CN110157477A - A kind of high olefin gasolines desulfurization of high-sulfur proposes high-octane method and apparatus - Google Patents
A kind of high olefin gasolines desulfurization of high-sulfur proposes high-octane method and apparatus Download PDFInfo
- Publication number
- CN110157477A CN110157477A CN201810899464.9A CN201810899464A CN110157477A CN 110157477 A CN110157477 A CN 110157477A CN 201810899464 A CN201810899464 A CN 201810899464A CN 110157477 A CN110157477 A CN 110157477A
- Authority
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- Prior art keywords
- gasoline
- hydrogen
- line
- desulfurization
- sulfur
- Prior art date
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- Pending
Links
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 72
- 239000011593 sulfur Substances 0.000 title claims abstract description 72
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 51
- 230000023556 desulfurization Effects 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 44
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 42
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 15
- 238000012545 processing Methods 0.000 claims abstract description 15
- 238000010521 absorption reaction Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000003921 oil Substances 0.000 claims description 27
- 239000002808 molecular sieve Substances 0.000 claims description 24
- 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 24
- 239000000203 mixture Substances 0.000 claims description 21
- 239000004215 Carbon black (E152) Substances 0.000 claims description 19
- 229930195733 hydrocarbon Natural products 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims description 17
- 238000009835 boiling Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000005194 fractionation Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000284 extract Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- 230000029936 alkylation Effects 0.000 claims description 8
- 238000005804 alkylation reaction Methods 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 150000004767 nitrides Chemical class 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 230000003009 desulfurizing effect Effects 0.000 claims description 5
- 150000001993 dienes Chemical class 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
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- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 238000004523 catalytic cracking Methods 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 4
- 238000006317 isomerization reaction Methods 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
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- 239000012013 faujasite Substances 0.000 claims description 2
- 210000003918 fraction a Anatomy 0.000 claims description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000391 magnesium silicate Substances 0.000 claims description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 2
- 235000019792 magnesium silicate Nutrition 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 2
- 238000007254 oxidation reaction Methods 0.000 claims 2
- 238000009992 mercerising Methods 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000047 product Substances 0.000 description 28
- 230000003197 catalytic effect Effects 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- -1 Sulphur compound Chemical class 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 229910001868 water Inorganic materials 0.000 description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
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- 238000005265 energy consumption Methods 0.000 description 4
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
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- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
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- 241000899793 Hypsophrys nicaraguensis Species 0.000 description 1
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- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
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- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
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- 239000000470 constituent Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
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- 230000001681 protective effect Effects 0.000 description 1
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- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical class [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 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
- 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
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages 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
- C10G2300/20—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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A kind of high olefin gasolines ultra-deep desulfurization of high-sulfur proposes high-octane method and apparatus, and the present invention first contacts feed gasoline with difunctional catalyst, while carrying out desulfurization-isomery aromatisation processing, and second step will treated that gasoline fraction is fractionated, and removes H2S simultaneously cuts light petrol and heavy petrol, and heavy petrol is further contacted with desulfurization-raising octane number catalyst, strips de- H2S, heavy petrol and light petrol are molten as up to standard, can straight connecting device.If not up to standard, light petrol and/or heavy petrol carry out absorption desulfurization-raising octane number processing after mixing with hydrogen, achieve the purpose that the high olefin gasolines ultra-deep desulfurization production super-low sulfur high-knock rating gasoline of high-sulfur.
Description
Technical field
The present invention relates to a kind of high olefin gasolines desulfurization of high-sulfur to propose high-octane method and apparatus, and it is clear to belong to petrochemical industry
Clean Oil Production field.
Background technique
In China's motor petrol, the produced catalytically cracked gasoline of high-sulfur Catalytic Unit and/or catalytic cracking gasoline (under
Abbreviation catalytic gasoline) shared by ratio reach 70% or so.Since 2019, it is desirable that VI motor petrol standard of state of enforcement,
In sulfur content be less than 10ppm, arene content is less than 35%, and olefin(e) centent is less than 15%.
