CN107286988B - A kind of process handling poor ignition quality fuel - Google Patents
A kind of process handling poor ignition quality fuel Download PDFInfo
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- CN107286988B CN107286988B CN201610225966.4A CN201610225966A CN107286988B CN 107286988 B CN107286988 B CN 107286988B CN 201610225966 A CN201610225966 A CN 201610225966A CN 107286988 B CN107286988 B CN 107286988B
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- 238000000034 method Methods 0.000 title claims abstract description 91
- 230000008569 process Effects 0.000 title claims abstract description 72
- 239000000446 fuel Substances 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 85
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 238000009835 boiling Methods 0.000 claims abstract description 56
- 238000002407 reforming Methods 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 238000005336 cracking Methods 0.000 claims abstract description 18
- 239000003502 gasoline Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 9
- 238000012545 processing Methods 0.000 claims abstract description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 66
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 66
- 239000002808 molecular sieve Substances 0.000 claims description 65
- 239000004411 aluminium Substances 0.000 claims 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 description 61
- 238000002360 preparation method Methods 0.000 claims description 56
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 45
- 239000010703 silicon Substances 0.000 claims description 45
- 229910052710 silicon Inorganic materials 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 230000032683 aging Effects 0.000 claims description 30
- 239000003292 glue Substances 0.000 claims description 27
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 23
- 239000002283 diesel fuel Substances 0.000 claims description 22
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 22
- 239000005995 Aluminium silicate Substances 0.000 claims description 20
- 235000012211 aluminium silicate Nutrition 0.000 claims description 20
- 239000004927 clay Substances 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 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 claims description 16
- 239000004033 plastic Substances 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000012670 alkaline solution Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims description 13
- 229910052682 stishovite Inorganic materials 0.000 claims description 13
- 229910052905 tridymite Inorganic materials 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 238000005260 corrosion Methods 0.000 claims description 8
- 230000007797 corrosion Effects 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000004523 catalytic cracking Methods 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005299 abrasion Methods 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000002671 adjuvant Substances 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- 241000269350 Anura Species 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims 2
- 230000004048 modification Effects 0.000 claims 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 1
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 230000003197 catalytic effect Effects 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 11
- 229910001388 sodium aluminate Inorganic materials 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 5
- 229910019975 (NH4)2SiF6 Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910004074 SiF6 Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 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
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- -1 galapectite Chemical compound 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 235000021050 feed intake Nutrition 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 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 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 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
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011378 shotcrete Substances 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
-
- 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
- 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
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/633—
-
- 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
Abstract
The invention discloses a kind of processes for handling poor ignition quality fuel.Enter boiling bed hydrogenation cracking reaction area after poor ignition quality fuel raw material is mixed with hydrogen, carries out hydrocracking reaction in the presence of boiling bed hydrogenation reforming catalyst；Obtained reaction, which generates, enters boiling bed hydrogenation processing reaction zone after oil is mixed with hydrogen, hydrogenation reaction is carried out in the presence of boiling bed hydrogenation treatment catalyst, obtains gasoline products and diesel product after separation.The process is applied in combination using two-stage ebullating bed reactor area, and boiling bed hydrogenation reforming catalyst is used in combination, and realizes that poor ignition quality fuel adds hydrogen, cracking and aromatic hydrocarbons orientation conversion performance, to produce high-knock rating gasoline blend component.
Description
Technical field
The present invention relates to a kind of technique for handling poor ignition quality fuel, especially a kind of catalytic diesel oil boiling bed hydrogenation conversion production
The technique of high-knock rating gasoline blend component.
Background technique
Aromatic hydrocarbons and nitrogen content are high in catalytic diesel oil, and density is big, and Cetane number is low, add hydrogen removing impurities matter difficult, are diesel qualities
The difficult point of upgrading.How catalytic diesel oil component is cost-effectively utilized, is the universal face in one section of period oil refining enterprise at present and in the future
The difficult point and hot issue faced.
Catalytic diesel oil inferior can be partially converted into the clean gasoline tune of high added value by catalytic diesel oil hydro-conversion technology
And component brings considerable economic benefit while alleviating enterprise's diesel quality upgrading problem for enterprise.
Low-voltage high-temperature is conducive to catalytic diesel oil hydro-conversion production high-knock rating gasoline blend component, at present exploitation and industry
The fixed bed hydrogenation cracking technology of application, temperature rise is big, operation cycle is short, and the octane number of start of run production is relatively
It is low.Catalytic diesel oil is processed using ebullated bed, distinctive be hydrocracked of ebullated bed carries out simultaneously with heat cracking reaction, be conducive to promote
Into the further Efficient Conversion of catalytic diesel oil；Full back-mixing state is in fluidized bed reactor, reaction heat is by a large amount of in reactor
The cold hydrogen dosage of cracker can be greatly lowered in the problems such as liquid dilutes rapidly, no temperature runaway and bed pressure drop, have certain warp
Ji property；Catalyst can replace online, guarantee that product property is stablized in entire operation cycle, operation cycle is long.
Catalytic diesel oil boiling bed hydrogenation reforming catalyst is the important component part of the technology, and existing be hydrocracked is urged
Agent and Hydrobon catalyst can not meet catalytic diesel oil simultaneously and add hydrogen, cracking and aromatic hydrocarbons orientation conversion performance, boil simultaneously
Rising bed process also has higher requirement to the abrasion resistance of catalyst, it is therefore necessary to catalytic diesel oil boiling bed hydrogenation be cooperated to convert work
Skill develops matched catalyst system.
US6174429 discloses a kind of hydrocracking catalyst, which contains at least one acid of 1wt%~99wt%
The [amorphous containing aluminium changed, a kind of cell parameter of 0.1wt%~80wt% are 2.438nm, SiO2/Al2O3Chemical molar ratio is
8 or so, SiO2/Al2O3The Y type molecular sieve that framework mole ratio is 20 or so, at least one group VIII of 0.1wt%~30wt%
Metal component, at least one vib metals component of 1wt%~40wt%, the auxiliary agent of 0.1wt%~20wt% and 0~20wt%'s
At least one V Group IIA element.The catalyst using first preparing carrier, after support the preparation method of hydrogenation metal, catalyst tool
There are preferable activity and stability, but hydro-conversion performance has to be strengthened, heavy naphtha and boat yield of coal be not high.
