CN112745925A - Method for treating gasoline - Google Patents
Method for treating gasoline Download PDFInfo
- Publication number
- CN112745925A CN112745925A CN201911048197.5A CN201911048197A CN112745925A CN 112745925 A CN112745925 A CN 112745925A CN 201911048197 A CN201911048197 A CN 201911048197A CN 112745925 A CN112745925 A CN 112745925A
- Authority
- CN
- China
- Prior art keywords
- gasoline
- catalyst
- desulfurization
- fraction
- molecular sieve
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 122
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 89
- 230000023556 desulfurization Effects 0.000 claims abstract description 89
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 238000001179 sorption measurement Methods 0.000 claims abstract description 58
- 150000001336 alkenes Chemical class 0.000 claims abstract description 40
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 37
- 239000011593 sulfur Substances 0.000 claims abstract description 37
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000005520 cutting process Methods 0.000 claims abstract description 12
- 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 74
- 239000002808 molecular sieve Substances 0.000 claims description 73
- 229910052751 metal Inorganic materials 0.000 claims description 43
- 239000002184 metal Substances 0.000 claims description 43
- 238000005899 aromatization reaction Methods 0.000 claims description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 8
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 230000000274 adsorptive effect Effects 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 238000004523 catalytic cracking Methods 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010937 tungsten Substances 0.000 claims description 3
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- 239000010949 copper Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
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- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000004227 thermal cracking Methods 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 24
- 239000002253 acid Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 22
- 239000013078 crystal Substances 0.000 description 15
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
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- 238000002156 mixing Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
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- 150000002431 hydrogen Chemical class 0.000 description 7
- 150000007524 organic acids Chemical class 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000005995 Aluminium silicate Substances 0.000 description 6
- 235000012211 aluminium silicate Nutrition 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 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 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000010561 standard procedure Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
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- 101710169936 Bacteriocin lactococcin-A Proteins 0.000 description 3
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- 230000009471 action Effects 0.000 description 3
- 150000003863 ammonium salts Chemical class 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
- 229910052681 coesite Inorganic materials 0.000 description 3
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- 150000001993 dienes Chemical class 0.000 description 3
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- 229930195733 hydrocarbon Natural products 0.000 description 3
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- 238000004519 manufacturing process Methods 0.000 description 3
- -1 octane olefins Chemical class 0.000 description 3
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- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 2
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- BLZKSRBAQDZAIX-UHFFFAOYSA-N 2-methyl-1-benzothiophene Chemical class C1=CC=C2SC(C)=CC2=C1 BLZKSRBAQDZAIX-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- General Chemical & Material Sciences (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for treating gasoline, which comprises the following steps: cutting a gasoline raw material to obtain a light gasoline fraction and a heavy gasoline fraction; sending the obtained light gasoline fraction into a hydrotreating reactor to contact with a hydrogenation catalyst for mild hydrodesulfurization reaction to obtain desulfurized light gasoline; and (3) feeding the obtained heavy gasoline fraction into a fluidized reactor to contact with an adsorption desulfurization catalyst and carrying out adsorption desulfurization reaction to obtain the desulfurized heavy gasoline. The method provided by the invention can reduce the sulfur content in the gasoline, retain the olefin to the maximum extent and maintain or improve the octane number of the gasoline.
Description
Technical Field
The present invention relates to a method for treating gasoline.
Background
Air pollution caused by automobile exhaust emission is increasingly serious. With the increasing importance of people on environmental protection, China speeds up the pace of upgrading the quality of automotive fuel, and GB17930-2016 requires that the sulfur content in gasoline is not more than 10 mug/g and the volume fraction of olefin is not more than 18%.
The catalytic cracking gasoline is the main component of the motor gasoline in China, accounts for about 75% in a gasoline pool, and is characterized by having higher contents of olefin and sulfur. It is not difficult to realize deep desulfurization of gasoline and reduce the content of olefin in catalytically cracked gasoline by adopting a hydrogenation technology, but because olefin is a high-octane component, the great reduction of the content of olefin causes serious loss of the gasoline octane number, thereby affecting the automotive performance of gasoline and the economic benefit of a refinery, and therefore, the deep desulfurization of gasoline is realized while the gasoline octane number is kept to be a hotspot of clean gasoline production in China.
At present, the deep desulfurization of gasoline mainly adopts a hydrodesulfurization method or an adsorption desulfurization method.
Selective hydrodesulfurization is one of the main modes for removing thiophene sulfides at present, but the reactions such as olefin saturation and the like also occur in large quantity, so that the octane number loss is large. In addition, a deep hydrogenation method for recovering octane number is also accepted, and a second reactor is arranged to promote cracking, isomerization and alkylation reactions of hydrocarbons with low octane number while deep desulfurization and olefin saturation are carried out, so that the aim of recovering octane number is fulfilled. The adsorption process for removing sulfur-containing compound from fuel oil is to use adsorbent to make hydrogen reaction adsorption on light oil to produce metal sulfide or to use sulfide polarity to remove sulfur, so that it has low hydrogen consumption and high desulfurizing efficiency, and can produce gasoline with sulfur content below 10 microgram/g. Although the adsorption process realizes deep desulfurization of gasoline under the condition of low hydrogen consumption, the octane number of the gasoline product still has slight loss, and particularly when the gasoline raw material with high olefin content and high sulfur content is treated, the octane number loss of the gasoline is still large.
Chinese patent CN101845322A discloses a method for reducing sulfur and olefin content in gasoline, the raw material catalytically cracked gasoline is first passed through a prehydrogenation reactor to remove diolefin, then is passed through a fractionating tower to be cut and fractionated into light gasoline and heavy gasoline, the light gasoline is undergone the process of hydrodesulphurization by hydrogen adsorption, the heavy gasoline is passed through a selective hydrogenation reactor to undergo hydrodesulfurization, the reaction effluent is passed through a hydro-upgrading reactor to undergo hydro-upgrading so as to reduce olefin content, and the heavy gasoline after being upgraded is blended with light gasoline adsorption desulfurization product to obtain the clean gasoline meeting the standard requirements. The adsorption desulfurization is carried out in the presence of hydrogen, and can saturate olefins in the catalytic cracking gasoline, especially light gasoline, and the octane number of olefin components in the light gasoline is high, so that the octane number of the gasoline is greatly lost.
Disclosure of Invention
Hair brushThe present inventors have discovered that catalytic gasoline olefins are primarily concentrated in the light gasoline fraction, especially the high octane C5、C6The most important of the olefin, whether adsorption desulfurization or hydrodesulfurization, is to optimize the catalyst and process conditions as much as possible during the desulfurization process to retain the light gasoline olefin and reduce octane number loss.
