CN109954513A - A kind of reduction-state bimetallic catalyst for hydrocracking diesel oil - Google Patents
A kind of reduction-state bimetallic catalyst for hydrocracking diesel oil Download PDFInfo
- Publication number
- CN109954513A CN109954513A CN201711406397.4A CN201711406397A CN109954513A CN 109954513 A CN109954513 A CN 109954513A CN 201711406397 A CN201711406397 A CN 201711406397A CN 109954513 A CN109954513 A CN 109954513A
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- China
- Prior art keywords
- catalyst
- preparation
- diesel oil
- ammonium
- zeolite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 52
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 25
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002808 molecular sieve Substances 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 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 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 14
- 229910017464 nitrogen compound Inorganic materials 0.000 claims abstract description 13
- 150000002830 nitrogen compounds Chemical class 0.000 claims abstract description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 6
- RFQDDXWZZVRLKO-UHFFFAOYSA-N benzo[g]quinoline Chemical compound N1=CC=CC2=CC3=CC=CC=C3C=C21 RFQDDXWZZVRLKO-UHFFFAOYSA-N 0.000 claims abstract description 3
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 238000002360 preparation method Methods 0.000 claims description 42
- 238000005984 hydrogenation reaction Methods 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 20
- 239000010457 zeolite Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 229910021536 Zeolite Inorganic materials 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 14
- 150000003863 ammonium salts Chemical class 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000002161 passivation Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- -1 nitrogenous compound Chemical class 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 claims description 4
- 206010021143 Hypoxia Diseases 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 208000018875 hypoxemia Diseases 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 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
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 235000021050 feed intake Nutrition 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 238000010129 solution processing Methods 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims 1
- 239000005695 Ammonium acetate Substances 0.000 claims 1
- 229940043376 ammonium acetate Drugs 0.000 claims 1
- 235000019257 ammonium acetate Nutrition 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 9
- 230000002378 acidificating effect Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005336 cracking Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 abstract description 4
- 239000010953 base metal Substances 0.000 abstract description 2
- 238000002513 implantation Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000003776 cleavage reaction Methods 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000007017 scission Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000010219 correlation analysis Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000010913 used oil Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 238000005406 washing Methods 0.000 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 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 240000005702 Galium aparine Species 0.000 description 1
- 235000014820 Galium aparine Nutrition 0.000 description 1
- UHIFJPAQGVQMPP-UHFFFAOYSA-N N.[Si+4] Chemical compound N.[Si+4] UHIFJPAQGVQMPP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000131316 Panax pseudoginseng Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 241000612118 Samolus valerandi Species 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 241000519996 Teucrium chamaedrys Species 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005303 weighing 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
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/54—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A kind of reduction-state bimetallic catalyst for hydrocracking diesel oil, it is as carrier while to load base metal and noble metal hydrogenating component by the first modified zeolite, the second modified zeolite and aluminium oxide, after being restored with hydrogen partial pressure, then it is passed through and is obtained after the processing of at least one of pyridine, quinoline, isoquinolin, naphthazine and aza-phenanthrenes gaseous nitrogen compound.In the acidity of catalyst cracking component-molecular sieve implantation high activity reduction-state bimetallic catalyst for hydrocracking diesel oil, makes open loop while adding hydrogen to be saturated of the condensed-nuclei aromatics in diesel oil, simplify process flow, equipment investment can be saved, save operating cost.And be passivated using acid centre of the gaseous nitrogen compound to catalyst, the acidic site of molecular sieve is weakened, alkylolysis reaction is reduced, improves purpose product quality and yield.
Description
Technical field
The present invention relates to a kind of reduction-state bimetallic catalyst for hydrocracking diesel oil, are related to preparation method, more particularly to
A kind of catalyst of diesel oil condensed-nuclei aromatics hydro-conversion, belongs to hydrogenation catalyst technical field.
Background technique
The main component of catalytic diesel oil is condensed-nuclei aromatics, and Cetane number is very low.Enhancing with people to environmental consciousness,
Environmental protection institution also proposed harsher requirement to diesel oil index, define the arene content and minimum hexadecane of diesel oil
Value.Therefore, market needs low fragrant high cetane number diesel production technology.
Chinese patent CN96109877.5 discloses a kind of catalyst for hydrocracking diesel oil, it is to be provided to add hydrogen by base metal
Activated centre, molecular sieve provide acidic cleavage center, disclose a kind of diesel modifying technique in conjunction with Chinese patent CN1156752A
Technology, by controlling reaction system N+ α NH3Value weakens acidic zeolite position in the appropriate range, controls alkyl cleavage reaction,
It realizes diesel oil open loop not chain rupture in hydroconversion process, improves Cetane number.The technology has more set commercial plants to make at home
With there are problems to be: its open loop not chain rupture is to be unable to Arene removal to an aromatic ring hydrocracking in condensed-nuclei aromatics；
It improves Cetane number and also only carries out in aromatic hydrocarbons, limited extent.In order to meet new spec index request, product also needs
Further take off virtue.