CN98114489.6 discloses a kind of hydrocracking catalyst, is prepared using coprecipitation method.Wherein, with the weight of catalyst
On the basis of amount, amorphous silica-alumina 10wt%~60wt%, Modified Zeolite Y 1wt%~40wt%, vib metals oxide are accounted for
10wt%~40wt%, group VIII metal oxide account for 1wt%~10wt%, and group ivb metal oxide accounts for 1wt%~10, is used for
One-stage serial hydrocracking produces intermediate oil, and the N content of cracking section feeding is up to 100 μ g/g.The catalyst has preferable
Catalytic activity, catalyst also has very high anti-nitrogen, but preparation method is more complex, and preparation cost is also higher, naphtha
Product yield is lower.
CN1191123C discloses a kind of preparation method of cracking catalyst for petroleum hydrocarbon, it is to handle clay slurry acid
Afterwards, boehmite, water glass solution is added, adds Aluminum sol, adds molecular sieve pulp, spray drying, washing, gained catalysis
The small-bore agent < 5nm proportion is larger.This method preparation is catalytic cracking catalyst, the cracking suitable for petroleum hydrocarbon
Reaction.
CN201310540464.7 discloses a kind of catalytic cracking diesel oil hydrogenating conversion process.In this method, catalytic diesel oil
It is introduced into hydrofining reactor after mixing with hydrogen and carries out hydrofining reaction, hydrofining reaction effluent, which is directly entered, to be added
Hydrogen cracker, the catalyst bed haptoreaction with gradation in cracker；Wherein setting in hydrocracking reactor
At least two Cracking catalyst beds, according to the flow direction of reaction mass, the hydrogenation activity of hydrocracking catalyst is in reduction
Trend；Hydrocracking reaction effluent obtains naphtha and diesel oil by separation and fractionation.Since this method uses fixed bed work
Skill, there are still temperature rises greatly, has pressure drop and hot issue, and operation cycle is short.
Summary of the invention
Aiming at the shortcomings in the prior art, the present invention provides a kind of process for handling poor ignition quality fuel, the process
It can be achieved poor ignition quality fuel hydro-conversion obtaining high-knock rating gasoline blend component.Present invention process makes full use of boiling bed process
Temperature rise is small, without hot spot temperature runaway, cold hydrogen dosage is few, low energy consumption, product property is stable, operation cycle is long the advantages that, while cooperation makes
With poor ignition quality fuel boiling bed hydrogenation reforming catalyst, realize that poor ignition quality fuel adds hydrogen, cracking and aromatic hydrocarbons orientation conversion performance, thus raw
Produce high-knock rating gasoline blend component.
The present invention provides a kind of process for handling poor ignition quality fuel, and the process includes following content:
(1) enter boiling bed hydrogenation cracking reaction area after poor ignition quality fuel raw material is mixed with hydrogen, converted in boiling bed hydrogenation
Hydrogenation reaction is carried out under catalyst action；
(2) reaction that step (1) obtains, which generates, enters boiling bed hydrogenation processing reaction zone after oil is mixed with hydrogen, boiling
Hydrogenation reaction is carried out in the presence of bed hydroprocessing processing catalyst, obtains gasoline products and diesel product after separation；
Wherein, the boiling bed hydrogenation reforming catalyst that boiling bed hydrogenation cracking reaction area uses in step (1) is with high silicon
Aluminium oxide and molecular sieve are carrier, using group VIII metal and vib metals as active metal component, wherein high silicon aluminium
The property of carrier is as follows: the content of silica be 30wt%~75wt%, preferably 35wt%~75wt%, more preferably 45wt%~
0.65~0.90mL/g of 75wt%, Kong Rongwei, specific surface area are 280~350m2/ g, pore size distribution are as follows: the hole of bore dia < 4nm
Kong Rong account for total pore volume 10% hereinafter, the Kong Rong in the hole of preferably 3%~8%, bore dia > 15nm account for the 15% of total pore volume hereinafter,
Meleic acid total acid content is 0.35~0.60mmol/g, and preferably 0.38~0.60mmol/g, B acid amount is 0.04~0.12mmol/g
, preferably 0.05~0.10mmol/g.
Boiling bed hydrogenation reforming catalyst of the invention is using high silicon aluminium and molecular sieve as carrier, with group VIII gold
Belong to and vib metals are active metal component, on the basis of the weight of catalyst, the content of high silicon aluminium is 30%~
70%, the content of molecular sieve is 10%~50%, and content of the group VIII metal in terms of oxide is 1wt%~9wt%, group VIB gold
The content belonged in terms of oxide is 10wt%~30wt%.
In boiling bed hydrogenation reforming catalyst of the invention, group VIII metal is preferably Ni and/or Co, group VIB gold
Belonging to is preferably W and/or Mo.
The property of boiling bed hydrogenation reforming catalyst of the present invention is as follows: specific surface area is 250~450m2/ g, Kong Rong are
0.30~0.50mL/g.
In boiling bed hydrogenation reforming catalyst of the present invention, the molecular sieve can be using common in hydrocracking catalyst
Molecular sieve, molecular sieve generally comprise Y type molecular sieve, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesoporous molecular
One or more of sieve, preferably Y type molecular sieve, required molecular sieve can require to carry out suitable change according to service performance
Property, more preferably use Modified Zeolite Y.
In boiling bed hydrogenation reforming catalyst of the present invention, it is preferred to use following Modified Zeolite Y, the modified Y type point
Son sieve property is as follows: average grain diameter is 2.0~5.0 μm, preferably 2.0~4.5 μm, more preferably 3.0~4.5 μm, relatively
Crystallinity 110~150%, SiO2/Al2O3Molar ratio is 10~50,2.436~2.450nm of cell parameter, and bore dia is 2~6nm
The Kong Rong in hole account for the 60~90% of total pore volume, preferably 70~85%.In the Modified Zeolite Y, the total aluminium of non-framework aluminum Zhan
0.1wt%~1.0wt %, preferably 0.1wt%~0.5wt%.0.35~0.50cm of Kong Rongwei of the Modified Zeolite Y3/
G, specific surface area are 750~950m2/g.The infrared total acid content of the Modified Zeolite Y is 0.5~1.0mmol/g.It is described to change
In property Y type molecular sieve, Na2The content of O is 0.15wt% or less.
The preparation method of above-mentioned Modified Zeolite Y, includes the following steps:
(A) preparation of big crystal grain NaY type molecular sieve；
(B) the resulting big crystal grain NaY type molecular sieve of step (A) is prepared into big crystal grain NH4NaY；
(C) hydro-thermal process is carried out to Y type molecular sieve obtained by step (B)；Hydrothermal conditions be gauge pressure 0.05~
0.25MPa, handles 0.5~5.0h of time by 400~550 DEG C of temperature；
(D) (NH is used4)2SiF6Aqueous solution is contacted with step (C) resulting material, is then filtered and is dried, and is made
Modified Zeolite Y of the invention.