The invention aims to provide a method for treating gasoline, which can reduce the sulfur content in the gasoline, retain olefin to the maximum extent and maintain or improve the octane number of the gasoline.
In order to achieve the above object, the present invention provides a method for treating gasoline, comprising:
cutting a gasoline raw material to obtain a light gasoline fraction and a heavy gasoline fraction;
sending the obtained light gasoline fraction into a hydrotreating reactor to contact with a hydrogenation catalyst for mild hydrodesulfurization reaction to obtain desulfurized light gasoline;
and (3) feeding the obtained heavy gasoline fraction into a fluidized reactor to contact with an adsorption desulfurization catalyst to carry out adsorption desulfurization reaction, thereby obtaining the desulfurized heavy gasoline.
Compared with the prior art, the invention has the following technical effects:
1. the light gasoline fraction is subjected to mild hydrotreating, so that high-octane olefin is retained to the maximum extent while the sulfur content is reduced;
2. according to the method, after the high-sulfur gasoline raw material is cut and separated into the light gasoline fraction and the heavy gasoline fraction, the light gasoline fraction is subjected to mild hydrotreating, so that the sulfur content is reduced, and simultaneously olefin is retained to the maximum extent; the method contacts the heavy gasoline fraction with the adsorption desulfurization catalyst to carry out desulfurization reaction, and can greatly improve the desulfurization rate of the heavy gasoline fraction.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic flow diagram of one embodiment of the method of treating gasoline of the present invention.
Description of the reference numerals
1 gasoline feed 2 fractionating column 3 heavy gasoline fractions
4 hydrogen 5 fluidized reactor 6 desulfurization product/desulfurization and aromatization product
7 high-pressure separator 8 tail gas 9 desulfurization heavy gasoline
10 light gasoline fraction 11 pretreatment unit 12 moderating light gasoline before hydrogenation
13 hydrogen 14 hydrotreatment reactor 15 hydrodesulfurization product
16 fractionating tower 17 tail gas 18 desulfurized light gasoline
19 Mixer 20 gasoline product
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The RIPP test method can be found in petrochemical analysis, Yangcui and other editions, 1990 edition.
The invention provides a method for treating gasoline, which comprises the following steps: cutting a gasoline raw material to obtain a light gasoline fraction and a heavy gasoline fraction; sending the obtained light gasoline fraction into a hydrotreating reactor to contact with a hydrogenation catalyst for mild hydrodesulfurization reaction to obtain desulfurized light gasoline; and (3) feeding the obtained heavy gasoline fraction into a fluidized reactor to contact with an adsorption desulfurization catalyst to carry out adsorption desulfurization reaction, thereby obtaining the desulfurized heavy gasoline.
According to the present invention, mild hydrodesulfurization is meant to refer to contacting the light gasoline fraction with a hydrogenation catalyst under mild conditions of temperature and pressure to reduce the sulfur content of the light gasoline fraction while reducing the degree to which the olefins are saturated during hydrogenation to produce a high octane desulfurized light gasoline. The desulfurized light gasoline can be used as a gasoline octane value blending component, and can also be mixed with heavy gasoline fractions to be used as a full-range gasoline product.
For example, the step of moderating the hydrodesulfurization reaction may comprise: contacting the light gasoline fraction with a hydrogenation catalyst to convert sulfur in sulfur-containing compounds in the light gasoline fraction into hydrogen sulfide, and removing the hydrogen sulfide from a reaction effluent by a vapor-liquid separation, fractionation or stripping method to obtain the desulfurized light gasoline, wherein the conditions for moderating the hydrodesulfurization reaction comprise: the temperature can be 200-400 ℃, preferably 210-320 ℃, the reaction pressure can be 1-4MPa, preferably 1.2-3MPa, and the liquid hourly space velocity can be 1-10h-1Preferably 2-8h-1The hydrogen-oil volume ratio can be 100-600, preferably 100-300, wherein the reaction temperature refers to the average temperature of the reactor bed layer, and the reaction pressure refers to the hydrogen pressure at the inlet of the reactor. The preferred mild hydrodesulfurization reaction conditions described above can further reduce the sulfur content of the light gasoline fraction while maximizing the retention of high octane olefins.
The hydroprocessing reactor according to the present invention may be of a kind conventional in the art, for example one or more of a fixed bed hydrogenation reactor, a moving bed reactor and a fluidized bed reactor, preferably a fixed bed reactor. For example, a gasoline fraction may be introduced into a fixed bed hydrotreating reactor, contacted with a catalyst bed containing the above-mentioned hydrogenation catalyst, subjected to mild hydrodesulfurization reaction,
one embodiment for moderating the hydrodesulfurization reaction: contacting the light gasoline fraction with a hydrogenation catalyst to convert sulfur in sulfur-containing compounds in the light gasoline fraction into hydrogen sulfide to obtain desulfurized light gasoline, wherein the conditions for moderating hydrodesulfurization reaction comprise: the average temperature of a reactor bed layer is 250--1The volume ratio of hydrogen to oil is 110-140.
According to the present invention, the hydrogenation catalyst may be a conventional hydrodesulfurization catalyst, and in one embodiment, the hydrodesulfurization catalyst comprises a carrier and a metal active component loaded on the carrier, wherein the metal active component comprises at least one of a group VIII metal element and a group VIB metal element. Preferably, the group VIB metal is selected from molybdenum and/or tungsten and the group VIII metal is selected from cobalt and/or nickel. More preferably, the group VIII metal element in the hydrogenation catalyst is cobalt and the group VIB metal element is molybdenum.
According to the sulfided hydrodesulfurization catalyst system of the present invention, the content of each metal component in the catalyst may be a conventional content. Preferably, the group VIII metal element may be present in an amount of 0.3 to 6 wt.%, such as 1 to 5.5 wt.% or 0.4 to 6 wt.%, and the group VIB metal element in an amount of 4 to 25 wt.%, such as 5 to 24 wt.% or 6.5 to 22.5 wt.%, respectively, calculated as oxides, based on the total weight of the catalyst.