Summary of the invention
To solve the de- virtue of diesel oil in the prior art and improving defect existing for the catalyst in Cetane number, the present invention is quasi- to be mentioned
For a kind of reduction-state bimetallic catalyst for hydrocracking diesel oil, by acidic cleavage group used in catalyst for hydrocracking diesel oil
Point --- molecular sieve is implanted into a kind of high-activity hydrogenation saturation catalyst agent, makes the condensed-nuclei aromatics in catalytic diesel oil that hydrogen added to be saturated
While also carry out ring-opening reaction, simplify low fragrant high cetane number diesel production process；Utilize gaseous nitrogen compound molecule bone
Nitrogen weakens acidic zeolite position in frame, and catalyst is made to have very strong opening cyclic paraffins performance and very weak alkylolysis
Performance.
To realize the above-mentioned technical purpose, the invention adopts the following technical scheme:
The technical purpose of first aspect present invention is to provide a kind of preparation side of reduction-state bimetallic catalyst for hydrocracking diesel oil
Method, comprising the following steps:
(1) it prepares the first modified zeolite: soluble ammonium salting liquid being contacted with NaY zeolite, is stirred to react 0.5 in 50~100 DEG C
~5 hours, filtering was added ammonium salt solution and repeats the above reaction, again until Na in NaY zeolite2O mass content reaches 2.0%
Below；By ammonium salt solution, treated that zeolite is placed in hydro-thermal process furnace carries out steam treatment, is warming up to 250~850 DEG C, rises
Be passed through nitrogen during temperature, keep temperature to carry out hydro-thermal process 0.5 hour or more later, the zeolite after steam treatment using
Contain H+And NH4 +Two kinds of cationic buffer solution processing, obtain Modified NaY Zeolite；Obtain the first modified zeolite；
(2) it prepares the second modified zeolite: raw material Y type molecular sieve and water being mixed and made into slurries, 50~120 DEG C are warming up to, with six
Ammonium fluosilicate haptoreaction isolates molecular sieve pulp and is filtered, washed and dried, obtains low-Na and high-Si Y-type molecular sieve,
Temperature is 600 ~ 650 DEG C, under 0.05 ~ 0.10MPa of pressure, hydro-thermal process 0.5 ~ 1.0 hour, obtains the second modified zeolite；
(3) prepare catalyst carrier: will (1) preparation the first modified zeolite, (2) preparation the second modified zeolite, aluminium oxide and
Extrusion aid mixing through kneading, molding, drying and roasts obtained catalyst carrier, first, second modified zeolite and aluminium oxide
Mass ratio be 30 ~ 70:10 ~ 30:15 ~ 50；
(4) it loads hydrogenation component: catalyst carrier prepared by (3) is successively supported into non-noble metal hydrogenation component and noble metal hydrogenation
Oxidation state bimetallic catalyst for hydrocracking diesel oil is made in component；
(5) drying of oxidation state bimetallic catalyst for hydrocracking diesel oil is made in (4), after restoring with hydrogen partial pressure, then is passed through choosing
From at least one of pyridine, quinoline, isoquinolin, naphthazine and aza-phenanthrenes gaseous nitrogen compound, temperature is at 420 ~ 550 DEG C
Reason, is made the reduction-state bimetallic catalyst for hydrocracking diesel oil.
Further, in above-mentioned preparation method, the reduction of hydrogen partial pressure described in step (5) uses hydrogen and indifferent gas
The mixed gas of body, the volume fraction of hydrogen is 1% ~ 99%, preferably 20% ~ 80%, more preferably 60% ~ 80% in mixed gas；
The inert gas is selected from least one of helium, neon, argon and krypton；Reduction temperature be 400~550 DEG C, preferably 420 ~ 550
DEG C, more preferably 480~510 DEG C；Pressure is 0.01 ~ 2.00Mpa；Mixed gas and catalyst 100 ~ 1500:1 by volume,
Preferably 500 ~ 1200:1 is mixed, and the recovery time is 1 ~ 96 hour, preferably 24 ~ 72 hours.
Further, the hydrogen in the mixed gas, which can be selected, falls C by adsorbing and removing or hydrogenolysis2 +The reformation of hydrocarbon
Hydrogen, the hydrogen of refinery's pressure-variable adsorption separator production or the electrolysis hydrogen by molecular sieve dehydration.
