated exchanged two times, obtains HY
Molecular sieve；HY molecular sieve is placed in hydrothermal aging stove, under 660 DEG C of pressure 0.2MP of temperature at hydro-thermal
Reason 2h；150g powder after hydrothermal treatment consists is loaded in there-necked flask, adds 1000mL containing 0.27mol/L
Ethylenediaminetetraacetic acid and the nitric acid niobium solution of 0.005mol/L, at a temperature of 90 DEG C after mechanical agitation backflow 4h,
To mix in turbid liquid loading autoclave and after Dynamic Hydrothermal process 10h, carry out sucking filtration at a temperature of 180 DEG C
Separate, be washed to neutrality, in 150 DEG C of dry 6h, i.e. obtain modified Y molecular sieve.Gained modification Y divides
Son sieve is labeled as GY-3, and its physico-chemical property is as shown in Table-1.
The physico-chemical property of table-1 modified Y molecular sieve
Embodiment-4
By 100.0g modification GY-1 molecular sieve (contents on dry basis 90%), 87.5g amorphous silica-alumina (SiO2's
Mass content 42%, contents on dry basis 80%), 55.6g SB powder body (contents on dry basis 75%), 6.0g sesbania powder
And put into kneading machine mixed grind 10min, by 220.0g by water, nitric acid, Fructus Citri Limoniae after the mixing of 4.0g methylcellulose
Acid, the acid solution of tartaric acid preparation gradually add in dry powder, and first kneading is to toothpaste-squeezable shape thing, spherical by tooth
Orifice plate is extruded, through the stretching of belt transmission equipment, after broken strip, after to obtain diameter 2.5mm tooth through pelletizing spherical
Carrier；By wet for gained carrier prior to health preserving 24h in 30 DEG C of baking ovens, in 150 DEG C of baking ovens, it is dried 8h,
Finally it is placed on Muffle furnace Program and is warming up to 520 DEG C of roasting 3h, i.e. obtain carrier ZT-1.
Embodiment-5
By 109.0g modification GY-2 molecular sieve (contents on dry basis 92%), 87.5g amorphous silica-alumina (SiO2's
Mass content 42%, contents on dry basis 80%), 41.6g macroporous aluminium oxide (contents on dry basis 72%), 6.0g field
Cyanines powder and 4.0g methylcellulose mixing after put into kneading machine mixed grind 10min, by 216.0g by water, nitric acid,
The acid solution of citric acid, oxalic acid preparation gradually adds in dry powder, and first kneading is to toothpaste-squeezable shape thing, by tooth ball
Shape orifice plate is extruded, through the stretching of belt transmission equipment, after broken strip, after obtain diameter 2.5mm tooth ball through pelletizing
Shape carrier；By wet for gained carrier prior to health preserving 24h in 30 DEG C of baking ovens, in 150 DEG C of baking ovens, it is dried 8h,
Finally it is placed on Muffle furnace Program and is warming up to 520 DEG C of roasting 3h, i.e. obtain carrier ZT-2.
Embodiment-6
By 125.0g modification GY-3 molecular sieve (contents on dry basis 88%), 75g amorphous silica-alumina (SiO2Matter
Amount content 42%, contents on dry basis 80%), 40.0g SB powder body (contents on dry basis 72%), 6.0g sesbania powder and
4.0g methylcellulose mixing after put into kneading machine mixed grind 10min, by 226.0g by water, nitric acid, citric acid,
The acid solution of tartaric acid preparation gradually adds in dry powder, and first kneading is to toothpaste-squeezable shape thing, by the spherical orifice plate of tooth
Extrusion, through the stretching of belt transmission equipment, after broken strip, after obtain diameter 2.5mm tooth ball type carrier through pelletizing；
By wet for gained carrier prior to health preserving 24h in 30 DEG C of baking ovens, in 120 DEG C of baking ovens, it is dried 8h, finally puts
Put and be warming up to 520 DEG C of roasting 3h at Muffle furnace Program, i.e. obtain carrier ZT-3.
Embodiment-7
7.5g citric acid (Tianjin, analytical pure), 29.6g six liquid glauber salt is dissolved successively in 50mL deionized water
Acid nickel (Tianjin, analytical pure), 20.2g ammonium metatungstate (Tianjin, analytical pure), 1.8g phosphoric acid, by impregnation liquid
It is settled to 85mL, takes ZT-1 carrier 100.0g and place in maceration tank, pour impregnation liquid into, use equal-volume leaching
After stain 4h, by the carrier after dipping prior to health preserving 12h in 30 DEG C of baking ovens, it is dried in 120 DEG C of baking ovens
8h, is finally placed on Muffle furnace Program and is warming up to 500 DEG C of roasting 2h, i.e. obtain catalyst HC-1, urge
The physico-chemical property of agent refers to table 2.