According to the invention, the support of the hydrogenation catalyst may be an alumina support and/or a silica-alumina support, preferably an alumina support. The alumina can be one or more of various existing aluminas used as catalyst carriers, such as gamma-alumina, alpha-alumina and eta-alumina. More preferably, the first support may have an average pore size of 6 to 15nm, preferably 8 to 12nm, more preferably 8.5 to 10 nm. Alumina satisfying the above properties can be obtained by various methods, and for example, can be prepared from pseudo boehmite powder by shaping in an appropriate manner. For example, the pseudo-boehmite is added with proper amount of water, peptizer and extrusion aid and is shaped by a strip extruding machine. The shaped profiles include, but are not limited to, cylinders, clovers, butterflies, allotypes, and the like. And drying and roasting the molded carrier to obtain the alumina carrier. The specific surface area of the pseudoboehmite powder for preparing the carrier is preferably 300-600m2The pore volume is 0.6-1.5 mL/g.
According to the invention, the process for the mild hydrodesulphurization of light gasoline fractions may comprise the sulphidation of the above hydrogenation catalyst and the subsequent passing of the light gasoline fraction in such a way that it is in contact with the above hydrogenation catalyst under mild hydrodesulphurization conditions.
According to the invention, in order to directly produce the gasoline of national V or even VI, the method can further comprise the following steps: and mixing the obtained desulfurized light gasoline and desulfurized heavy gasoline to obtain a gasoline product.
According to the present invention, the conditions of the adsorption desulfurization reaction may vary within a wide range, and preferably, the adsorption desulfurization conditions may include: the reaction temperature is 350-500 ℃, the preferable temperature is 380-420 ℃, and the weight hourly space velocity is 2-20h-1Preferably 5 to 10 hours-1The reaction pressure is 2.0-3.5MPa, preferably 2.5-3.0MPa, and the volume ratio of hydrogen to heavy gasoline fraction (at 0 deg.C (273K) in standard conditions (STP), 1.01X 105Pa) of 10 to 500, preferably 50 to 200.
According to the present invention, the adsorption desulfurization catalyst is well known to those skilled in the art, and may contain silica, alumina, zinc oxide, and a desulfurization active metal, which may be at least one selected from the group consisting of cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin, and vanadium.
In one embodiment, the adsorbed desulfurization catalyst comprises 10-90 wt.% zinc oxide, 5-85 wt.% silica, and 5-30 wt.% alumina, based on the dry weight of the adsorbed desulfurization catalyst and based on the weight of the oxides; the content of the desulfurization active metal in the adsorption desulfurization catalyst is 5-30 wt% based on the dry weight of the adsorption desulfurization catalyst and calculated by the weight of elements.
According to the invention, the adsorptive desulfurization catalyst may also contain 1 to 10 wt.% of coke-like substances. Industrial practice shows that the carbon content of the adsorption desulfurization catalyst has an influence on the desulfurization efficiency of the adsorption desulfurization catalyst and the octane number loss of gasoline, and the desulfurization efficiency of the adsorption desulfurization catalyst is gradually reduced along with the increase of the carbon content of the adsorption desulfurization catalyst, so that the octane number loss of the gasoline is reduced. Likewise, it is essential that the adsorptive desulfurization catalyst maintain a certain sulfur content. Practice shows that the sulfur carrying amount of the spent adsorption desulfurization catalyst is 9-10 wt%, the sulfur carrying amount of the regenerated adsorption desulfurization catalyst is 5-6 wt%, and the sulfur difference between the spent adsorption desulfurization catalyst and the regenerated adsorption desulfurization catalyst is about 4 wt%. In order to reduce the octane number loss of gasoline, the operation of small sulfur difference and large circulation amount which is generally considered reasonable can be adjusted to the operation of small circulation amount and large sulfur difference, the sulfur content of the regenerated adsorption desulfurization catalyst is reduced, the sulfur content of the spent adsorption desulfurization catalyst is improved, the octane number loss is reduced, the two operations are substantially the operations of keeping the higher sulfur carrying amount of the adsorption desulfurization catalyst participating in the reaction in a reactor, reducing the activity of the adsorption desulfurization catalyst and reducing the octane number loss.
According to the present invention, the heavy gasoline fraction can be contacted with a mixed catalyst containing an adsorption desulfurization catalyst and an aromatization catalyst to carry out desulfurization and aromatization reactions. For example, in one embodiment, the heavy gasoline fraction may be fed into a fluidized reactor to contact a mixed catalyst comprising the adsorption desulfurization catalyst and the olefin aromatization catalyst described above and subjected to desulfurization and aromatization reactions in the presence of hydrogen. The embodiment can reduce the sulfur content of the gasoline and simultaneously carry out mild cracking and aromatization on the olefin in the gasoline, thereby reducing the olefin content in the gasoline and improving the octane number of the gasoline; and two catalysts are adopted to be carried out in one fluidized reactor, so that the reaction efficiency is improved, the investment cost is reduced, and the reactor does not need to be increased or changed.
According to the present invention, the desulfurization and aromatization reaction refers to a process of desulfurizing heavy gasoline fraction in the presence of hydrogen under the combined action of an adsorption desulfurization catalyst and an olefin aromatization catalyst and converting olefins into aromatics, accompanied by a cracking reaction, and the conditions of the desulfurization and aromatization reaction may be the same as or different from the conditions of the adsorption desulfurization reaction, for example, the conditions of the desulfurization and aromatization reaction may include: the reaction temperature is 350-500 ℃, the preferable temperature is 380-420 ℃, and the weight hourly space velocity is 2-20h-1Preferably 5 to 10 hours-1The reaction pressure is 2.0-3.5MPa, preferably 2.5-3.0MPa, and the volume ratio of hydrogen to heavy gasoline fraction (at 0 deg.C (273K) in standard conditions (STP), 1.01X 105Pa) of 10 to 500, preferably 50 to 200.
According to the present invention, the olefin aromatization catalyst refers to a catalyst capable of converting hydrocarbons such as olefins in a gasoline feedstock into aromatic hydrocarbons. For example, the olefin aromatization catalyst may comprise 15 to 60 weight percent natural minerals, 10 to 30 weight percent inorganic oxide binder, and 20 to 80 weight percent phosphorus-containing and metal-loaded MFI structural molecular sieve, based on the dry weight of the olefin aromatization catalyst.
Preferably, n (SiO) of the molecular sieve in the olefin aromatization catalyst2)/n(Al2O3) Greater than 100; with P2O5The phosphorus content of the molecular sieve is 0.1-5 wt% based on the dry weight of the molecular sieve; the supported metal content of the molecular sieve is 0.5-5 wt% calculated on the supported metal oxide and based on the dry weight of the molecular sieve.