Further, in above-mentioned preparation method, gaseous nitrogen compound described in step (5) is preferably quinoline or pyridine.Institute
The intake for stating gaseous nitrogen compound is the 0.05% ~ 1% of catalyst quality, preferably 0.1% ~ 0.3% in terms of nitrogen.With gas
The temperature of state nitrogen compound processing is preferably 450 ~ 550 DEG C, and more preferably 480~510 DEG C；Pressure is 0.01~2.00MPa；Gas
Agent ratio is 100~1500(h-1), preferably 100~1200(h-1)；Reaction time is 0.5~3h, preferably 0.5~1h.This place
Stating the reaction time is feed time and the isothermal reaction time of system heating-up time for removing material.
Further, dry successively dry including negative pressure drying, hypoxemia nitrogen described in step (5) in above-mentioned preparation method
Dry and oxygen-enriched nitrogen is dry.Wherein, the operation item of the negative pressure drying are as follows: vacuum degree > 66kPa, temperature are 200~300 DEG C,
It is preferred that 230~270 DEG C；Constant temperature time is 2~8h, preferably 3~6h.The hypoxemia nitrogen dries gases used middle oxygen content
0.2~1.5 v%, preferably 0.5~1 v%；Drying temperature is 270~420 DEG C, and gas agent ratio is 100~1500 h-1, preferably
500~1200 h-1, drying time is 2~8h, preferably 3~6h.The oxygen-enriched nitrogen it is dry it is gases used in oxygen content be
3v%~10v%, preferably 5v%~8v%；Drying temperature is 400~480 DEG C, preferably 420~460 DEG C；Gas agent ratio be 100~
1500 h-1, preferably 500~1200 h-1；Constant temperature time is 2~8h, preferably 3~6h.
Further, in above-mentioned preparation method, solubility ammonium salt described in (1) is selected from ammonium nitrate, ammonium sulfate, acetic acid
At least one of ammonium and ammonium chloride, ammonium salt concentration be 0.5 ~ 5mol/L, ammonium salt solution mix with zeolite by weight be 0.1 ~
10:1.It is handled by ammonium salt solution, Na2The control preferably 1.0% of O mass content is hereinafter, more preferably 0.5% or less.
Further, in above-mentioned preparation method, the temperature that hydro-thermal process is carried out in (1) is preferably 450 ~ 750 DEG C；System
P in systemH2O/ P is 0.2 ~ 0.9, preferably 0.3 ~ 0.8, PNH3/ P is 0.1 ~ 0.8, preferably 0.2 ~ 0.7, NH therein3It is by ammonium
The NH that molecular sieve after exchange carries4 +Ion volatilization generates.The time of hydro-thermal process is preferably 1 ~ 5 hour.
Further, in above-mentioned preparation method, H in buffer solution in (1)+It can be provided by acid, NH4 +It can be mentioned by ammonium salt
For；The pH of buffer solution is 4 ~ 6, preferably 4 ~ 5.
Further, in above-mentioned preparation method, the first modified zeolite has the feature that aperture is greater than 1.7 in (1)
×10-10The pore volume of rice accounts for 45% or more total pore volume, and surface area is greater than 750 ~ 900m2/g；SiO2/Al2O3Than 8 ~ 15；Structure cell ginseng
2.423 ~ 2.545nm of number, crystallinity 95 ~ 110%, sodium weight content 0.05% ~ 0.25%, pyridine adsorption IR-TPD total acid content 0.5 ~
1.5mmol/g, DTA structure destroy 920 ~ 1100 DEG C of peak temperature.
Further, in above-mentioned preparation method, in (2) in the second modified zeolite preparation process, by Y type molecular sieve:
Ammonium hexafluorosilicate mass ratio is that 10:2 ~ 5 feed intake.Further, the additional amount of ammonium hexafluorosilicate, on an hourly basis every 100 grams of Y types
Molecular sieve is added most 30 grams, and preferably 5~25 grams of speed carry out.
Further, in above-mentioned preparation method, Y type molecular sieve described in (2) is NH4NaY molecular sieve, Na2O content
Best≤5m%.Reaction time is preferably 0.5 ~ 5h.
Further, in above-mentioned preparation method, the second modified zeolite is NH in (2)4NaY molecular sieve hexafluorosilicic acid
The low sodium Y type molecular sieve of high silicon of aqueous ammonium processing, is preferably modified according to the method introduced in CN90102645.X, then
It is obtained with hydro-thermal process.The lattice constant of second modified zeolite is generally 2.449-2.453nm, crystallinity > 95%, SiO2/
Al2O3Molar ratio 5-40.