In the preparation method of above-mentioned Modified Zeolite Y, the property of big crystal grain NaY type molecular sieve described in step (A)
It is as follows: average grain diameter be 2.0~5.0 μm, preferably 2.0~4.5 μm, more preferably 3.0~4.5 μm, bore dia be 1~
The Kong Rong in the hole of 10nm accounts for the 70%~90% of total pore volume, preferably 70%~85%, and relative crystallinity is 110%~150%, structure cell ginseng
Number 2.460nm~2.465nm, SiO2/Al2O3Molar ratio 3.5~6.5, preferably 4.0~6.0.
In the preparation method of above-mentioned Modified Zeolite Y, the big crystal grain NH of step (B) preparation4The weight of sodium oxide molybdena in NaY
Content is 2.5%~5.0%.
In the preparation method of above-mentioned Modified Zeolite Y, the hydro-thermal process in step (C) is to be handled to walk with saturated steam
Suddenly the molecular sieve that (B) is obtained, treatment conditions: 0.05~0.25MPa of gauge pressure, preferably 0.10~0.20MPa, temperature 400~550
DEG C, it preferably 450~550 DEG C, handles the time 0.5~5.0 hour, preferably 1.0~3.0 hours.
In the preparation method of above-mentioned Modified Zeolite Y, step (D) is by material obtained in step (C) and (NH4)2SiF6Aqueous solution contact, detailed process is as follows: being first beaten the molecular sieve that step (C) obtains in aqueous solution, liquid weighs admittedly
For amount than being 3:1~8:1, temperature is 70~90 DEG C；Then (NH is added into slurry4)2SiF6Aqueous solution, according to every 100 grams of Y types
10~35 grams of (NH are added in molecular sieve4)2SiF6Ratio be added (NH4)2SiF6Aqueous solution, every 100gY type molecular sieve adds per hour
Enter 3~30 grams of (NH4)2SiF6, add (NH4)2SiF6After aqueous solution, slurry is in the case where temperature is 80~120 DEG C, stirring 0.5~5.0
Hour, then filtration drying, obtains product.
In the preparation method of above-mentioned Modified Zeolite Y, the preparation method of NaY type molecular sieve in step A, including walk as follows
It is rapid:
(I) gel is prepared: at 20~40 DEG C, at preferably 25~35 DEG C, according to molar ratio Na2O:Al2O3: SiO2: H2O=
10~15:1:10~20:500~600 feed intake, and it is molten that waterglass is slowly added into high alkali deflection aluminium acid sodium under agitation
It is uniformly mixed in liquid, then sequentially adds aluminum sulfate solution and low alkali aluminium acid sodium solution, stir evenly at the temperature disclosed above；So
Constant temperature aging in confined conditions afterwards, obtains gel；
(II) crystallization: hydrothermal crystallizing 12~24 is small at 80~120 DEG C and under conditions of stirring for the gel that step (I) is obtained
When, it is filtered, washed after crystallization, dried, obtain big crystal grain NaY type molecular sieve.
In the preparation method of above-mentioned NaY type molecular sieve, according to molar ratio Na in step (I)2O:Al2O3: SiO2: H2O=10~
15:1:10~20:500~600 feed intake, and wherein water can be individually added into, and can also be added together with solution.
In the preparation method of above-mentioned NaY type molecular sieve, in step (I), aluminum sulfate, high alkali deflection aluminium acid sodium and low alkali meta-aluminic acid
The ratio of the additional amount of sodium, is calculated as 1:(0.5~0.7 with aluminium oxide): (0.6~0.8).
In the preparation method of above-mentioned NaY type molecular sieve, step (I) is added without directed agents, template, table in the reaction system
The additives such as face activating agent synthesize big crystal grain using a hydrothermal crystallizing by selecting suitable raw material and optimization preparation process
The utilization efficiency of NaY type molecular sieve, silicon source and silicon source is high, and process flow is simple, at low cost.The NaY type molecule of this method preparation
The granularity of sieve reaches 2.0~5.0 μm, and silica alumina ratio is high, effective pore sife distribution is more concentrated, thermal stability and hydrothermal stability are good
It is good.
The shape of boiling bed hydrogenation reforming catalyst of the present invention can be spherical or bar shaped, preferably spherical, granularity is 0.1~
1.0mm, preferably 0.3~0.8mm, abrasion index≤2.0% of catalyst.
It can also include one of adjuvant component, such as P, B, Ti, Zr in boiling bed hydrogenation reforming catalyst of the present invention
Or it is several, content is 5wt% or less to the additional amount of auxiliary agent in the catalyst based on the element.Auxiliary agent can be in carrier preparation process
It introduces, can also be introduced when impregnating active metal component.
The preparation method of poor ignition quality fuel boiling bed hydrogenation reforming catalyst of the invention, including prepare high silicon aluminium and do
Glue, then with it is molecular sieve molded, dry and roasting obtains carrier, loads hydrogenation active metal component using infusion process, is catalyzed
Agent；Wherein, high silicon aluminium dry glue preparation the following steps are included:
(1) high-temperature roasting after crushing clay original soil, modified clay obtained are pulverized and sieved, and obtain granularity greater than 160
Purpose is modified clay；
(2) step (1) modified clay is added in lye containing aluminium and suspension is made, control the suspension of alkalinity containing aluminium temperature
It is 40~65 DEG C；
(3) suspension for obtaining step (2) and acidic silicasol cocurrent are added in reaction kettle, and control gelling temperature is 40
~65 DEG C, plastic pH value is 4.5~6.5；
(4) when after reaction, then into the slurries of step (3) alkaline solution is added in step (3), make slurry pH value
7.0~9.0, preferably 7.0~8.5；Wherein control gelling temperature is 40~65 DEG C；
(5) step (4) resulting slurries filter after aging, are dried to obtain high silicon aluminium dry glue.
Clay described in step (1) is one or more of kaolin, montmorillonite, galapectite, diatomite etc., described
Roasting condition are as follows: maturing temperature is 600~900 DEG C, and calcining time is 0.5~6.0 hour.
Alkaline solution containing aluminium described in step (2) is the meta-aluminate solution of alkali metal, preferably sodium metaaluminate, meta-aluminic acid
Potassium or their mixture, more preferably sodium metaaluminate, the concentration of the alkaline solution containing aluminium are 100~300gAl2O3/ L, causticity
It is 2.1~13.0, preferably 2.1~7.2 than (molar ratio of alkali metal oxide and aluminium oxide).The additional amount of modified clay is 60
Alkaline solution (i.e. in every liter alkaline solution containing aluminium be added 60~120g modified clay) of the modified clay/L of~120g containing aluminium.