China is in addition to Daqing crude oil sulfur content is lower, and the sulfur content of most of crude oil of most of crude oil especially import is all
It is relatively high, cause the sulfur content of catalytic gasoline in 200-2000ppm, it is 25%-50%, arene content 18%- that alkene, which contains,
28%, octane number is lower.It therefore, is the requirement for meeting VI standard of state, the deep desulfuration of catalytic gasoline, appropriateness reduce alkene and contain
Amount increases isohydrocarbon and arene content, improves octane number, is the pass with VI super-low sulfur high-knock rating gasoline of catalytic gasoline producing country
Key step.
CN01142833.3, a kind of technique removing sulfur-containing compound in catalytically cracked gasoline, it is characterized in that: sulphur will be contained
The catalytically cracked gasoline of the sulfur-containing compounds such as alcohol, thiophene-based and alkadienes is sent into first reactor, and mercaptan etc. is low-boiling to be contained
Sulphur compound generates the higher sulfur-bearing chemical combination of boiling point with diene hydrocarbon reaction in the case where active component is the catalyst action of nickel and/or palladium
Object；Material after first reactor reaction enters a conventional distil-lation tower, obtains the gasoline light fraction of low sulfur content from tower top, other
Fraction enters a catalytic distillation tower；The Hydrobon catalyst loaded in catalytic distillation tower or selective hydrodesulfurization catalysis
Under agent effect, the higher sulfur-containing compound of boiling point is reacted with hydrogen generates hydrogen sulfide, and gasoline reform point is discharged from tower reactor.
US6083379, a kind of sulfur removal technology of cracking gasoline feedstock, comprising: cracking gasoline charging is divided into hydrocarbon ils
Light fraction, the heavy distillat of hydrocarbon ils；Under the reaction condition of hydrocarbon ils aromatization, connect light fraction with the catalyst containing a kind of zeolite
Touching, a kind of produced intermediate product and heavy distillat mixing；Intermediate product is fractionated into the overhead stream containing light olefin and is contained
The tower base stream of aromatic hydrocarbons；Under the conditions of hydrocarbon oil containing surphur desulphurization reaction, make a part of above-mentioned tower base stream and a part of heavy distillat with
The contact of Hydrobon catalyst composition, generates a kind of desulfurization product；The remainder of tower base stream, heavy distillat remainder
Divide, the mixed total octane number of product stream after overhead stream and desulfurization, at least equal to the octane number of cracking gasoline charging.
WO9838265, it is a kind of for containing more difficult removing alkyl-substituted heterocyclic sulfur compounds hydrocarbon stream plus hydrogen essence
Technique processed, comprising: in the first reaction zone, under hydrodesulfurizationconditions conditions, make hydrocarbon stream and a kind of sulfide, promoted with transition metal
Into molybdenum, tungsten or molybdenum and tungsten catalyst contact；Discharge is closed containing the vulcanization of light and weight more difficult removing from the first reaction zone
The logistics of object；Light sulphur compound is isolated from logistics, forms the second object of the heterocyclic sulfur compounds containing more difficult removing
Stream；In second reaction zone, under conditions of hydrodesulfurization and isomerization, urge the second logistics and hydrogen with a kind of solid acid
Agent contact, solid acid catalyst effectively make the alkyl substituent isomery being present on the heterocyclic sulfur compounds of more difficult removing
Change；The logistics flowed out from second reaction zone is back to first reaction zone, logistics is made to carry out hydrodesulfurization.Hydrodesulfurization
Catalyst is Ni/Co-Mo/Al2O3, solid acid catalyst is zeolite or a kind of heteropoly compound.Transition metal is selected from Mn,
Fe, Co, Ni, Cu, Zn and their mixture.
US5599441, a kind of cracking stone of the hydrocarbon of the olefin gasolines boiling point range rich in alkene and thiophene sulphur compound
The upgrading process of cerebrol charging is included the steps that following continuous: firstly, making the boiling range C5Boiling point is to 420 ℉ (216 DEG C)
Charging in alkylation zone, contacted under alkylating conditions with a kind of alkylation catalyst particle of acidity, in naphtha
Alkene, i.e. monoolefine and alkadienes make alkylating agent, thiophene compound be alkylated, and generates a kind of thiophene including after alkylation
The logistics of the hydrocarbon of pheno compound and olefin gasolines boiling point range；By distilling the thiophene compound and olefin gasolines after alkylation
The hydrocarbon of boiling point range separates；Recycle the product stream of the hydrocarbon stream reduced containing thiopheneic compound content.Thiophene after alkylation
Compound concentrates in the heavy constituent of naphtha, and the naphtha of surplus is hydrogenated desulfurization.In the light component of naphtha, cracking
Alkene in naphtha is converted, light naphthar component then without hydrotreating, in this way, octane number related with hydrogen is added and
Hydrogen gas consumption is reduced to minimum.