Further, in above-mentioned preparation method, aluminium oxide described in (3) is oxygen general in hydrogenation catalyst field
Change aluminum feedstock, includes but are not limited to the HT of SB powder aluminium oxide, HP aluminium oxide or high temperature precipitations the method production of Ziegler method production
Aluminium oxide.
Further, in above-mentioned preparation method, extrusion aid described in (3) is selected from sesbania powder, citric acid, oxalic acid and fibre
Tie up at least one of element.
Further, in above-mentioned preparation method, (3) are described to be shaped to sheet, spherical, cylindrical bars or irregular bar (such as
Clover, bunge bedstraw herb etc.), preferably cylindrical bars or irregular bar.
Further, in above-mentioned preparation method, drying condition described in (3) are as follows: dry 2 ~ 12 at 110 DEG C ± 10 DEG C
Hour.The condition of the roasting be 450 ~ 750 DEG C of temperature, preferably 500 ~ 650 DEG C, calcining time be 2 ~ 24 hours, preferably 2
~ 8 hours.
Further, in above-mentioned preparation method, non-noble metal hydrogenation group described in (4) is selected from Ni, W, Mo and Co
At least one of, the noble metal hydrogenating component is selected from least one of Ru, Rh, Pd, Os, Ir and Pt, with metallic element
Mass content meter in the catalyst, the loading of the non-noble metal hydrogenation component are 0.5% ~ 10.0%, and the noble metal adds
The loading of hydrogen component is 0.1% ~ 2.0%.
Further, in above-mentioned preparation method, infusion process carrying metal component is used in the 4th step, when dipping will contain
The maceration extract of metal component is mixed with catalyst carrier with 1.5 ~ 3:1 volume ratio, is impregnated 6 ~ 24 hours, and stir simultaneously, pH control
System is dried in the shade 8 ~ 24 hours after 2 ~ 10, dipping, then dry at 80 ~ 120 DEG C, is roasted at 550 ~ 590 DEG C.
The technical purpose of second aspect of the present invention is to provide is urged by the reduction-state bimetallic diesel oil hydrogenation conversion of above method preparation
Agent.
Catalyst prepared by the present invention, by acidic cleavage component used in catalyst for hydrocracking diesel oil --- molecular sieve is planted
Enter in a kind of high-activity hydrogenation saturation catalyst agent, opens the condensed-nuclei aromatics in catalytic diesel oil also while adding hydrogen to be saturated
Ring reaction simplifies low fragrant high cetane number diesel production process；In catalyst of the invention, gaseous nitrogen compound molecule is utilized
Nitrogen weakens acidic zeolite position in skeleton, makes catalyst that there is very strong opening cyclic paraffins performance and very weak alkyl to split
Solve performance.
The technical purpose of third aspect present invention is to provide application of the above-mentioned catalyst in diesel oil hydrogenation conversion.
When above-mentioned reduction-state bimetallic catalyst for hydrocracking diesel oil is converted for diesel oil hydrogenation, need to carry out before use
Ammonia passivation and presulfurization.It wherein needs to carry out ammonia passivation on large industrialized device, the midget plant in laboratory can omit this step
Suddenly.The ammonia passivation is to inject ammonia in recyclegas or can generate the nitrogenous compound of ammonia, passivation temperature 230 in hydrogen
~300 DEG C, passivation time is 1.0~10.0 hours.Its injection rate is calculated as the 3.0~7.0% of catalyst quality with nitrogen.Institute
Stating presulfurization is that sulfur-containing compound is injected in recyclegas, pre-curing temperature be 400~430 DEG C, prevulcanisation time be 0.5~
3.0 hour.Sulfur-containing compound used in presulfurization is that H can be generated in hydrogen2The compound of S, preferably H2S, the note of sulfur-containing compound
Enter amount with H2S is calculated as the 0.1~0.3% of catalyst quality.After ammonia passivation and presulfurization, reduction-state bimetallic bavin of the present invention
Oily hydrogenation conversion catalyst can be contacted with feedstock oil, produce low fragrant high cetane number diesel oil.
When carrying out the conversion of above-mentioned diesel oil hydrogenation, diesel oil distillate is the straight(-run) diesel distillate or stone that boiling range is 160 ~ 360 DEG C
The diesel oil distillate that boiling range is 160 ~ 360 DEG C in coking, catalytic cracking process production in oil processing.The operating condition of hydrogenation process
Reaction are as follows: 2 ~ 15MPa of pressure, preferably 3 ~ 10MPa；200 ~ 400 DEG C of reaction temperature, preferably 250 ~ 350 DEG C；Volume when reaction solution
0.5 ~ 5.0h of air speed-1, preferably 1.0 ~ 3.0h-1, reaction hydrogen to oil volume ratio is 500 ~ 1800, preferably 800 ~ 1200.