Further preferably, the molecular sieve has an Al distribution parameter d (Al) satisfying: 0.6-D (Al) -0.85, wherein D (Al) -Al (S)/Al (C), Al (S) represents the aluminum content of a region which is arbitrarily more than 100 square nanometers in the distance from the edge of a crystal face of the molecular sieve crystal grain to the inside H of the crystal face measured by a TEM-EDS method, Al (C) represents the aluminum content of a region which is arbitrarily more than 100 square nanometers in the distance from the geometric center of the crystal face of the molecular sieve crystal grain to the outside H of the geometric center measured by the TEM-EDS method, wherein H is 10 percent of the distance from a certain point on the edge of the crystal face to the geometric center of the crystal face; the molecular sieve has a supported metal distribution parameter D (M) satisfying: d ≦ d (m) ≦ 10, where d (m) ═ m (s)/m (c), m(s) represents the supported metal content of the molecular sieve crystal grains measured by TEM-EDS method in any region greater than 100 square nanometers within the distance H inward of the edges of the crystal faces, m (c) represents the supported metal content of the molecular sieve crystal grains measured by TEM-EDS method in any region greater than 100 square nanometers within the distance H outward of the geometric centers of said crystal faces; the proportion of the mesopore volume of the molecular sieve to the total pore volume is 40-80%, and the proportion of the mesopore volume with the pore diameter of 2-20 nm to the total mesopore volume is more than 90%; the ratio of the strong acid amount of the molecular sieve to the total acid amount is 60-80%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 15-80. Preferably, n (SiO) of the molecular sieve2)/n(Al2O3) Greater than 120; with P2O5The phosphorus content of the molecular sieve is 0.2-4 wt% based on the dry weight of the molecular sieve; calculated as the metal-bearing oxide and based on the dry weight of the molecular sieveThe content of the load metal of the molecular sieve is 0.5-3 wt%; the molecular sieve has an Al distribution parameter D (Al) satisfying: d (Al) is more than or equal to 0.65 and less than or equal to 0.8; the molecular sieve has a supported metal distribution parameter D (M) satisfying: d is more than or equal to 3 and less than or equal to 6 (M); the proportion of the mesopore volume of the molecular sieve to the total pore volume is 50-70%, and the proportion of the mesopore volume with the pore diameter of 2-20 nm to the total mesopore volume is more than 92%; the ratio of the strong acid amount of the molecular sieve to the total acid amount is 65-75%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 20-50.
According to the present invention, the supported metal refers to a metal supported on the molecular sieve by a supporting method, and does not include aluminum and alkali metals such as sodium and potassium, and may be zinc and/or gallium, and may also include other metals, and the present invention is not limited thereto.
According to the invention, the method for measuring the aluminum content and the supported metal content of the molecular sieve by using the TEM-EDS method is well known by persons skilled in the art, wherein the geometric center is also well known by persons skilled in the art and can be obtained by calculation according to a formula, the invention is not repeated, the geometric center of a general symmetrical graph is the intersection point of connecting lines of all relative vertexes, for example, the geometric center of a hexagonal crystal face of a conventional hexagonal plate-shaped ZSM-5 molecular sieve is at the intersection point of connecting lines of three relative vertexes, the crystal face is one face of a regular crystal grain, and the inward direction and the outward direction both refer to the inward direction and the outward direction on the crystal face.
According to the invention, the proportion of the mesopore volume of the molecular sieve to the total pore volume is measured by a nitrogen adsorption BET specific surface area method, wherein the mesopore volume is the pore volume with the pore diameter of more than 2 nanometers and less than 100 nanometers; the strong acid amount of the molecular sieve is NH in proportion to the total acid amount3The TPD method, the acid centre of which is NH3Desorbing the corresponding acid center at the temperature of more than 300 ℃; and the ratio of the acid amount of the B acid to the acid amount of the L acid is measured by adopting a pyridine adsorption infrared acidity method.
According to the present invention, the natural mineral substance means a natural simple substance or compound formed under the combined action of various substances of the earth's crust (referred to as geological action) and having a specific chemical composition expressed by a chemical formula and a relatively fixed chemical composition, and may include, for example, at least one selected from kaolin, halloysite, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite, and the inorganic oxide binder means an inorganic oxide that plays a role of binding each component in a catalyst, and may include, for example, at least one selected from silica, alumina, zirconia, titania and amorphous silica-alumina.
One embodiment of the method for producing the olefin aromatization catalyst according to the present invention: mixing and pulping the preparation raw material of the olefin aromatization catalyst and water and spray drying; wherein the preparation raw materials comprise 15-60 wt% of natural minerals, 10-30 wt% of precursors of inorganic oxide binders and 20-80 wt% of MFI structure molecular sieves containing phosphorus and supported metals, based on the weight of the preparation raw materials on a dry basis.
According to the present invention, the preparation step of the phosphorus-containing and metal-loaded MFI structure molecular sieve may include: a. filtering and washing the crystallized MFI structure molecular sieve slurry to obtain a water-washed molecular sieve; wherein the sodium content of the washed molecular sieve is less than 3 wt% based on the total dry basis weight of the washed molecular sieve calculated as sodium oxide; b. b, carrying out desiliconization treatment on the washed molecular sieve obtained in the step a in an alkali solution, and filtering and washing to obtain a desiliconized molecular sieve; c. b, performing ammonium exchange treatment on the desiliconized molecular sieve obtained in the step b to obtain an ammonium exchange molecular sieve; wherein the ammonium exchanged molecular sieve has a sodium content of less than 0.2 wt.% based on sodium oxide and based on total dry basis weight of the ammonium exchanged molecular sieve; d. c, dealuminizing the ammonium exchange molecular sieve obtained in the step c in a composite acid dealuminizing agent solution consisting of fluosilicic acid, organic acid and inorganic acid, and filtering and washing to obtain a dealuminized molecular sieve; e. d, carrying out phosphorus modification treatment and loading treatment of loaded metal on the dealuminized molecular sieve obtained in the step d to obtain a modified molecular sieve; f. and e, carrying out hydrothermal roasting treatment on the modified molecular sieve obtained in the step e to obtain the MFI structure molecular sieve containing phosphorus and loaded metal.
According to the present invention, the slurry of the MFI structure molecular sieve obtained by crystallization is well known to those skilled in the art, and the present invention is not repeated, wherein the MFI structure molecular sieve is also well known to those skilled in the art, and can be obtained by crystallization without amine, or can be a molecular sieve prepared by a template method, wherein the molecular sieve obtained by crystallization without amine does not need to be calcined, the molecular sieve prepared by the template method needs to be dried and then calcined in air, and the silica-alumina ratio of the ZSM-5 molecular sieve is generally less than 100.