Embodiment-8
7.5g citric acid (Tianjin, analytical pure), 19.5g six liquid glauber salt is dissolved successively in 50mL deionized water
Acid nickel (Tianjin, analytical pure), 22.9g ammonium metatungstate (Tianjin, analytical pure), 1.8g phosphoric acid, by impregnation liquid
It is settled to 85mL, takes ZT-1 carrier 100.0g and place in maceration tank, pour impregnation liquid into, use equal-volume leaching
After stain 4h, by the carrier after dipping prior to health preserving 12h in 30 DEG C of baking ovens, it is dried in 120 DEG C of baking ovens
8h, is finally placed on Muffle furnace Program and is warming up to 500 DEG C of roasting 2h, i.e. obtain catalyst HC-2, urge
The physico-chemical property of agent refers to table 2.
Embodiment-9
12.0g citric acid (Tianjin, analytical pure), 12.7g alkali formula it is sequentially added in 50mL deionized water
Nickelous carbonate (Tianjin, analytical pure), 18.0g molybdenum trioxide (Tianjin, analytical pure), 1.8g phosphoric acid, will dipping
Liquid is settled to 85mL, takes ZT-1 carrier 100.0g and places in maceration tank, pour impregnation liquid into, uses equal-volume
After dipping 4h, by the carrier after dipping prior to health preserving 12h in 30 DEG C of baking ovens, dry in 120 DEG C of baking ovens
Dry 8h, is finally placed on Muffle furnace Program and is warming up to 480 DEG C of roasting 2h, i.e. obtain catalyst HC-3,
The physico-chemical property of catalyst refers to table 2.
Embodiment-10
7.5g ethylenediaminetetraacetic acid (Tianjin, analytical pure), 21.2g is dissolved successively in 50mL deionized water
Six water nickel nitrates (Tianjin, analytical pure), 17.2g ammonium metatungstate (Tianjin, analytical pure), 1.3g phosphoric acid, will
Impregnation liquid is settled to 84mL, takes ZT-2 carrier 100.0g and places in maceration tank, pours impregnation liquid, employing etc. into
After volume impregnation 4h, by the carrier after dipping prior to health preserving 12h in 30 DEG C of baking ovens, then at 120 DEG C of baking ovens
In be dried 8h, be finally placed on Muffle furnace Program and be warming up to 500 DEG C of roasting 2h, i.e. obtain catalyst HC-4,
The physico-chemical property of catalyst refers to table 2.
Embodiment-11
12.0g citric acid (Tianjin, analytical pure), 8.2g alkali formula carbon it is sequentially added in 50mL deionized water
Acid nickel (Tianjin, analytical pure), 15.3g molybdenum trioxide (Tianjin, analytical pure), 1.7g phosphoric acid, by impregnation liquid
It is settled to 86mL, takes ZT-3 carrier 100.0g and place in maceration tank, pour impregnation liquid into, use equal-volume leaching
After stain 4h, by the carrier after dipping prior to health preserving 12h in 30 DEG C of baking ovens, it is dried in 120 DEG C of baking ovens
8h, is finally placed on Muffle furnace Program and is warming up to 480 DEG C of roasting 2h, i.e. obtain catalyst HC-5, urge
The physico-chemical property of agent refers to table 2.
Comparison example-1
Taking the most industrialized domestic light oil type catalyst is DHC-1.The main acidic components of this catalyst are
A kind of modified Y molecular sieve and amorphous silica-alumina, metal active constituent is Ni-Mo, its main physico-chemical property
As shown in table-2.
Table-2 embodiment catalyst and the physico-chemical property of Reference Example catalyst
Embodiment-12
The present embodiment is introduced by the hydrocracking catalyst prepared by the present invention and the activity rating of comparative catalyst.
Using single hop cascade reaction technique, evaluate on 200mL fixed bed hydrogenation cracking unit, the first reactor is
Hydrogenation pretreatment catalyst, the second reactor is hydrocracking catalyst, and its reaction condition is: reaction pressure
14.0MPa, hydrogen to oil volume ratio 850:1, weighted BMO spaces average reaction temperature is 380 DEG C, volume space velocity 0.8
h-1；Being hydrocracked average reaction temperature is 390 DEG C, volume space velocity 1.2h-1.Evaluating raw material is CNOOC's refining
Factory VGO (85wt%)+CGO (15wt%), its character as shown in Table-3, commenting of hydrocracking catalyst
Valency result is as shown in table-4.