Step (3) the acidic silicasol pH value is 2~4, and concentration is 50~90gSiO2/L.Step (3) the plastic temperature
Preferably 40~65 DEG C of degree.
Alkaline solution described in step (4) is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, carbonic acid
One of hydrogen potassium etc. is a variety of, and the weight concentration of the alkaline solution is 5%~10%.
Aging pH value described in step (5) is 6~9, and aging temperature is 40~65 DEG C, and ageing time is 0.5~4.0h；It is dry
Dry condition is 110~120 DEG C 4~6 hours dry.
In the preparation method of boiling bed hydrogenation reforming catalyst of the present invention, high silicon aluminium dry glue and molecular sieve were being formed
Shaping assistant can be added in journey to complete, shaping assistant is adhesive, peptizing agent or extrusion aid etc., carrier drying and roasting
Condition is as follows: 100 DEG C~150 DEG C of drying temperature, drying time 2~for 24 hours；400 DEG C~650 DEG C of maturing temperature, calcining time 2~
8h。
In the preparation method of boiling bed hydrogenation reforming catalyst of the present invention, active metal component is born using conventional method
It carries, i.e., the metal salt containing active metal component is configured to dipping solution, then loads to carrier, urged through dry and roasting
Agent, wherein 100 DEG C~150 DEG C of drying temperature, drying time 2~for 24 hours.Catalyst is in 400 DEG C~600 DEG C 2~8h of roasting.
Boiling bed hydrogenation treatment catalyst property used in boiling bed hydrogenation processing reaction zone of the present invention is as follows: Kong Rongwei
0.30 ~ 0.45mL/g, specific surface area are 180 ~ 250m2/g.Using group VIII metal and vib metals as hydrogenation active metals
Component, the group VIII metal are preferably Ni and/or Co, and vib metals are preferably W and/or Mo.With the weight of catalyst
On the basis of, content of the group VIII metal in terms of oxide is 4wt% ~ 9wt%, and content of the vib metals in terms of oxide is
18wt%~30wt%.The boiling bed hydrogenation treatment catalyst can be prepared according to existing method, such as according to
It is prepared by method disclosed in CN201210442630.5, CN200510047534.0 patent.The present invention handles poor ignition quality fuel
Process in, the poor ignition quality fuel be catalytic cracking diesel oil, property are as follows: (20 DEG C) of density be 0.88~0.99g/cm3,
Doing is 360~400 DEG C, and arene content is 50wt%~90wt%.The sulfur content of catalytic cracking diesel oil is 0.2wt%~2.0wt%,
Nitrogen content is 500~2000 μ g/g.
The present invention is handled in the process of poor ignition quality fuel, the operating condition in boiling bed hydrogenation cracking reaction area are as follows: reaction
Pressure is 5~10MPa, and temperature is 370~450 DEG C, and volume space velocity is 1.0~5.0h when liquid-1, hydrogen to oil volume ratio be 100~
1000.The operating condition of boiling bed hydrogenation processing reaction zone are as follows: reaction pressure is 5~8MPa, and temperature is 280~350 DEG C, when liquid
Volume space velocity is 1.0~5.0h-1, hydrogen to oil volume ratio is 100~1000.
Boiling bed hydrogenation reforming catalyst of the present invention is using high silicon aluminium dry glue, to be modified clay as part silicon
Source is added in the lye containing aluminium of high causticity ratio, is dissolved to the silicon in clay, so that ion is formed, during plastic
Silicon is set to be uniformly dispersed.Two-step precipitation is used during high silicon aluminium dry glue plastic, and the part aluminium in clay can be made in low pH
Under the conditions of participate in reaction, and the part silicon in clay is participated under higher pH condition react, to make silicon better disperse, simultaneously
To be modified clay as the crystal seed of plastic, the good high silicon aluminium of the comprehensive performances such as pore structure and Acidity can be prepared, it is special
Not suitable for poor ignition quality fuel hydroconversion process.And the high silicon aluminium dry glue has good peptization, and it is easy to form,
Especially improve prior art preparation it is siliceous more when high silicon aluminium dry glue when its peptization be deteriorated the shortcomings that.
Present invention process method processes poor ignition quality fuel using two sections of ebullated bed tandem process, and it is distinctive to have played ebullated bed
It is hydrocracked the advantage carried out simultaneously with heat cracking reaction, may advantageously facilitate the further Efficient Conversion of poor ignition quality fuel, ebullated bed
Full back-mixing state is in reactor, reaction heat is diluted rapidly by quantity of fluid big in reactor, and no temperature runaway and bed pressure drop etc. are asked
Topic, can be greatly lowered the cold hydrogen dosage of cracker, have certain economy；Catalyst can replace online, guarantee entire fortune
Product property is stablized in the turn-week phase, and operation cycle is long.
Present invention process method is poor ignition quality fuel hydro-conversion to be produced high-knock rating gasoline blend component, while obtaining
Diesel oil property can be used as the blending component of diesel oil.The process make full use of ebullated bed temperature rise it is small, without hot spot temperature runaway, cold hydrogen
Dosage lacks the advantages that low energy consumption, product property is stable, operation cycle is long, while being used cooperatively boiling bed hydrogenation reforming catalyst,
Realize that poor ignition quality fuel adds hydrogen, cracking and aromatic hydrocarbons orientation conversion performance, to produce high-knock rating gasoline blend component.The technique side
Method is easy to operate, poor ignition quality fuel can be made to be utilized effectively.
Specific embodiment
It is addressed further under technical characteristic of the invention below by embodiment, but is not limited to the embodiment, is related to percentage
It is weight percentage, i.e. wt%.
Specific surface area, Kong Rong and external surface area, pore size distribution are measured using low temperature liquid nitrogen physisorphtion in the present invention, phase
Crystallinity and cell parameter are measured using X-ray diffraction method, the specific low temperature for using Merck & Co., Inc, U.S. ASAP2420 model
N2 adsorption instrument measures；Detailed process: taking a small amount of sample to be vacuum-treated 3 ~ 4h at 300 DEG C, and it is low that product is finally placed in liquid nitrogen
Nitrogen suction-desorption test is carried out under the conditions of warm (- 200 DEG C).Wherein surface area is obtained according to BET equation, pore-size distribution and hole body
Product is obtained according to BJH model.