According to the present invention, the desiliconization treatment with an alkaline solution is well known to those skilled in the art, the alkaline solution in step b may be selected from sodium hydroxide solution and/or potassium hydroxide solution, preferably sodium hydroxide solution, and the conditions of the desiliconization treatment may include: the weight ratio of the molecular sieve to the alkali in the alkali solution on a dry basis is 1: (0.1-1), preferably 1: (0.15-0.4); the desiliconization treatment is carried out at a temperature of room temperature to 100 ℃, preferably 50 to 85 ℃, for 15 minutes to 8 hours, preferably 30 minutes to 4 hours.
According to the present invention, the ammonium exchange treatment is well known to those skilled in the art, for example, the base treated desilicated molecular sieve in step c can be prepared according to the following molecular sieve: ammonium salt: h2O is 1: (0.1-1): (5-10) weight ratio, exchanging at room temperature to 100 deg.C for 0.5-2 hr, filtering to make Na on zeolite2The O content is less than 0.2 wt%. The ammonium salt may be a commonly used inorganic ammonium salt, for example, at least one selected from the group consisting of ammonium chloride, ammonium sulfate and ammonium nitrate.
According to the present invention, the organic acid and the inorganic acid in step d are well known to those skilled in the art, for example, the organic acid may be at least one selected from ethylenediaminetetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, preferably oxalic acid; the inorganic acid may be at least one selected from hydrochloric acid, sulfuric acid and nitric acid, and is preferably hydrochloric acid.
The dealumination treatment in step d according to the present invention is well known to those skilled in the art, but the use of a mineral acid, an organic acid and a fluosilicic acid together for dealumination treatment has not been reported. The dealumination treatment can be carried out once or for multiple times, organic acid can be firstly mixed with the ammonium exchange molecular sieve, and then fluosilicic acid and inorganic acid are mixed with the ammonium exchange molecular sieve, namely, the organic acid is firstly added into the ammonium exchange molecular sieve, and then the fluosilicic acid and the inorganic acid are slowly and concurrently added, or the fluosilicic acid is firstly added and then the inorganic acid is added, preferably the fluosilicic acid and the inorganic acid are slowly and concurrently added. The dealumination treatment conditions may be: the weight ratio of the molecular sieve, the fluosilicic acid, the organic acid and the inorganic acid is 1: (0.02-0.5): (0.05-0.5): 0.05-0.5), preferably 1: (0.05-0.3): (0.1-0.3): 0.1-0.3); the treatment temperature is 25-100 ℃, and the treatment time is 0.5-6 hours.
According to the present invention, the phosphorus modification treatment and the supporting treatment of the supported metal are well known to those skilled in the art, and the phosphorus modification treatment in step e may include: impregnating and/or ion-exchanging the molecular sieve with at least one phosphorus-containing compound selected from phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate; the loading treatment of the loaded metal in the step e may include: dissolving soluble salt containing at least one load metal selected from zinc and gallium in deionized water, adjusting pH value with ammonia water to precipitate the load metal in the form of hydroxide, and mixing the obtained precipitate and molecular sieve uniformly.
According to the present invention, the hydrothermal calcination treatment of the molecular sieve is well known to those skilled in the art, and the hydrothermal calcination treatment conditions in step f may be: the atmosphere of the roasting treatment is a water vapor atmosphere; the roasting temperature is 400-800 ℃, and the roasting time is 0.5-8 hours.
The washing described in the present invention is well known to the person skilled in the art and can be carried out in the following manner: and (3) leaching the filtered molecular sieve by using water with the temperature of 30-60 ℃ which is 5-10 times that of the filtered molecular sieve.
According to the present invention, the precursor of the inorganic oxide binder refers to a raw material for preparing a catalytic cracking catalyst for generating the inorganic oxide binder in the catalytic cracking catalyst, and may include, for example, at least one selected from the group consisting of silica sol, alumina sol, peptized pseudo-boehmite, silica-alumina sol, and phosphorus-containing alumina sol.
The ratio of the adsorption desulfurization catalyst and the olefin aromatization catalyst in the fluidized reactor may vary depending on the contents of olefins and sulfur in gasoline, and for example, the ratio of the olefin aromatization catalyst to the mixed catalyst may be 1 to 30% by weight, preferably 3 to 15% by weight, based on the weight of the mixed catalyst.
According to the present invention, the gasoline raw material is well known to those skilled in the art and may be at least one selected from the group consisting of catalytically cracked gasoline, coker gasoline, thermally cracked gasoline, and straight run gasoline. The gasoline treated according to the invention is preferably a high olefin and high sulfur gasoline, the olefin volume fraction of which is generally greater than 20% by volume, preferably greater than 30% by volume, more preferably greater than 40% by volume, and even more preferably greater than 50% by volume; the sulfur content is generally 100. mu.g/g or more, more preferably more than 500. mu.g/g, still more preferably more than 800. mu.g/g, and most preferably more than 1500. mu.g/g, and the organic sulfides in gasoline are generally mercaptans, thioethers, thiophenes, alkylthiophenes, benzothiophenes, methylbenzothiophenes, and the like.
According to the invention, the cut points of the light and heavy gasoline fractions may be between 60 and 90 ℃ and the cutting of the desulfurization and aromatization products is generally carried out in a fractionating column according to the distillation range from low to high, for example, the operating conditions of a gasoline cutting fractionating column are: the temperature at the top of the tower is 60-90 ℃, the temperature at the bottom of the tower is 120-160 ℃, and the operating pressure is 0.1-1.0 MPa.
Fluidized reactors according to the invention are well known to those skilled in the art and may be selected, for example, from fluidized beds, risers, downgoing line reactors, composite reactors comprising risers and fluidized beds, composite reactors comprising risers and downgoing lines, composite reactors comprising two or more risers, composite reactors comprising two or more fluidized beds, composite reactors comprising two or more downgoing lines, preferably riser reactors and/or fluidized bed reactors, each of which may be divided into two or more reaction zones. The fluidized bed reactor can be one or more selected from a fixed fluidized bed, a bulk fluidized bed, a bubbling bed, a turbulent bed, a fast bed, a conveying bed and a dense-phase fluidized bed; the riser reactor can be one or more selected from the group consisting of an equal-diameter riser, an equal-linear-speed riser and various variable-diameter risers. Preferably, the fluidization reactor is selected from dense phase fluidization reactors.