When carrying out the conversion of above-mentioned diesel oil hydrogenation, it is desirable that nitrogen content < 600 μ g/g, preferably < 300 μ g/g in feedstock oil, more
It is preferred that < 100 μ g/g.
Compared with prior art, present invention has the advantage that
(1) present invention is by acidic cleavage component --- molecular sieve is implanted into high activity reduction-state bimetallic catalyst for hydrocracking diesel oil
In, make open loop while adding hydrogen to be saturated of the condensed-nuclei aromatics in diesel oil, simplify process flow, equipment investment, section can be saved
Save operating cost.
(2) present invention will have weakly alkaline organic using the acidity of molecular sieve in bimetallic catalyst for hydrocracking diesel oil
Nitrogen compound is drawn into molecular sieve pore passage.Have the characteristics that dehydrogenation functionality using noble metal, allows organic nitrogen under dehydrogenation condition
Compound dehydrogenation, remaining skeleton are deposited in molecular sieve pore passage, and alkali center (nitrogen-atoms) can influence molecular sieve for a long time
It is acid.Because of alkaline nitrogen molecular (having group around nitrogen-atoms), the basic center (nitrogen of organonitrogen compound molecular skeleton after dehydrogenation
Atom) with the acid centre of molecular sieve always there is certain distance, alkali center only will affect without shielding acid site, and one
Alkali center can influence multiple acid sites, this can control the acid strength in acid site by adjusting the quantity at alkali center, make
The acidic site of molecular sieve weakens, and reduces alkylolysis reaction, improves purpose product quality and yield.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Oxidation state bimetallic catalyst for hydrocracking diesel oil used in following embodiment is prepared by the following method:
(1) it prepares the first modified zeolite: being placed in every liter of (NH containing 150g for 100 grams of industrial NaY zeolite4)2SO4It is water-soluble
It stirs, be warming up to 90 ~ 100 DEG C and kept for 1 hour in liquid, filtering, after repeating aforesaid operations three times, washing.By what is handled above
Product is placed in tube furnace, and 500 DEG C are warming up to while being passed through nitrogen, stops logical nitrogen, is kept pressure in 0.1MPa, is maintained 2
Temperature fall after hour.The product obtained after hydro-thermal process is placed in 1 liter of CH containing 154g3COONH4With 100g CH3The water of COOH
It is handled in solution, is then filtered, washed, dries to get the first modified zeolite, physico-chemical property is listed in table 1；
(2) it prepares the second modified zeolite: weighing the raw material NH of ammonium exchange degree about 80%, calcination loss of weight 27.1%4NaY molecular sieve
It 2057.6 grams, is put into white steel drum, is beaten with 9 liters of distilled water, and be heated to 95 DEG C under agitation, then with uniform
Speed the solution prepared by 495.0 grams of ammonium hexafluorosilicates and 3500 milliliters of distilled water is added dropwise, be added dropwise with 2 hour time,
This rear slurry maintains 2 hours under 95 DEG C of stirring conditions, stops stirring and stands about after ten minutes, is isolated and be deposited in decantation
Fluorine (silicon) ammonium aluminate sodium crystal of white steel drum bottom.The molecular sieve pulp being poured out is filtered, and with about 30 liters of hot distilled waters
It is rinsed when filtering, then takes out filter cake and be dried to get product low-Na and high-Si Y-type molecular sieve.By the molecular sieve in temperature
It is 650 DEG C, under the pressure of pressure 0.1MPa, hydro-thermal process 1 hour to get the second modified zeolite.Its physico-chemical property is shown in Table 1；
Table 1.
(3) catalyst carrier is prepared: the second modified zeolite 75.5g of the first modified zeolite 113g, (2) preparation that take (1) to prepare
Mix and roll with aluminium oxide 120g, extrusion, 110 DEG C drying 4 hours, 550 DEG C roast 5 hours.
(4) it loads hydrogenation component: the catalyst carrier that (3) obtain being impregnated with nickel nitrate solution, obtains Ni weight content
For 3.8% carrier, 110 DEG C drying 4 hours, 550 DEG C roast 5 hours；Pd (NH is used again4)NO3Solution impregnates above-mentioned carrier containing Ni,
110 DEG C drying 4 hours, 550 DEG C roast 5 hours；Obtaining Pd weight content is that the oxidation state that 0.8%, Ni weight content is 3.8% is double
Metal catalyst for hydrocracking diesel oil C.