Silica alumina ratio is measured using chemical analysis in the present invention, and the grain size of molecular sieve uses SEM(scanning electron
Microscope) mode measure, the SEM(scanning electron microscope of the specific JSM-7500F type produced using JEOL company, Japan),
It is equipped with EDAX-EDS, acceleration voltage: 20Kv, operating distance: 8mm, resolution ratio: 1nm.
Meleic acid amount is measured using U.S. Buddhist nun high-tensile strength IR6700 type Fourier transformation infrared spectrometer in the present invention, before measurement
First sample is deaerated in high vacuum system purification be surface-treated, using pyridine as probe molecule, under certain vapour pressure into
The gas-solid absorption of row, then uses determination of infrared spectroscopy acidity.Experimental condition: sample purifies 500 DEG C in reaction tube, under 60mPa
4h drops to room temperature, is evacuated to 0.1mPa Adsorption of Pyridine, and B acid and L acid are measured at 160 DEG C.Abrasion index uses air gunite
Measurement.
It is as follows that the embodiment of the present invention 1 prepares feedstock property used in big crystal grain NaY molecular sieve:
High alkali deflection aluminium acid sodium solution: Na2O content 291g/L, Al2O3Content 42g/L；
Low alkali aluminium acid sodium solution: Na2O content 117g/L, Al2O3Content 77g/L；
Aluminum sulfate solution: Al2O3Content 90g/L；
Waterglass: SiO2Content 250g/L, modulus 3.2.
Boiling bed hydrogenation treatment catalyst used in boiling bed hydrogenation processing reaction zone in the embodiment of the present invention and comparative example
It is prepared by method disclosed in CN201210442630.5 patent, property are as follows: Kong Rong 0.308mL/g, specific surface 181m2/
G, WO3: 18.61%, MoO3: 7.18%, NiO:8.12%.
Embodiment 1
The present embodiment is to prepare big crystal grain NaY molecular sieve using the method for the present invention.
The preparation of big crystal grain NaY molecular sieve LY-1
A, the preparation of gel: temperature is 25 DEG C, under stirring condition, is slowly added into the high alkali deflection aluminium acid sodium solution of 63mL
165mL waterglass sequentially adds the aluminum sulfate solution and 35.6mL low alkali aluminium acid sodium solution of 42.5mL after mixing, permanent
Temperature stirring 0.5 hour, then by obtained Synthesis liquid static aging 1 hour at the temperature disclosed above, obtains gel；
B, crystallization: under agitation, the gel in synthesis reactor is raised to 100 DEG C with 2.5 DEG C/minute of heating rate, perseverance
Temperature stirring crystallization 16 hours, after crystallization, is quickly cooled down with cold water, and open synthesis reactor and take out synthetic molecular sieve, is passed through
It is filtered, washed and dried, obtains product big crystal grain NaY molecular sieve LY-1, property is listed in table 1；
C, ammonium exchange is carried out to raw material big crystal grain NaY molecular sieve LY-1.Compound concentration is 0.5mol/L aqueous ammonium nitrate solution
10 liters.2000 grams of small crystal grain NaY molecular sieve are weighed, is dissolved in 10 liters of prepared aqueous ammonium nitrate solutions, speed of agitator is
300rpm, constant temperature stirs 1 hour at 90 DEG C, and then filtering molecular sieves, and stays sample, analyzes Na2O content；Repeat above-mentioned behaviour
Make, until Na in molecular sieve2O content reaches 2.5~5wt%, and the sample number into spectrum after being dried is LYN-1；
D, it weighs 200g LYN-1 molecular sieve to be put into pipe type water heat-treatment furnace, temperature programming is to 430 DEG C, in gauge pressure
It handles 2.0 hours, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, temperature 90 under 0.1MPa
DEG C, speed of agitator 300rpm.Within 2 hours time, it is water-soluble that 195mL ammonium hexafluorosilicate is added at the uniform velocity into molecular sieve slurry
19.5 grams of ammonium hexafluorosilicates are added in liquid altogether, and then constant temperature constant speed stirs 2 hours, filter, dry, obtain product number LYNS-1,
Property is listed in table 2.
Embodiment 2
It weighs 200g LYN-1 molecular sieve to be put into pipe type water heat-treatment furnace, temperature programming is to 530 DEG C, in gauge pressure
It handles 1 hour, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, temperature 80 under 0.15MPa
DEG C, speed of agitator 300rpm.Within 2 hours time, it is water-soluble that 286mL ammonium hexafluorosilicate is added at the uniform velocity into molecular sieve slurry
28.6 grams of ammonium hexafluorosilicates are added in liquid altogether, and then constant temperature constant speed stirs 2 hours, filter, dry, obtain product number LYNS-2,
Property is listed in table 2.
The property of 1 NaY type molecular sieve of table
The property of 2 Y type molecular sieve of table
Embodiment 3
(1) preparation of high silicon aluminium dry glue
Kaolin is taken, it is crushed on pulverizer, smashed kaolin is in high temperature kiln roasting, maturing temperature
It is 900 DEG C, calcining time 3h, the kaolin after roasting obtains modified kaolin after the sieving of the sieve of 160 mesh.
Preparation sodium aluminate solution concentration is 150gAl2O3/ L, Crater corrosion 3.5 amount to 1L, after weighing 100g sieving
Kaolin is added in sodium aluminate solution and suspension is made, and control solution temperature is 50 DEG C.
It is 3 by the suspension containing kaolinic sodium metaaluminate and pH value, concentration is 60g SiO2The acidic silicasol of/L
3.0L cocurrent is added in reaction kettle, and control gelling temperature is 50 DEG C, and plastic pH value is 5.0.After cemented into bundles, it is added 5wt%'s
It is 8.0 that sodium carbonate liquor, which adjusts pH value, subsequently into the ageing step, 50 DEG C of aging temperature, and ageing time 1h.Slurries after aging
Be washed till neutrality with 70 DEG C of deionized water, 110 DEG C drying 5 hours, obtain high silicon aluminium dry glue A.
(2) catalyst preparation
Weigh high silicon aluminium dry glue A 100g, the Y type molecular sieve LYNS-1 50g of step (1) preparation, methylcellulose
9.8g is uniformly mixed, and distilled water 150g is then added, and kneading, at ball forming obtains grain in 120 DEG C of dry 2h, 550 DEG C of roasting 3h
Degree is 0.4~0.6mm carrier A.