Both at home and abroad production clean gasoline patent literature report it is very much, but really industrialized technology only have it is several.It is external
The SCANFining technique and French stone that industrialized catalyzed gasoline hydrogenation desulfurization technology mainly has ExxonMobil company to develop
The IFP Prime-G technique of oily research institute's exploitation, industrialized gasoline hydrodesulfurizationmethod technology mainly has RSDS technique in China
With OCT-M technique.Their feature is that feed gasoline is first fractionated into light gasoline fraction and heavy naphtha, and heavy petrol evaporates
Divide after carrying out hydrodesulfurization, then reconciled with light fraction, removes mercaptan through alkali cleaning.
It either by feed gasoline elder generation weighted BMO spaces, is fractionated as light petrol and heavy petrol, Etherification of Light FCC Gasoline, heavy petrol are de-
After sulphur restores octane number, the two is reconciled into out device, process flow is as shown in Figure 1.
Feed gasoline first has to by weighted BMO spaces reactor 1, by low-boiling sulfide and alkadienes or monoolefine
It is alkylated reaction, high boiling sulfide is generated, is enriched in sulfide in heavy petrol；Second step by fractionating column 2 into
Row fractionation, the light petrol separated is etherified into etherificate unit 5, to reduce alkene and improve octane number；The weight that third step separates
Gasoline carries out one-stage hydrogenation desulfurization into selective hydrodesulfurization reactor 3；4th step one-stage hydrogenation product is using secondary hydrogenation
The reaction product of 4th step is removed H by stripper by desulfurization and recovery octane number processing, the 5th step2S；6th step, by vapour
The heavy petrol for proposing processing carries out caustic wash desulfuration alcohol, could be up to standard.
The shortcoming of this technical solution is:
1. needing light petrol carrying out pre-hydrotreating and etherification process for the loss for reducing alkene He making up octane number
Etc. processes.
2., in fractionation, cutting is pressed very low, or even be transferred to 60 DEG C or so to reduce the sulfur content in light petrol,
The quantity of distillate for making light petrol is only 25%-30%, and the heavy petrol of 70%-75% needs hydrotreating at least twice up to standard.
3. caustic wash desulfuration alcohol can generate spent lye, need to be further processed；
4. the catalytic gasoline raw material of these techniques (200-600ppm or so) lower for content of sulphur compounds has preferably
Effect.
For the catalytic gasoline raw material of high-sulfur (being greater than 1000ppm) high alkene, production total sulfur content is super less than 10 μ g/g
Low-sulphur oil is then relatively difficult.There are two main causes: first is that sulphur compound contained in the light gasoline fraction being fractionated, special
It is not that Macromolecule mercaptan sulfur content is higher, is difficult to by alkali cleaning up to standard；Second is that heavy naphtha deep hydrogenation, be easy to cause pungent
The loss of alkane value is excessive.
It can be seen that above-mentioned process flow is longer, process is complicated, energy consumption is higher, investment is larger.Therefore, it develops a kind of new
The high olefin gasolines desulfurization of technology especially high-sulfur to propose high-octane technology be meaningful.
Summary of the invention
It is an object of the invention to by developing, one kind is with low investment, low energy consumption, the simple catalytic gasoline of technical process produces
The technology of super-low sulfur clean gasoline provides a kind of high olefin gasolines desulfurization of high-sulfur and proposes high-octane method and apparatus.