Following embodiment prepares reduction-state bimetallic catalyst for hydrocracking diesel oil with catalyst C:
Embodiment 1
Take 40 milliliters of catalyst C(31.3g) it is packed into the reactor that 100 milliliters of single tube hydrogen once pass through device, on device
It heats up and vacuumizes, it is 4 hours dry under the conditions of 250 DEG C of temperature, vacuum degree > 66kPa；With the nitrogen vacuum breaker of the oxygen containing 1v%,
And 400 DEG C are warming up to the speed of 20 DEG C/h under the conditions of pressure 0.1MPa, tail gas amount 48NL/h, use the nitrogen of the oxygen containing 6v% instead,
In pressure 0.1MPa, tail gas amount 48NL/h, under the conditions of constant temperature 4 hours, replaced with the mixed gas of 70v% hydrogen and 30v% argon gas
Fall nitrogen, adjust pressure 0.1MPa, tail gas amount 28NL/h, is warming up to 510 DEG C, carries out reduction 48 hours；With 30 DEG C/h of speed
Rate is cooled to 420 DEG C；Adjustment pressure 0.5MPa, circulating flow rate 48NL/h, contain 0.3 gram of quinoline with 4 hours time injection 320mL
The hexamethylene of quinoline；520 DEG C of constant temperature 0.5h are warming up to the speed of 15 DEG C/h, obtain reduction-state bimetallic diesel oil hydrogenation conversion catalyst
Agent RC1, property are listed in table 2.
Table 2.
Embodiment 2
In addition to the dosage of quinoline is changed to 0.6 gram, other operations are the same as embodiment 1.Obtain catalyst RC2.
Embodiment 3
In addition to the dosage of quinoline is changed to 0.9 gram, other operations are the same as embodiment 1.Obtain catalyst RC3.
The catalyst of above embodiments is used for diesel oil hydrogenation transformation experiment:
The catalyst of embodiment 1 ~ 3 is subjected to presulfurization；Keeping temperature is 420 DEG C, adjusts pressure 0.5MPa, circulating flow rate
48NL/h contains the hexamethylene of 0.032 gram of sulphur into vulcanization oil mass 80mL/h, with 4 hours time injection 320mL；With 15 DEG C/h
Speed be cooled to 320 DEG C, adjustment pressure 8.0MPa, circulating flow rate 48NL/h, by the oil inlet quantity of 45g/h into feedstock oil, raw material
Oil is by 160~360 DEG C of fraction of triumph catalytic diesel oil of desulfuration purification.It operates 300 hours post-samplings and makees correlation analysis, test
Raw materials used oil nature is shown in Table 3, and test result is shown in Table 4.
3. raw material oil nature of table
Comparative example 1
The step of being introduced with embodiment 1 only carries out reduction process, and is passed through quinoline treatment process without final step.?
DRC is denoted as to catalyst editorial afterword.
Catalyst DRC is subjected to presulfurization；Keeping temperature is 420 DEG C, adjusts pressure 0.5MPa, circulating flow rate 48NL/h,
Contain the hexamethylene of 0.032 gram of sulphur into vulcanization oil mass 80mL/h, with 4 hours time injection 320mL；It is dropped with the speed of 15 DEG C/h
Temperature to 320 DEG C, adjustment pressure 8.0MPa, circulating flow rate 48NL/h, by the oil inlet quantity of 45g/h into feedstock oil.After operating 300 hours
Correlation analysis is made in sampling, tests raw materials used oil as by 160~360 DEG C of fractions of triumph catalytic diesel oil of desulfuration purification, test
It the results are shown in Table 4.
Table 4.
Comparative example 2
Hydro-conversion is carried out to diesel oil using the common hydrocatalyst for saturating BHC+3963 catalyst of the prior art:
Wherein, the preparation process of hydrocatalyst for saturating BHC is as follows:
The first step, NaY zeolite are modified: being placed in every liter of (NH containing 150g for 100 grams of industrial NaY zeolite4)2SO4It is water-soluble
It stirs, be warming up to 90 ~ 100 DEG C and kept for 1 hour in liquid, filtering, after repeating aforesaid operations three times, washing.By what is handled above
Product is placed in tube furnace, and 500 DEG C are warming up to while being passed through nitrogen, stops logical nitrogen, is kept pressure in 0.1MPa, is maintained 2
Temperature fall after hour.The product obtained after hydro-thermal process is placed in 1 liter of CH containing 154g3COONH4With 100g CH3The water of COOH
It is handled in solution, is then filtered, washed, dries to get Modified NaY Zeolite.