Phosphoric acid 32.50g is weighed, distilled water 450mL is added, then sequentially adds molybdenum oxide 94.60g, basic nickel carbonate
Solution is settled to 500mL to after being completely dissolved, with distilled water, obtains solution L-1 by 40.46g, heating stirring.By carrier A solution
L-1 solution saturation dipping, obtains catalyst C-A in 110 DEG C of dry 2h, 480 DEG C of roasting 5h.
Embodiment 4
The amount of modified kaolin is only increased to 120g with embodiment 3 by other conditions, and plastic pH value is 6.0, plastic temperature
60 DEG C of degree, obtains high silicon aluminium dry glue B, carrier B and catalyst C-B.
Embodiment 5
(1) preparation of high silicon aluminium dry glue
Kaolin is only changed to montmorillonite with embodiment 3 by other conditions, is added in sodium aluminate solution, plastic temperature
45 DEG C of degree, plastic pH value are 4.5, adjust pH value 7.0 after cemented into bundles, obtain high silicon aluminium dry glue C.
(2) catalyst preparation
High silicon aluminium dry glue A 100g, Y type molecular sieve the LYNS-2 80g, nitric acid 14.8g for weighing step (1) preparation are mixed
It closes uniformly, distilled water 120g is then added, kneading, at ball forming obtains granularity and be in 110 DEG C of dry 4h, 500 DEG C of roasting 3h
0.4~0.6mm support C.
Support C is saturated with solution L-1 solution and is impregnated, obtains catalyst C-C in 120 DEG C of dry 2h, 500 DEG C of roasting 4h.
Embodiment 6
(1) preparation of high silicon aluminium dry glue
Kaolin is taken, it is crushed on pulverizer, smashed kaolin is in high temperature kiln roasting, maturing temperature
It is 700 DEG C, calcining time 3h, the kaolin after roasting obtains modified kaolin after the sieving of the sieve of 160 mesh.
Preparation sodium aluminate solution concentration is 200gAl2O3/ L, Crater corrosion 6.0 amount to 0.5L, after weighing 60g sieving
Kaolin is added in sodium aluminate solution and suspension is made, and control solution temperature is 60 DEG C.
It is 2 by the suspension containing kaolinic sodium metaaluminate and pH value, concentration is 80g SiO2The acidic silicasol of/L
4.3L cocurrent is added in reaction kettle, and control gelling temperature is 55 DEG C, and plastic pH value is 5.5.After cemented into bundles, it is added 8wt%'s
It is 7.5 that sodium carbonate liquor, which adjusts pH value, subsequently into the ageing step, 55 DEG C of aging temperature, and ageing time 2h.Slurries after aging
Be washed till neutrality with 100 DEG C of deionized water, 120 DEG C drying 3 hours, obtain high silicon aluminium dry glue D.
(2) catalyst preparation
Weigh high silicon aluminium dry glue A 100g, Y type molecular sieve the LYNS-1 100g, sesbania powder 2.0g of step (1) preparation
It is uniformly mixed with methylcellulose 12.8g, is then added distilled water 160g, kneading, at ball forming, in 120 DEG C of dry 2h, 500
DEG C roasting 3h obtain granularity be 0.4~0.6mm carrier D.
Phosphoric acid 37.49g is weighed, distilled water 450mL is added, then sequentially adds molybdenum oxide 135.77g, basic nickel carbonate
Solution is settled to 500mL to after being completely dissolved, with distilled water, obtains solution L-2 by 51.02g, heating stirring.By carrier D solution
L-2 solution saturation dipping, obtains catalyst C-D in 110 DEG C of dry 2h, 480 DEG C of roasting 5h.
Comparative example 1
(1) preparation of high silicon aluminium dry glue
Kaolin is taken, it is crushed on pulverizer, smashed kaolin is in high temperature kiln roasting, maturing temperature
It is 900 DEG C, calcining time 3h, the kaolin after roasting obtains modified kaolin after the sieving of the sieve of 160 mesh.
Preparation sodium aluminate solution concentration is 150gAl2O3/ L, Crater corrosion 3.5 amount to 1L, after weighing 100g sieving
Kaolin is added in sodium aluminate solution and suspension is made, and control solution temperature is 50 DEG C.
It is 3 by the suspension containing kaolinic sodium metaaluminate and pH value, concentration is 60g SiO2The acidic silicasol of/L
3.0L cocurrent is added in reaction kettle, and control gelling temperature is 50 DEG C, and plastic pH value is 5.0.After cemented into bundles, into aging rank
Section, 50 DEG C of aging temperature, ageing time 1h.Slurries after aging are washed till neutrality with 70 DEG C of deionized water, and 110 DEG C of dryings 5 are small
When, obtain high silicon aluminium dry glue F.
(2) catalyst preparation
Comparative catalyst C-F is prepared with embodiment 3 in catalyst preparation conditions.
Comparative example 2
(1) preparation of high silicon aluminium dry glue
Preparation sodium aluminate solution concentration is 150gAl2O3/ L, Crater corrosion 3.5 amount to 1L.By sodium aluminate solution with
PH value is 3, and concentration is 60g SiO2The acidic silicasol 3.0L cocurrent of/L is added in reaction kettle, and control gelling temperature is 50
DEG C, plastic pH value is 5.0.After cemented into bundles, into the ageing step, 50 DEG C of aging temperature, ageing time 1h.Slurries after aging
Be washed till neutrality with 70 DEG C of deionized water, 110 DEG C drying 5 hours, obtain high silicon aluminium dry glue G.
(2) catalyst preparation
Comparative catalyst C-G is prepared with embodiment 3 in catalyst preparation conditions.
Comparative example 3
(1) preparation of high silicon aluminium dry glue
Referring to the silicon-containing alumina of CN102029192A method preparation.
Preparation sodium aluminate solution concentration is 150gAl2O3/ L, Crater corrosion 3.5 amount to 1.2L.Measuring pH value is 3, dense
Degree is 60g SiO2The acidic silicasol 3.0L of/L, for use.
Kaolin is taken, it is crushed on pulverizer, smashed kaolin is in high temperature kiln roasting, maturing temperature
It is 900 DEG C, calcining time 3h, the kaolin after the sieve of 160 mesh is sieved of the kaolin after roasting.
Weigh 100g sieving after kaolin, be added 1mol/L nitric acid 300mL and 2mol/L citric acid 100mL, heat into
Row reaction, reaction temperature are 60 DEG C, reaction time 8h.
It is poured into reaction kettle after 700mL distilled water is added into modified kaolin slurry, solid content is in slurries
Sodium aluminate solution and acidic silicasol is added in 9.1wt%, cocurrent, and control gelling temperature is 50 DEG C, and plastic pH value is 5.0.Plastic
After, into the ageing step, 50 DEG C of aging temperature, ageing time 1h.Slurries after aging are washed till with 70 DEG C of deionized water
Neutrality, 110 DEG C drying 5 hours, obtain high silicon aluminium dry glue H.