It is as follows to realize that the object of the invention provides technical solution:
A kind of high olefin gasolines desulfurization of high-sulfur proposes high-octane method, includes the following steps:
Step 1, in the first hydrogenator, gasoline stocks are contacted with the first hydrogenation catalyst simultaneously with hydrogen, are being added
It is reacted under hydroformylation reaction condition, the diene hydrogenation saturation in catalytically cracked gasoline raw material, monoolefine, alkane isomery aromatization
Change, alkylation, and sulfide, nitride, the oxide in gasoline are hydroconverted into H2S, NH3And H2O；
Step 2, the logistics flowed out in the first hydrogenator of step (1) is fractionated in fractionating column, is removed step (1)
React the H generated2S, NH3And H2O；The logistics is divided into light gasoline fraction A and heavy naphtha B simultaneously；
Step 3, in the second hydrogenator, by one kind or two of light petrol A and heavy naphtha B in step (2)
Kind is contacted with after hydrogen mixing with the second hydrogenation catalyst, and hydrogenation reaction is carried out under hydroconversion condition, carries out deep hydrodesulfurizationof
And make some olefin and alkane in heavy naphtha that hysomer and aromatization occur；
Step 4, gasoline fraction step 3 obtained carries out the processing of Stripping Desulfuration hydrogen, obtains gasoline component C；
Step 5, if gasoline component A, B, C are up to standard, device can be gone out as product or blend component respectively or after blending；
It if not up to standard, can be mixed respectively or after reconciling with hydrogen, carry out absorption desulfurization-raising octane number processing.
In above-mentioned steps, combination can be optimized according to different material and product requirement, optional 2 step therein or 3
Step or 4 steps or 5 steps.
High sulfur oil refers to gasoline of the sulfur content within the scope of 200-3000ppm in the present invention；High alkene refers to that alkene contains
Measure the gasoline within the scope of 18%-50%.
First hydrogenation catalyst, the second hydrogenation catalyst, adsorption desulfurizing agent can commercially available or self-controls.
Wherein, the first hydrogenation catalyst includes carrier and active component, and carrier is selected from porous inorganic oxide or porous
Carbonaceous material, active component is selected from VI B race metallic element, one or more of metallic element of VIII race or they are each
From one of compound or more than one mixture.
Second hydrogenation catalyst includes carrier, molecular sieve and active component, and carrier is in porous inorganic oxide
A kind of or their mixture, active component are selected from VI B race metallic element, one or more of the metallic element of VIII race, or
One of their own compound of person or more than one mixture.
The carrier of first hydrogenation catalyst be selected from aluminium oxide, titanium oxide, zirconium oxide, zinc oxide, magnesia, silicon carbide, two
Silica, silica gel, natural clay, alumina silicate, one of magnesium silicate or more than one mixture, active component are selected from cobalt,
Molybdenum, nickel, one or more of tungsten or their own oxide, sulfide, nitride, one of phosphide or several
Kind, it further include auxiliary agent, auxiliary agent Na, K, Mg, Ca, P, V, Cr, F, B, Mn, Fe, Cu, Zn, Zr, auxiliary agent in the first hydrogenation catalyst
Element can for one kind, can also be a variety of combinations.
The carrier of second hydrogenation catalyst is selected from aluminium oxide, titanium oxide, magnesia, one of silica or it is a kind of with
On mixture, active component be selected from cobalt, molybdenum, nickel, one or more of tungsten or their own oxide, sulfide,
Nitride, one or more of phosphide, the molecular sieve are selected from phosphate aluminium molecular sieve, A type molecular sieve, X-type molecular sieve, Y
Type molecular sieve, super Y type molecular sieve, Beta molecular sieve, modenite, ZSM type zeolite, faujasite, SAPO-11, in diatomite
One or more kinds of mixtures, the molecular sieve used additives, auxiliary agent Na, K, Mg, Ca, P, V, Cr, F, B, Mn,
The element of Fe, Cu, Zn, Zr, auxiliary agent can be one kind, can also be a variety of combinations.
Molecular sieve is preferably selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57,
ZSM-58, M41-S or MCM-22 molecular sieve.Molecular sieve is preferably ZSM-5 molecular sieve.
It is selected from one of V, Cr, Mo, W at sour metallic element used in the modified molecular screen, at alkali or amphoteric metal
Element is selected from one of Mg, Ti, Zr, Nb, Al, Fe, Co, Ni, Zn, Sb.
The preparation method of the absorbing desulfurization catalyst authorizes patent of invention CN103789038B referring to this team.