According to the present invention, the light gasoline fraction is preferably pretreated to remove impurities such as sulfides and dienes before undergoing mild hydrodesulfurization to extend the life of the hydrogenation catalyst. Therefore, the method of the present invention may further comprise: and (2) pretreating the light gasoline fraction, and then performing mild hydrodesulfurization treatment, wherein the pretreatment can be at least one selected from alkali liquor extraction treatment, mercaptan conversion treatment and selective hydrogenation treatment. The alkali liquor extraction treatment uses alkali liquor to extract the mercaptan of the light gasoline fraction into the alkali liquor for removal; the mercaptan conversion treatment can be carried out by converting the small-molecular mercaptan into other sulfides, and the removal can be carried out by adopting a conventional alkali-free deodorization process, pre-hydrogenation and other modes, and the used catalyst and the catalyst promoter can be catalysts commonly used in the field. Selective hydrotreating is well known to those skilled in the art for the removal of diolefins from gasoline and can isomerize 3-methyl-1-butene to 2-methyl-1-butene.
A specific embodiment of the present invention will be provided with reference to the accompanying drawings, but the present invention is not limited thereto.
As shown in fig. 1, a high-sulfur gasoline raw material 1 is firstly sent into a fractionating tower 2 for cutting and fractionating into a light gasoline fraction 10 and a heavy gasoline fraction 3, wherein the cutting points of the light gasoline fraction and the heavy gasoline fraction are about 70-80 ℃. The light gasoline fraction 10 enters a pretreatment unit 11, is subjected to pretreatment such as mercaptan removal and the like to obtain light gasoline 12 before mild hydrogenation, is mixed with hydrogen 13 and enters a hydrotreating reactor 14 for reaction, and a hydrodesulfurization product 15 is fractionated by a fractionating tower 16 to obtain desulfurized light gasoline 18 and tail gas 17. And mixing the heavy gasoline fraction 3 and hydrogen 4, then feeding the mixture into a fluidized reactor 5, contacting with an adsorption desulfurization catalyst to perform adsorption desulfurization reaction, and feeding a desulfurization product 6 into a high-pressure separator 7 to obtain desulfurized heavy gasoline 9 and tail gas 8. The desulfurized heavy gasoline 9 is mixed with the desulfurized light gasoline 18 in a mixer 19 to obtain a gasoline product 20.
In another embodiment, as shown in fig. 1, a high-sulfur gasoline raw material 1 is first sent to a fractionating tower 2 for cutting and fractionating into a light gasoline fraction 10 and a heavy gasoline fraction 3, wherein the cutting points of the light gasoline fraction and the heavy gasoline fraction are about 70-80 ℃. The light gasoline fraction enters a pretreatment unit 11, is subjected to mercaptan removal and other pretreatments to obtain light gasoline 12 before mild hydrogenation, is mixed with hydrogen 13 and enters a hydrotreating reactor 14 for reaction, and a hydrodesulfurization product 15 is fractionated by a fractionating tower 16 to obtain desulfurized light gasoline 18 and tail gas 17. The heavy gasoline fraction 3 and hydrogen 4 are mixed and then enter a fluidized reactor 5, and are contacted with a mixed catalyst containing an adsorption desulfurization catalyst and an aromatization catalyst to carry out adsorption desulfurization and aromatization reaction, and a desulfurization and aromatization product 6 enters a high-pressure separator 7 to obtain desulfurized heavy gasoline 9 and tail gas 8. The desulfurized heavy gasoline 9 is mixed with the desulfurized light gasoline 18 in a mixer 19 to obtain a gasoline product 20.
The following examples further illustrate the invention but are not intended to limit the invention thereto.
The crystallinity of the present invention is determined by the standard method of ASTM D5758-2001(2011) e 1.
N (SiO) of the invention2)/n(Al2O3) I.e. the silicon to aluminium ratio is calculated from the contents of silica and alumina, the contents of silica and alumina being takenGB/T 30905-2014The standard method was used for the determination.
Phosphorus content of the inventionGB/T 30905-2014The standard method is adopted for determination, and the content of the loaded metal is adoptedGB/T 30905-2014The sodium content is determined by standard methodGB/T 30905-2014The standard method was used for the determination.
The total specific surface area of the invention is measured by an AS-3, AS-6 static nitrogen adsorption instrument produced by Quantachrome instruments.
The full cut of gasoline feedstock used in the examples and comparative examples was stabilized gasoline a from the petrochemical winnowing china, the properties of which are listed in table 1.
The adsorptive desulfurization catalysts used in the examples and comparative examples were produced by catalyst division of petrochemical Co., Ltd., China, under the product number FCAS, and the aromatization catalyst used was a laboratory-made catalyst under the brand number OTAZ-C-3, and the adsorptive desulfurization catalysts had the properties shown in Table 3. The preparation method of the olefin aromatization catalyst is as follows:
the properties of the raw materials used were as follows: kaolin (Kaolin, Suzhou, China, 75 wt% solids), pseudoboehmite (Kaolin, Shandong, 65 wt% solids, peptized with 31 wt% hydrochloric acid at a molar ratio of 0.20 based on alumina).
The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)2)/n(Al2O3) 27) the mother liquor was filtered off and washed with water to Na2The content of O is lower than 3.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0% NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added4Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na2The O content is lower than 0.2 weight percent, and a molecular sieve filter cake is obtained after filtering and washing; taking 50g (dry basis) of the molecular sieve, adding water to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 11g of oxalic acid while stirring, then adding 110g of hydrochloric acid (mass fraction is 10 percent) and 92g of fluosilicic acid (mass fraction is 3 percent) in a concurrent flow manner, and adding for 30 min; heating to 65 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into the filter cake and pulping to obtain molecular sieve slurry with the solid content of 45 weight percent; 1.2g H3PO4(concentration 85% by weight) and 3.3gZn (NO)3)2·6H2Dissolving O in 10g of water, adding ammonia water to adjust the pH value to 6, then adding the mixture into the molecular sieve slurry, uniformly mixing, drying, and roasting at 550 ℃ for 2 hours in a 100% water vapor atmosphere. The molecular sieve A was obtained, and the physicochemical properties are shown in Table 4.
Mixing pseudoboehmite with kaolin, preparing slurry with the solid content of 30 weight percent by using decationized water, uniformly stirring, adjusting the pH value of the slurry to 2.5 by using hydrochloric acid, keeping the pH value, standing and aging for 1 hour at 50 ℃, stirring for 1 hour to form colloid, and adding the prepared molecular sieve A and water to form catalyst slurry (with the solid content of 35 weight percent). Continuously stirring and then spray-drying to prepare the microsphere catalyst. Then roasting the microspherical catalyst for 1 hour at 500 ℃ to obtain the aromatization catalyst used by the invention, wherein the dry raw materials of the aromatization catalyst comprise 25 weight percent of kaolin, 25 weight percent of pseudo-boehmite and 50 weight percent of molecular sieve A.