(2) catalyst preparation
Comparative catalyst C-H is prepared with embodiment 3 in catalyst preparation conditions.
The physico-chemical property of obtained high silicon aluminium and catalyst above is listed in table 3.
The physico-chemical property of 3 high silicon aluminium of table
The property of 4 catalyst of table
The boiling bed hydrogenation reforming catalyst and boiling bed hydrogenation treatment catalyst of preparation are loaded into 4L ebullated bed respectively
On two sections of tandem arrangements, activity rating is carried out, raw materials used oil nature is shown in Table 5, and evaluation condition and evaluation result are shown in Table 6.
5 raw material oil nature of table
Table 6 evaluates process conditions and evaluation result
From data in table 6 it can be seen that catalytic diesel oil is after this patent process, obtaining gasoline composition be can satisfy
The requirement of blending component, and obtained diesel oil distillate property significantly improves.
Claims (44)
1. a kind of process for handling poor ignition quality fuel, the process includes following content:
(1) enter boiling bed hydrogenation cracking reaction area after poor ignition quality fuel raw material is mixed with hydrogen, in boiling bed hydrogenation conversion catalyst
Hydrocracking reaction is carried out in the presence of agent；
(2) step (1) obtains reaction generates after oil mix with hydrogen into boiling bed hydrogenation processing reaction zone, in ebullated bed plus
Hydrogenation reaction is carried out in the presence of hydrogen processing catalyst, obtains gasoline products and diesel product after separation；
Wherein, the boiling bed hydrogenation reforming catalyst that boiling bed hydrogenation cracking reaction area uses in step (1) is with high silicon
Aluminium and molecular sieve are carrier, using group VIII metal and vib metals as active metal component, the wherein property of high silicon aluminium
Matter is as follows: the content of silica be 30wt%~75wt%, 0.65~0.90mL/g of Kong Rongwei, specific surface area be 280~
350m2/ g, pore size distribution are as follows: the Kong Rong in the hole of bore dia < 4nm accounts for the 10% of total pore volume hereinafter, the hole of bore dia > 15nm
Kong Rong accounts for the 15% of total pore volume hereinafter, meleic acid total acid content is 0.35~0.60mmol/g, and B acid amount is 0.04~0.12mmol/g；
Wherein, high silicon aluminium dry glue preparation the following steps are included:
(2.1) high-temperature roasting after crushing clay original soil, modified clay obtained are pulverized and sieved, and obtain granularity greater than 160 mesh
Modification clay；
(2.2) step (2.1) modified clay is added in lye containing aluminium and suspension is made, control the suspension of alkalinity containing aluminium temperature
It is 40~65 DEG C；
(2.3) suspension for obtaining step (2.2) and acidic silicasol cocurrent are added in reaction kettle, and control gelling temperature is 40
~65 DEG C, plastic pH value is 4.5~6.5；
(2.4) when after reaction, then into the slurries of step (2.3) alkaline solution is added in step (2.3), make slurry pH value
7.0~9.0, wherein control gelling temperature is 40~65 DEG C；
(2.5) step (2.4) resulting slurries filter after aging, are dried to obtain high silicon aluminium dry glue.
2. process described in accordance with the claim 1, it is characterised in that: the content of silica is 35wt%~75wt%.
3. process described in accordance with the claim 1, it is characterised in that: the content of silica is 45wt%~75wt%.
4. process described in accordance with the claim 1, it is characterised in that: the Kong Rong in the hole of bore dia < 4nm accounts for total pore volume
3%~8%.
5. process described in accordance with the claim 1, it is characterised in that: meleic acid total acid content is 0.38~0.60mmol/g, B
Acid amount is 0.05~0.10mmol/g.
6. process described in accordance with the claim 1, it is characterised in that: the boiling bed hydrogenation reforming catalyst is with catalyst
Weight on the basis of, the content of high silicon aluminium is 30%~70%, and the content of molecular sieve is 10%~50%, group VIII metal with
The content of oxide meter is 1wt%~9wt%, and content of the vib metals in terms of oxide is 10wt%~30wt%.
7. process described in accordance with the claim 1, it is characterised in that: the group VIII metal is Ni and/or Co, the
Group vib metal is W and/or Mo.
8. process described in accordance with the claim 1, it is characterised in that: the property of the boiling bed hydrogenation reforming catalyst is such as
Under: 250~450m of specific surface area20.30~0.50mL/g of/g, Kong Rong.
9. process described in accordance with the claim 1, it is characterised in that: described in the boiling bed hydrogenation reforming catalyst
Molecular sieve includes one of Y type molecular sieve, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve
Or it is several.
10. according to process described in claim 1 or 9, it is characterised in that: in the boiling bed hydrogenation reforming catalyst,
The molecular sieve is Y type molecular sieve.
11. process according to claim 9, it is characterised in that: required molecular sieve according to service performance require into
The suitable modification of row.
12. process according to claim 11, it is characterised in that: the molecular sieve is Modified Zeolite Y, described
Modified Zeolite Y property is as follows: average grain diameter is 2.0~5.0 μm, relative crystallinity 110~150%, SiO2/Al2O3
Molar ratio be 10~50,2.436~2.450nm of cell parameter, bore dia be 2~6nm hole Kong Rong account for total pore volume 60~
90%。
13. process according to claim 12, it is characterised in that: the Modified Zeolite Y property is as follows: crystal grain
Average diameter is 2.0~4.5 μm, and bore dia is that the Kong Rong in the hole of 2~6nm accounts for the 70~85% of total pore volume.
14. according to process described in claim 12 or 13, it is characterised in that: the Modified Zeolite Y property is as follows:
Average grain diameter is 3.0~4.5 μm.
15. process according to claim 12, it is characterised in that: in the Modified Zeolite Y, non-framework aluminum is accounted for
0.1wt%~1.0wt % of total aluminium.
16. according to process described in claim 12 or 15, it is characterised in that: in the Modified Zeolite Y, non-skeleton
0.1wt%~0.5wt% of the total aluminium of aluminium Zhan.
17. process according to claim 12, it is characterised in that: the Kong Rongwei 0.35 of the Modified Zeolite Y
~0.50cm3/ g, specific surface area are 750~950m2/g。
18. process according to claim 12, it is characterised in that: the infrared total acid content of the Modified Zeolite Y
For 0.5~1.0mmol/g.