In the first hydrogenator, reaction condition are as follows: 0.2~5.0MPa of pressure, 100 DEG C~450 DEG C of temperature, oily air speed
0.5~15.0h-1, 50~1000v/v of hydrogen-oil ratio.Preferred reaction condition are as follows: 1.0~2.5MPa of pressure, temperature 160 DEG C~350
DEG C, oily 1.0~6.0h of air speed-1, 100~600v/v of hydrogen-oil ratio.
In the second hydrogenator, reaction condition are as follows: pressure is 0.2~5.0MPa, and temperature is 100 DEG C~450 DEG C, oil
Air speed is 0.5~15.0h-1, hydrogen-oil ratio is 50~1000v/v.Preferred reaction condition are as follows: 1.0~2.5MPa of pressure, temperature
200 DEG C~400 DEG C, oily 1.0~6.0h of air speed-1, hydrogen-oil ratio is 100~600v/v.
Heavy naphtha in second hydrogenator contains the more difficult removing of the higher organosulfur compound of boiling point, while portion
Divide alkene and alkane that hysomer and aromatization also occurs, therefore, reaction temperature is higher than the first hydrogenation reaction
Reaction temperature in device.
Heavy naphtha after adding hydrogen carries out depriving hydrogen sulphide processing using steam stripped method, can when using gas stripping process
To make stripping gas with vapor or inert gas such as nitrogen.Can also be as needed, light petrol and/or heavy petrol are mixed with hydrogen
Absorption desulfurization-raising octane number processing is carried out after conjunction.
It is as follows that the high olefin gasolines desulfurization of high-sulfur provided by the invention improves octane number device
It include: gasoline stocks tank, pump, hydrogen gas lines, the first hydrogenator, an anti-hydrogenation products outflow line, heat exchanger,
Fractionating column, cooler, knockout drum, H2Line, overhead reflux line is discharged in the gases such as S, and tower top adds hydrogen light petrol to extract line, tower bottom out
Heavy petrol flows out line, and reboiler mends hydrogen line, the second hydrogenator, and two anti-hydrogenation products flow out line, heat exchanger, stripper, tower
Push up condenser, knockout drum, H2Line, overhead reflux line is discharged in the gases such as S, and tower top light oil extracts line out, and stripping tower bottom adds hydrogen weight
Gasoline stream outlet；Reboiler, adsorbs desulfurizing tower, and product gasoline extracts line out；
Wherein, head tank is connected with oil pump, by the raw material catalytic cracking gasoline in head tank after oil pump boosts with hydrogen
Hydrogen mixing in pipeline；Hydrogen gas lines are connected in the first hydrogenator, and the mixture in hydrogen gas lines is preheated and is entered
It is contacted with the first hydrogenation catalyst and carries out hydrodesulfurization-isomerization reaction；First hydrogenator is connected with heat exchanger, and by object
Stream is connected by the laggard fractionating column of heat exchanger heat exchange, fractionating column with cooler, and cooler is connected with knockout drum, gas-liquid separation
H is equipped with above tank2Line is discharged in the gases such as S；
Part light gasoline fraction is flowed back into the top of fractionating column by knockout drum through overhead reflux line, to control point
Evaporate precision；Another part light gasoline fraction adds the extraction line extraction of hydrogen light petrol through tower top as the product after hydrodesulfurization；
Fractionating column is connected with reboiler, and fractionating column returns to the heavy hydrocarbon component of the high-sulfur low octane rating of tower bottom after reboiler
Fractionating column；Fractionation column base connects tower bottom heavy petrol and flows out line, and tower bottom heavy petrol flows out line and connect with hydrogen line is mended, by fractionation column
The heavy hydrocarbon component of the high-sulfur low octane rating at bottom enters the second hydrogenator and contacts progress deep hydrogenation with the second hydrogenation catalyst
Desulfurization；
Second hydrogenator successively flows out line, heat exchangers with two anti-hydrogenation products, connect stripper connection；
Stripper overhead connects overhead condenser, and overhead condenser connects knockout drum, H in knockout drum2S, NH3
The H that equal gases pass through setting above knockout drum2Line discharge is discharged in the gases such as S, into recovery system；In the middle part of knockout drum
Light gasoline fraction is divided to beat the top for flowing back into stripper through top return wire；Another part light gasoline fraction is made in knockout drum
Line extraction is extracted out through tower top light oil for the product after hydrodesulfurization；
Stripper tower bottom is separately connected reboiler and stripping tower bottom hydrogenated heavy gasoline outflow line；
Stripper is connect with adsorpting desulfurization device, and the adsorpting desulfurization device is connected with product gasoline extraction line.