The physical parameter of table-3 raw oil
The catalytic performance of catalyst and comparative example catalyst implemented by table-4
Claims (10)
1. a voluminous hydrocracking catalyst for naphtha, it is characterised in that: described voluminous naphtha type hydrocracking catalyst
Agent composition weight content is: modified Y molecular sieve is 20～40wt%, amorphous silica-alumina 10～30wt%, group vib metal
Be 10～16wt%, group VIII metal be 2～6wt%, auxiliary agent be 0～2wt%, remaining component is alumina powder；Described
Auxiliary agent is the one in F and P or two kinds；
The specific surface area of described voluminous hydrocracking catalyst for naphtha is 320～480m2/ g, pore volume is 0.35～0.55
cm3/ g, pyridine meleic acid amount is 0.50～1.00mmol/g, and B-acid/L acid ratio is 0.5～0.8；
Described modified Y molecular sieve, its character is as follows: average grain diameter is 150～650nm, skeleton SiO2/Al2O3
Mol ratio 10.0～25.0, sodium oxide content < 0.05wt%, cell parameter 2.438～2.450nm, relative crystallinity
95～125%, pyridine-meleic acid amount 0.60～1.2mmol/g, in strong B-acid content account for the 75～85% of total acid content, specific surface
Amass is 550～850m2/ g, pore volume is 0.40～0.85mL/g, and the weight/mass percentage composition of rare-earth oxide is
0.2～1.0wt%；
Its character of described amorphous silica-alumina is as follows: SiO2With Al2O3Mass ratio 0.25～1.0, specific surface area is 350～600
m2/ g, pore volume is 0.80～1.40cm3/ g, most probable pore size 10.0～15.0nm, pyridine meleic acid amount is 0.40～0.80
mmol/g。
Fecund hydrocracking catalyst for naphtha the most according to claim 1, it is characterised in that described voluminous stone
Brain oil type hydrocracking catalyst profile is tooth ball-type.
3. the preparation method of the voluminous hydrocracking catalyst for naphtha described in a claim 1, it is characterised in that bag
Include following steps:
1) preparation of carrier: modified Y molecular sieve, amorphous silica-alumina, alumina powder are mixed homogeneously with extrusion aid, joins
Make the former powder of mixing, add kneading after acid solution become can plasticized body, through being squeezed into bar, stretching, pelletizing obtain
To carrier；
2) preparation of impregnation liquid: organic acid, soluble activating group vib metal and VIII will be sequentially added in deionized water
Race's slaine and the presoma of auxiliary agent, uniform stirring is heated to dissolving, obtains stable impregnation liquid after constant volume；
3) load of active component: use equi-volume impregnating active metal is loaded to step 2) described in carrier on,
Then by the carrier after dipping through health preserving, be dried, obtain hydrocracking catalyst after roasting；
Wherein, described modified Y molecular sieve comprises the following steps:
1) NaY molecular sieve is placed in the solution of ammonium salt-containing and mineral acid, exchange at a temperature of temperature 80～100 DEG C
2～12h, exchange 2～6 times, after drying, roasting, obtain HY molecular sieve；
2) HY molecular sieve is first after processing 0.5～8h in 580～800 DEG C of hydro-thermal stoves, then places containing organic acid and rare earth gold
Belong in the dynamic response still of saline solution, hydrothermal treatment consists 6～48h at a temperature of 80～200 DEG C, obtain modified Y after drying
Molecular sieve.
Method the most according to claim 3, it is characterised in that described vib metals is W or Mo, the
Group VIII metal is Ni, and wherein W/Ni atomic molar ratio is 0.5～1.5, and Mo/Ni atomic molar ratio is 0.8～2.0.
Method the most according to claim 3, it is characterised in that described modified Y molecular sieve preparation method step 1)
Described in ammonium salt be one or several in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium dihydrogen phosphate, ammonium oxalate, institute
State modified Y molecular sieve preparation method step 1) in mineral acid be one or more in nitric acid, sulphuric acid, hydrochloric acid；Institute
State modified Y molecular sieve preparation method step 2) in organic acid be citric acid, oxalic acid, tartaric acid, ethylenediaminetetraacetic acid,
One or several in succinic acid, wherein the molar concentration of organic acid is 0.4～5.0mol/L；Described rare earth metal is
La, Ce and one or more in Nd.
Method the most according to claim 3, it is characterised in that described modified Y molecular sieve preparation method step 1)
In liquid-solid mass ratio 5:1～20:1.
7. according to the method described in claim 3 or 5, it is characterised in that described modified Y molecular sieve preparation method walks
Rapid 1) NH in the solution in4 +The molar concentration of ion is 1.0～4.0mol/L, H+The molar concentration of ion is 0.05～0.80
mol/L。
Method the most according to claim 3, it is characterised in that described modified Y molecular sieve preparation method step 1)
In baking temperature be 100～150 DEG C, sintering temperature is 480～600 DEG C；Step 2) in baking temperature be 120～180
℃。
Method the most according to claim 3, it is characterised in that described method for preparing catalyst step 2) in have
Machine acid is acetic acid, tartaric acid, citric acid, malic acid, aminotriacetic acid, oxalic acid, maleic acid, cyclohexane diamine tetrem
One or more in acid.
10., according to an application for the arbitrary described voluminous hydrocracking catalyst for naphtha of claim 1～2, it is special
Levying and be, described voluminous hydrocracking catalyst for naphtha is applied to wax oil high-pressure hydrocracking after sulfuration, passivation
Produce in Petroleum.
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| CN112403507A (en) * | 2019-08-20 | 2021-02-26 | 中国石油天然气股份有限公司 | Productive naphtha type hydrocracking catalyst and application thereof |
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| CN112625742A (en) * | 2019-09-24 | 2021-04-09 | 中国石油天然气股份有限公司 | Hydro-upgrading treatment method for poor diesel oil |
| CN112742458A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN112742460A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Hydrocracking catalyst, preparation method and application thereof |
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