Second step, it is alumina modified: to take SB powder aluminium oxide (Al2O3Aluminium powder, contents on dry basis 75%) 120g and 100mL concentration is
The nitric acid glue of 0.2M melts, and obtained glue is melted object in the heatproof container of a capping, puts into hydro-thermal process furnace, is heated to
55 DEG C, constant temperature 72 hours, modified aluminas is made.
Third step prepares catalyst carrier: the modification for Modified NaY Zeolite 222g and the second step preparation for taking the first step to prepare
1 220g of alumina G mixing roll, extrusion, 110 DEG C drying 4 hours, 550 DEG C roasting 5 hours.
Step 4: load hydrogenation component: the catalyst carrier that third step is obtained is impregnated with nickel nitrate solution, obtains Ni weight
Measure content be 3.8% carrier, 110 DEG C drying 4 hours, 550 DEG C roasting 5 hours；Pd (NH is used again4)NO3Solution dipping is above-mentioned to urge
Agent, obtaining Pt weight content is the bimetallic high-activity hydrogenation saturation catalyst BHC that 0.8%, Ni weight content is 3.8%.Its
Property is shown in Table 5.
To above-mentioned 160~360 DEG C of fractions of triumph catalytic diesel oil by desulfuration purification carry out plus hydrogen saturation, evaluation condition and
As a result it is listed in table 6.
Secondly, above-mentioned plus hydrogen saturation generates oil as raw material with the, then with 3963 type selecting catalyst for cracking (Sinopec
Fushun branch company, joint-stock company catalyst plant industrial production) carry out open loop to it, catalyst composition is shown in Table 7, the condition of evaluation and
It the results are shown in Table 8.
5. BHC catalyst of table composition
Table 6.
Table 7.
Table 8.
From the above results, it can be seen that the method for the prior art not only complex process, and arene content is higher than technical solution of the present invention,
Cetane number is lower than technical solution of the present invention, and effect is nothing like catalyst of the invention.
Comparative example 3
Using the triumph catalytic diesel oil before being refined in above-mentioned table 3 as raw material, commented on FH-98/3963 type selecting catalyst for cracking
(FH-98 is Shenyang Catalyst Plant's industrial catalyst for refining to valence, it cooperates 3963 catalyst on mostly set commercial plant
Used), the condition of evaluation and it the results are shown in Table 9.
Table 9.
As it can be seen that the FH-98/3963 type selecting catalyst for cracking combination being industrially used in the prior art, with catalysis of the invention
Agent effect is mutually far short of what is expected.
Claims (19)
1. a kind of preparation method of reduction-state bimetallic catalyst for hydrocracking diesel oil, comprising the following steps:
(1) it prepares the first modified zeolite: soluble ammonium salting liquid being contacted with NaY zeolite, is stirred to react 0.5 in 50~100 DEG C
~5 hours, filtering was added ammonium salt solution and repeats the above reaction, again until Na in NaY zeolite2O mass content reach 2.0% with
Under；By ammonium salt solution, treated that zeolite is placed in hydro-thermal process furnace carries out steam treatment, is warming up to 250~850 DEG C, heating
It is passed through nitrogen in the process, keeps temperature to carry out hydro-thermal process 0.5 hour or more later, the zeolite after steam treatment is using containing
There is H+And NH4 +Two kinds of cationic buffer solution processing, obtain Modified NaY Zeolite；Obtain the first modified zeolite；
(2) it prepares the second modified zeolite: raw material Y type molecular sieve and water being mixed and made into slurries, 50~120 DEG C are warming up to, with six
Ammonium fluosilicate haptoreaction 0.1 ~ for 24 hours, it isolates molecular sieve pulp and is filtered, washed and dried, obtain low-Na and high-Si Y-type point
Son sieve is 600 ~ 650 DEG C in temperature, under 0.05 ~ 0.10MPa of pressure, hydro-thermal process 0.5 ~ 1.0 hour, obtains the second modified boiling
Stone；
(3) prepare catalyst carrier: will (1) preparation the first modified zeolite, (2) preparation the second modified zeolite, aluminium oxide and
Extrusion aid mixing through kneading, molding, drying and roasts obtained catalyst carrier, first, second modified zeolite and aluminium oxide
Mass ratio be 30 ~ 70:10 ~ 30:15 ~ 50；
(4) it loads hydrogenation component: catalyst carrier prepared by (3) is successively supported into non-noble metal hydrogenation component and noble metal hydrogenation
Oxidation state bimetallic catalyst for hydrocracking diesel oil is made in component；
(5) drying of oxidation state bimetallic catalyst for hydrocracking diesel oil is made in (4), after restoring with hydrogen partial pressure, then is passed through choosing
From at least one of pyridine, quinoline, isoquinolin, naphthazine and aza-phenanthrenes gaseous nitrogen compound, temperature is at 420 ~ 550 DEG C
Reason, is made the reduction-state bimetallic catalyst for hydrocracking diesel oil.