The present invention produces the method for super low-sulfur oil and the device of use has the advantage that
1, present invention process process is simple, and weighted BMO spaces unit and Etherification of Light FCC Gasoline unit is omitted, save investment,
Reduce energy consumption.
2, the present invention adds hydrogen and two steps that hydrogen is added to be all made of efficient bifunctional catalyst using a step, while reaching efficiently de-
Sulphur proposes high-octane purpose.Especially suitable for the high olefin catalytic gasoline production super-low sulfur high octane gasoline products of high-sulfur or its
Blend component.
3, of the invention since there is the first hydrogenation catalyst efficient selective desulfurization can make to cut in the fractionation of second step
The temperature of cutpoint is increased to 100-110 DEG C, and the light gasoline fraction of the low-sulfur of 60%-70% or so can be made to cut off, it is remaining need to be into
The heavy petrol of one step processing only has 30%-40%.To make the load of post-processing substantially reduce, make the investment and energy consumption drop of device
It is low.
4, the present invention is by configuring absorption desulfurization, first is that the treatment process of caustic wash desulfuration alcohol bring spent lye can be excluded,
It is more environmentally protective；Second is that absorption desulfurization the total sulfur content in gasoline can be made to be down to 5ppm hereinafter, than caustic wash desulfuration alcohol effect
It is better very much.
Detailed description of the invention
Fig. 1 catalytic gasoline desulfurization ether-based device principle flow chart.
The pre- hydrogenation unit of 1-, 2- fractionation unit, 3- selective hydrogenation reactor, 4- relay desulfurization/recovery octane number reaction
Device, 5- are etherified unit, 6- stripper, 7- products pot.
Fig. 2 high-sulfur catalytic gasoline desulfurization improves octane number process unit flow chart.
1- gasoline stocks tank, 2- pump, 3- hydrogen gas lines, the first hydrogenator of 4-, the anti-hydrogenation products of 5- mono- flow out line, 6-
Heat exchanger, 7- fractionating column, 8- cooler, 9- knockout drum, 10-H2Line, 11- overhead reflux line, 12- tower is discharged in the gases such as S
Top plus hydrogen light petrol extraction line, 13- tower bottom heavy petrol outflow line, 14- reboiler, 15- benefit hydrogen line, the second hydrogenator of 16-,
The anti-hydrogenation products of 17- bis- flow out line, 18- heat exchanger, 19- stripper, the suction of 20- overhead condenser, 21- knockout drum, 22-
H2Line, 23- overhead reflux line is discharged in the gases such as S, and 24- tower top light oil extracts line out, and 25- stripping tower bottom hydrogenated heavy gasoline flows out line,
26- reboiler, 27- adsorb desulfurizing tower, and 28- product gasoline extracts line out.
Specific embodiment
Describe technical characteristic and embodiment of the invention in detail below in conjunction with attached drawing.
The present invention makees the mogas production or tune of raw material production ultra-low sulfur using the catalytic gasoline of the high alkene of high-sulfur
It is combined point.
By taking two-stage hydrogenation+absorption desulfurization method as an example,
As shown in Fig. 2, the device of the invention work is that processing method is specific as follows:
Raw material catalytic cracking gasoline after the boosting of oil pump 2, is mixed in hydrogen gas lines 3 with hydrogen, mixture is pre- from head tank 1
Enter after heat through pipeline and add in the first hydrogenator 4, contacted with the first hydrogenation catalyst, carries out adding hydrogen at a lower temperature
Sulfide hydro-conversion therein is H by desulfurization-isomerization reaction2S, partial nitridation object, oxide hydro-conversion are NH3With
H2The reaction such as hydroisomerizing aromatisation, alkylation occurs for O, some olefin, alkane.