The preparation method of the hydrogenation catalyst comprises the following steps:
weighing 200 g (dry basis) of an alumina precursor (prepared by a sodium metaaluminate-sodium sulfate method, trade name of Changling dry glue powder, a product of catalyst Changling division, wherein the content of monohydrate bauxite is 68 wt%), extruding the alumina precursor into a three-blade strip with the diameter of an external circle of 1.4 mm on a strip extruder, drying the strip at 120 ℃, and roasting the strip at 600 ℃ for 4 hours to obtain the carrier.
Molybdenum and cobalt are introduced into the carrier by a step-by-step impregnation method. First, 8.325 g of ammonium molybdate was weighed out with 16% by weight of NH3Dissolving the aqueous solution of (A) to 90 ml of solution, impregnating 100g of the carrier with the solution for 4 hours, drying at 120 ℃ for 4 hours, and roasting at 420 ℃ for 4 hours; then, 5.0 g of nickel nitrate was weighed, dissolved in 80 ml of water, and the molybdenum-loaded carrier was impregnated again with this solution, dried at 120 ℃ for 4 hours, and calcined at 420 ℃ for 4 hours to obtain catalyst C2. The catalyst C2 had the composition, calculated as oxides and based on the total weight of the catalyst, of: 6.0 weight percent of molybdenum oxide and 1.2 weight percent of nickel oxide.
In each of the following examples and comparative examples, Na was contained in the catalyst2O、NiO、ZnO、Ga2O3、Al2O3、SiO2The content of (B) is determined by X-ray fluorescence, wherein Al is2O3、SiO2The content of (A) is determined by referring to RIPP 134-90, and the determination method of the rest components is similar.
The octane number RON of the gasoline in the examples and comparative examples of the invention was determined by GB/T5487-1995, the gasoline PONA was determined by simulated distillation and gasoline monomer hydrocarbon analysis (tested by ASTM D2887 and ASTM D6733-01(2011) respectively), and the gasoline sulfur content was determined by SH/T0689-2000.
Example 1
And distilling the stabilized gasoline A in a fractionating tower, cutting into a light fraction and a heavy fraction, and controlling the final distillation point of the light fraction to be 70-80 ℃ (according to the ASTM D86 standard). Wherein, the light gasoline fraction obtained by distilling the stable gasoline A is marked as LCN-A, the heavy gasoline fraction is marked as HCN-A, and the properties of the LCN-A and the HCN-A are respectively listed in the table 2-1.
The light gasoline fraction with the serial number of LCN-A is extracted and pretreated by alkali liquor, and then enters A hydrotreating reactor for mild hydrodesulfurization reaction under the conditions that the average reaction temperature of A bed layer is 250 ℃, the reaction pressure is 1.8MPA and the airspeed is 7.0h-1And the hydrogen-oil volume ratio is 120, so that the desulfurized light gasoline LCN-A-H is obtained.
The heavy gasoline fraction with the number of HCN-A is contacted with an adsorption desulfurization catalyst FCAS in A small continuous fluidized bed reactor to carry out adsorption desulfurization reaction. The operating conditions were: the reaction temperature is 400 ℃, the pressure of the reactor is 2.5MPa, and the weight hourly space velocity of the heavy gasoline fraction is 5 hours-1. And cooling and separating the desulfurization product obtained from the top of the reactor to obtain tail gas and desulfurized heavy gasoline HCN-A-H. The regeneration temperature of the catalyst is 550 ℃, and the regenerated catalyst returns to the reactor for recycling.
The desulfurized light gasoline LCN-A-H and the desulfurized heavy gasoline HCN-A-H are mixed to obtain refined gasoline A (gasoline product), and the properties are shown in Table 5.
Example 2
The heavy gasoline fraction numbered HCN-A in example 1 was contacted with A mixed catalyst comprising an adsorption desulfurization catalyst FCAS and an aromatization catalyst OTAZ-C-3(OTAZ-C-3 accounts for 7% of the total weight of the catalyst) in A small continuous fluidized bed reactor to perform adsorption desulfurization and aromatization reactions. The operating conditions were: the reaction temperature is 400 ℃, the pressure of the reactor is 2.5MPa, and the weight hourly space velocity of the heavy gasoline fraction is 5 hours-1. The desulfurization and aromatization products obtained from the top of the reactor are cooled and separated to obtain tail gas and desulfurized heavy gasoline HCN-B-H. The regeneration temperature of the mixed catalyst is 550 ℃, and the regenerated mixed catalyst returns to the reactor for recycling.
The desulfurized light gasoline LCN-A-H of example 1 and desulfurized heavy gasoline HCN-B-H were mixed to obtain refined gasoline B of this example, the properties of which are shown in Table 5.
Example 3
Basically the same operation as in example 2, exceptCharacterized in that: the hydrotreating reaction conditions are as follows: the reaction temperature is 330 ℃, the reaction pressure is 1.1MPa, and the space velocity is 7.0h-1And the hydrogen-oil volume ratio is 120, so that the desulfurized light gasoline LCN-C-H is obtained. The desulfurized light gasoline LCN-C-H and the desulfurized heavy gasoline HCN-A-H were mixed to obtain refined gasoline C of this example, the properties of which are shown in Table 5.
Example 4
Essentially the same operation as in example 2, except that: the reaction conditions of the hydrotreatment are that the reaction temperature is 220 ℃, the reaction pressure is 2.5MPa, and the airspeed is 7.0h-1And the hydrogen-oil volume ratio is 120, so that the desulfurized light gasoline LCN-D-H is obtained. The desulfurized light gasoline LCN-D-H and the desulfurized heavy gasoline HCN-A-H were mixed to obtain refined gasoline D of this example, the properties of which are shown in Table 5.
Comparative example 1
The method comprises the following steps of (1) distilling the stable gasoline A in a fractionating tower by adopting the conventional selective hydrodesulfurization process, cutting the stable gasoline A into light fraction and heavy fraction, and controlling the final distillation point of the light fraction to be 50-60 ℃ (according to the ASTM D86 standard); the light gasoline fraction obtained by distillation of the stabilized gasoline A was designated as LCN-E and the heavy gasoline fraction was designated as HCN-E, the properties of which are shown in tables 2-1, respectively. Extracting the light gasoline fraction with alkali liquor to obtain desulfurized light gasoline LCN-E-H; the heavy gasoline fraction enters a hydrogenation treatment reactor for hydrogenation desulfurization reaction under the conditions of reaction temperature of 310 ℃, reaction pressure of 1.8MPa and space velocity of 3.0h-1Obtaining desulfurized heavy gasoline HCN-E-H, wherein the volume ratio of hydrogen to oil is 350; mixing the desulfurized light gasoline and the desulfurized heavy gasoline to obtain refined gasoline E; the refined gasoline properties are listed in table 5.