2. preparation method according to claim 1, which is characterized in that the reduction of hydrogen partial pressure described in step (5) uses
It is the mixed gas of hydrogen and inert gas, the volume fraction of hydrogen is 1% ~ 99%, preferably 20% ~ 80% in mixed gas, more
Preferably 60% ~ 80%.
3. preparation method according to claim 1, which is characterized in that the temperature of reduction described in step (5) be 400~
550 DEG C, pressure is 0.01 ~ 2.00Mpa；100 ~ 1500:1 is mixed mixed gas by volume with catalyst, the recovery time
It is 1 ~ 96 hour.
4. preparation method according to claim 1, which is characterized in that gaseous nitrogen compound described in step (5) is quinoline
Or pyridine.
5. preparation method according to claim 1, which is characterized in that gaseous nitrogen compound described in step (5) is passed through
Amount is the 0.05% ~ 1% of catalyst quality in terms of nitrogen.
6. preparation method according to claim 1, which is characterized in that the temperature handled in step (5) with gaseous nitrogen compound
Degree is 450 ~ 550 DEG C, and pressure is 0.01~2.00MPa, and gas agent ratio is 100~1500h-1, the reaction time is 0.5~3h.
7. preparation method according to claim 1, which is characterized in that dry successively dry including negative pressure described in step (5)
Dry, the dry and oxygen-enriched nitrogen drying of hypoxemia nitrogen.
8. preparation method according to claim 1, which is characterized in that solubility ammonium salt described in step (1) is selected from nitric acid
At least one of ammonium, ammonium sulfate, ammonium acetate and ammonium chloride, are handled by ammonium salt solution, Na2O mass content is controlled 1.0%
Below.
9. preparation method according to claim 1, which is characterized in that P in system when hydro-thermal process in step (1)H2O/ P is
0.2~0.9。
10. preparation method according to claim 1, which is characterized in that the pH of buffer solution is 4 ~ 6 in step (1).
11. preparation method according to claim 1, which is characterized in that the second modified zeolite preparation process in step (2)
In, by Y type molecular sieve: ammonium hexafluorosilicate mass ratio is that 10:2 ~ 5 feed intake；The additional amount of ammonium hexafluorosilicate, on an hourly basis every 100
Gram Y type molecular sieve is added most 30 grams, and preferably 5~25 grams of speed carry out.
12. preparation method according to claim 1, which is characterized in that the sorting of non-noble metal hydrogenation group described in step (4)
From at least one of Ni, W, Mo and Co, the noble metal hydrogenating component in Ru, Rh, Pd, Os, Ir and Pt at least one
Kind.
13. preparation method according to claim 12, which is characterized in that with the mass content of metallic element in the catalyst
Meter, the loading of the non-noble metal hydrogenation component are 0.5% ~ 10.0%, the loading of the noble metal hydrogenating component is 0.1% ~
2.0%。
14. the reduction-state bimetallic catalyst for hydrocracking diesel oil of the preparation of method described in claim 1 ~ 13 any one.
15. application of the catalyst described in claim 14 in diesel oil hydrogenation conversion.
16. application according to claim 15, which is characterized in that when the catalyst is converted for diesel oil hydrogenation, make
With preceding needing to carry out ammonia passivation and presulfurization.
17. application according to claim 16, which is characterized in that ammonia passivation be injected in recyclegas ammonia or
The nitrogenous compound of ammonia can be generated in hydrogen, passivation temperature is 230~300 DEG C, and passivation time is 1.0~10.0 hours, note
Enter amount and is calculated as the 3.0~7.0% of catalyst quality with nitrogen.
18. application according to claim 16, which is characterized in that the presulfurization is to inject Containing Sulfur in recyclegas
Object is closed, pre-curing temperature is 400~430 DEG C, and prevulcanisation time is 0.5~3.0 hour, and the injection rate of sulfur-containing compound is with H2S
It is calculated as the 0.1~0.3% of catalyst quality.
19. application according to claim 15, which is characterized in that the catalyst diesel oil hydrogenation converts the reaction for being
Condition are as follows: 2 ~ 15MPa of pressure, 200 ~ 400 DEG C of reaction temperature, 0.5 ~ 5.0h of volume space velocity when reaction solution-1, react hydrogen to oil volume ratio
It is 500 ~ 1800.
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