19. process according to claim 12, it is characterised in that: in the Modified Zeolite Y, Na2The content of O
For 0.15wt% or less.
20. process described in accordance with the claim 1, it is characterised in that: the shape of the boiling bed hydrogenation reforming catalyst
For spherical or bar shaped.
21. according to process described in claims 1 or 20, it is characterised in that: the boiling bed hydrogenation reforming catalyst
Shape is spherical shape.
22. process described in accordance with the claim 1, it is characterised in that: the boiling bed hydrogenation reforming catalyst granularity is
0.1~1.0mm, abrasion index≤2.0% of catalyst.
23. according to the process described in claim 22, it is characterised in that: the boiling bed hydrogenation reforming catalyst granularity is
0.3~0.8mm.
24. process described in accordance with the claim 1, it is characterised in that: also wrapped in the boiling bed hydrogenation reforming catalyst
Include adjuvant component.
25. according to the process described in claim 24, it is characterised in that: the adjuvant component is one in P, B, Ti, Zr
Kind is several.
26. according to the process described in claim 24, it is characterised in that: the additional amount of the auxiliary agent is being catalyzed based on the element
Content is 5wt% or less in agent.
27. process described in accordance with the claim 1, it is characterised in that: the preparation of the boiling bed hydrogenation reforming catalyst
Method, including prepare high silicon aluminium dry glue, then with it is molecular sieve molded, dry and roasting obtains carrier, is loaded using infusion process
Hydrogenation active metal component obtains catalyst.
28. process described in accordance with the claim 1, it is characterised in that: when step (2.3) after reaction, then to step
(2.3) alkaline solution is added in slurries, makes slurry pH value 7.0~8.5.
29. process described in accordance with the claim 1, it is characterised in that: clay described in step (2.1) is kaolin, covers
One or more of de- soil, galapectite, diatomite.
30. process described in accordance with the claim 1, it is characterised in that: roasting condition described in step (2.1) are as follows: roasting
Temperature is 600~900 DEG C, and calcining time is 0.5~6.0 hour.
31. process described in accordance with the claim 1, it is characterised in that: the alkaline solution containing aluminium described in step (2.2) is
The meta-aluminate solution of alkali metal.
32. according to the process described in claim 31, it is characterised in that: the alkaline solution containing aluminium described in step (2.2)
For sodium metaaluminate, potassium metaaluminate or their mixture.
33. according to process described in claim 31 or 32, it is characterised in that: the alkalinity containing aluminium described in step (2.2)
Solution is sodium metaaluminate.
34. according to the process described in claim 31, it is characterised in that: the concentration of the alkaline solution containing aluminium is 100
~300gAl2O3/ L, Crater corrosion are 2.1~13.0, and Crater corrosion is the molar ratio of alkali metal oxide and aluminium oxide.
35. according to the process described in claim 34, it is characterised in that: the Crater corrosion is 2.1~7.2.
36. process described in accordance with the claim 1, it is characterised in that: the additional amount of modified clay is 60 in step (2.2)
~120g is modified alkaline solution of the clay/L containing aluminium.
37. process described in accordance with the claim 1, it is characterised in that: step (2.3) the acidic silicasol pH value is 2
~4, concentration is 50~90gSiO2/L。
38. process described in accordance with the claim 1, it is characterised in that: alkaline solution described in step (2.4) is hydroxide
One of sodium, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, saleratus are a variety of, the weight of the alkaline solution
Concentration is 5%~10%.
39. process described in accordance with the claim 1, it is characterised in that: aging pH value described in step (2.5) is 6~9,
Aging temperature is 40~65 DEG C, and ageing time is 0.5~4.0h；Drying condition is 110~120 DEG C 4~6 hours dry.
40. according to the process described in claim 27, it is characterised in that: the preparation method of boiling bed hydrogenation reforming catalyst
In, the condition of carrier drying and roasting is as follows: 100 DEG C~150 DEG C of drying temperature, drying time 2~for 24 hours；400 DEG C of maturing temperature
~650 DEG C, 2~8h of calcining time.
41. according to the process described in claim 27, it is characterised in that: the preparation method of boiling bed hydrogenation reforming catalyst
In, the metal salt containing active metal component is configured to dipping solution, then loads to carrier, is catalyzed through dry and roasting
Agent, wherein 100 DEG C~150 DEG C of drying temperature, drying time 2~for 24 hours, catalyst is in 400 DEG C~600 DEG C 2~8h of roasting.
42. process described in accordance with the claim 1, it is characterised in that: the poor ignition quality fuel is catalytic cracking diesel oil, property
Matter are as follows: 20 DEG C of density are 0.88~0.99g/cm3, doing is 360~400 DEG C, and arene content is 50wt%~90wt%, and catalysis is split
The sulfur content for changing diesel oil is 0.2wt%~2.0wt%, and nitrogen content is 500~2000 μ g/g.
43. process described in accordance with the claim 1, it is characterised in that: the operation in boiling bed hydrogenation cracking reaction area
Condition are as follows: reaction pressure is 5~10MPa, and temperature is 370~450 DEG C, and volume space velocity is 1.0~5.0h when liquid-1, hydrogen oil volume
Than being 100~1000.
44. process described in accordance with the claim 1, it is characterised in that: the operation of the boiling bed hydrogenation processing reaction zone
Condition are as follows: reaction pressure is 5~8MPa, and temperature is 280~350 DEG C, and volume space velocity is 1.0~5.0h when liquid-1, hydrogen to oil volume ratio
It is 100~1000.
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|---|---|---|---|---|
| EP0427547A1 (en) * | 1989-11-08 | 1991-05-15 | Mobil Oil Corporation | Production of gasoline and distillate fuels from light cycle oil |
| US7384542B1 (en) * | 2004-06-07 | 2008-06-10 | Uop Llc | Process for the production of low sulfur diesel and high octane naphtha |
| CN103102938A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Fluidized bed hydrotreatment method |
| CN103769122A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing hydro-treatment catalyst |
| CN103769069A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of alumina dry glue containing silicon |
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2016
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0427547A1 (en) * | 1989-11-08 | 1991-05-15 | Mobil Oil Corporation | Production of gasoline and distillate fuels from light cycle oil |
| US7384542B1 (en) * | 2004-06-07 | 2008-06-10 | Uop Llc | Process for the production of low sulfur diesel and high octane naphtha |
| CN103102938A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Fluidized bed hydrotreatment method |
| CN103769122A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing hydro-treatment catalyst |
| CN103769069A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of alumina dry glue containing silicon |
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