Comparative example 2
The existing adsorption desulfurization process is adopted, and the stable gasoline A is contacted with the adsorption desulfurization catalyst FCAS in a small continuous fluidized bed reactor to carry out adsorption desulfurization reaction. The operating conditions were: the reaction temperature is 400 ℃, the pressure of the reactor is 2.5MPa, and the weight hourly space velocity of the stable gasoline fraction is 5 hours-1. And cooling and separating the desulfurization product obtained from the top of the reactor to obtain tail gas and refined gasoline F. The regeneration temperature of the catalyst is 550 ℃, and the regenerated catalyst returns to the reactor for recycling. The refined gasoline properties are listed in table 5.
TABLE 1
TABLE 2-1
Tables 2 to 2
TABLE 3
| Catalyst and process for preparing same | FCAS |
| Chemical composition, weight | |
| Alumina oxide | |
| 13 | |
| Nickel oxide | 21 |
| Zinc oxide | 52 |
| |
14 |
| Apparent appearanceDensity, kg/m3 | 1010 |
| Sieving the components by weight percent | |
| 0 to 40 μm | 14.5 |
| 40 to 80 μm | 51.9 |
| >80 micron | 33.6 |
TABLE 4
| Item | Molecular sieve A |
| Degree of crystallization/%) | 90 |
| n(SiO2)/n(Al2O3) | 110 |
| P2O5Content/% | 1.5 |
| Content of supported metal oxide/%) | 1.6 |
| SBET/(m2/g) | 440 |
TABLE 5
As can be seen from Table 5, the methods of examples and comparative examples can achieve a sulfur content of the refined gasoline of 10. mu.g/g or less, but the RON of the refined gasoline of examples is increased by 1.9 to 3.6 units as compared with comparative example 1 and by about 1.5 to 3.2 units as compared with comparative example 2, which shows that the octane number of the gasoline product can be maintained or increased while the sulfur content is reduced by the method of the present invention.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (11)
1. A method of treating gasoline, the method comprising:
cutting a gasoline raw material to obtain a light gasoline fraction and a heavy gasoline fraction;
sending the obtained light gasoline fraction into a hydrotreating reactor to contact with a hydrogenation catalyst for mild hydrodesulfurization reaction to obtain desulfurized light gasoline;
and (3) feeding the obtained heavy gasoline fraction into a fluidized reactor to contact with an adsorption desulfurization catalyst to carry out adsorption desulfurization reaction, thereby obtaining the desulfurized heavy gasoline.
2. The method of claim 1, wherein the hydrogenation catalyst comprises a carrier and a metal active component loaded on the carrier, wherein the metal active component comprises at least one of a group VIII metal element and a group VIB metal element;
based on the total weight of the hydrogenation catalyst on a dry basis, the content of the VIII group metal element is 0.3-6 wt%, and the content of the VIB group metal element is 4-25 wt%, respectively calculated by oxides.
3. The method of claim 1, wherein the conditions that mitigate hydrodesulfurization reactions comprise: the reaction temperature is 200--1The volume ratio of hydrogen to oil is 100-600.
4. The process as claimed in claim 1, wherein the sulfur content in the gasoline feedstock is 100-2000 μ g/g, preferably 800-2000 μ g/g;
the gasoline raw material is at least one selected from catalytic cracking gasoline, coker gasoline, thermal cracking gasoline and straight-run gasoline.
5. The process according to claim 1, the cut points of the light and heavy gasoline fractions being between 60 and 90 ℃.
6. The method of claim 1, wherein the method further comprises: and (2) pretreating the light gasoline fraction, and then feeding the light gasoline fraction into the hydrotreating reactor, wherein the pretreatment is at least one selected from alkali liquor extraction treatment, mercaptan conversion treatment and selective hydrogenation treatment.
7. The method according to claim 1, wherein the adsorption desulfurization catalyst contains silica, alumina, zinc oxide, and a desulfurization active metal which is at least one selected from the group consisting of cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin, and vanadium;
based on the dry weight of the adsorption desulfurization catalyst and calculated by the weight of oxides, the adsorption desulfurization catalyst contains 10-90 wt% of zinc oxide, 5-85 wt% of silicon dioxide and 5-30 wt% of aluminum oxide; the content of the desulfurization active metal in the adsorption desulfurization catalyst is 5-30 wt% based on the dry weight of the adsorption desulfurization catalyst and calculated by the weight of elements.
8. The method of claim 1, wherein the conditions of the adsorptive desulfurization reaction comprise: the reaction temperature is 350-500 ℃, and the weight hourly space velocity is 2-20h-1The reaction pressure is 2.0-3.5MPa, and the volume ratio of the hydrogen to the heavy gasoline fraction is 10-500.
9. The process of claim 1 wherein the heavy gasoline fraction is fed into the fluidization reactor to contact a mixed catalyst comprising the adsorptive desulfurization catalyst and an olefin aromatization catalyst and undergo desulfurization and aromatization reactions in the presence of hydrogen.
10. The process of claim 9 wherein the olefin aromatization catalyst comprises 15 to 60 weight percent natural minerals, 10 to 30 weight percent inorganic oxide binder, and 20 to 80 weight percent phosphorus-containing and metal-loaded MFI structural molecular sieve, based on the dry weight of the olefin aromatization catalyst.
11. The process according to claims 9 and 10, wherein the proportion of the aromatization catalyst to the mixed catalyst is from 1 to 30 weight percent on a weight basis.
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| CN115725334A (en) * | 2021-08-31 | 2023-03-03 | 中国石油化工股份有限公司 | Method for treating gasoline raw material |
| CN115725335A (en) * | 2021-08-31 | 2023-03-03 | 中国石油化工股份有限公司 | Method for treating benzene and sulfur in gasoline raw material |
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| CN115725334A (en) * | 2021-08-31 | 2023-03-03 | 中国石油化工股份有限公司 | Method for treating gasoline raw material |
| CN115725335A (en) * | 2021-08-31 | 2023-03-03 | 中国石油化工股份有限公司 | Method for treating benzene and sulfur in gasoline raw material |
| CN115725335B (en) * | 2021-08-31 | 2024-04-02 | 中国石油化工股份有限公司 | Method for treating benzene and sulfur in gasoline raw material |
| CN115725334B (en) * | 2021-08-31 | 2024-04-02 | 中国石油化工股份有限公司 | Method for treating gasoline raw material |
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