The logistics flowed out by the first hydrogenator 4 exchanges heat laggard fractionating column 7 by heat exchanger 6, by H2S, NH3、H2O and
The logistics of the high-octane light hydrocarbon component of low-sulfur is distillated from tower top, cooling through subcooler 8,9 separation in knockout drum,
H2S, NH3Equal gases are by H above knockout drum2Line discharge is discharged in the gases such as S, into recovery system.Knockout drum lower part row
Liquid component out is mainly the high-octane light gasoline fraction of low-sulfur and a small amount of water, and water sedimentation separation therein removes,
Part light gasoline fraction beats the top for flowing back into fractionating column 7 through overhead reflux line 11, to control fractionation precision；Partially light vapour
Oil distillate adds hydrogen light petrol extraction line 12 to extract (being denoted as component A) out as the product after hydrodesulfurization through tower top.
The heavy hydrocarbon component of the high-sulfur low octane rating of 7 tower bottom of fractionating column is divided into two parts, and a part is returned through reboiler 14 steams
Tower is evaporated, to improve fractionating efficiency.Another part (being denoted as B component) mixes through tower bottom pipeline 13 with the hydrogen mended in hydrogen line 15 laggard
Enter the second hydrogenator 16, contacted with the second hydrogenation catalyst, is carried out under the reaction temperature for being higher than the first hydrogenator
Deep hydrodesulfurizationof, while making some olefin and alkane that hysomer and aromatization occur, improve octane number.
Second hydrogenator product stream exchanges heat by two anti-hydrogenation products outflow lines 17 and heat exchanger 18, into stripper
19。
In stripper 19, by two anti-hydrogenation reaction product H2S、NH3、H2O and the high-octane light hydrocarbon component of low-sulfur
It is distillated from tower top, it is cooling through subcooler 20, into knockout drum 21, wherein H2S, NH3Equal gases are by above knockout drum
H2Line discharge is discharged in the gases such as S, into recovery system.The liquid component of knockout drum lower part discharge is mainly low-sulfur higher octane
The light gasoline fraction of value and a small amount of water, water sedimentation separation therein remove, and part light gasoline fraction is returned through pushing up return wire 23
Stream enters the top of stripper 19, to control fractionation precision；Part light gasoline fraction is as the product after hydrodesulfurization through pipe
Line 24 extracts (being denoted as C1 component) out.
The heavy hydrocarbon component of the high-sulfur low octane rating of 19 tower bottom of stripper is divided into two parts, and a part returns to tower through reboiler 26
In, to improve fractionating efficiency.Another part extracts (being denoted as C2 component) out through tower bottom pipeline 25.
The desulfurization heavy petrol C2 component of 19 tower bottom of stripper can be with the light petrol that distillates at the top of stripper 19 as product
The light petrol component A that distillates at the top of C1 component and fractionating column 7 merges, if it is up to standard can straight connecting device, if exceeded pass through
Adsorpting desulfurization device 27 carries out ultra-deep absorption desulfurization-raising octane number processing, guarantees device out up to standard.
In above-mentioned steps, combination can be optimized according to different material and product requirement, optional 2 step therein or 3
Step or 4 steps or 5 steps.
Following embodiment is merely to illustrate the technology of the present invention feature, and application range of the invention is not limited except as.
Comparative example
The FCC gasoline that total sulfur content is 789 μ g/g is first fractionated by 90 DEG C of cut point, lower than 90 DEG C after fractionation
The total sulfur content of light gasoline fraction is 185 μ g/g, and the total sulfur content of the heavy naphtha higher than 90 DEG C is 1250 μ g/g.With industry
Hydrobon catalyst is by heavy naphtha hydrodesulfurization, and in reaction pressure 3.0MPa, 260~300 DEG C of reaction temperature, volume is empty
Fast 2.5h-1, under conditions of hydrogen-oil ratio 400v/v, desulfurization degree 90%, RON reduces by 8.3,
MON reduces by 4.2.Light gasoline fraction after the heavy naphtha after hydrogen and fractionation will be added to reconcile, the conduct after removal of mercaptans
Gasoline products, product total sulfur content are 165 μ g/g, and total desulfurization degree is that 78%, RON reduces by 1.9, MON reduction by 0.7.
Embodiment
Embodiment 1
The preparation of first hydrogenation catalyst:
The preparation of catalyst carrier is with 3 500g of industrial Al (OH), water 350g, alkaline metal oxide (magnesia 27g),
Nitric acid (65%) 50g makees peptizing agent, adds appropriate amount of addition agent (boric acid 27g, ammonium hydrogen phosphate 35g), and sesbania powder 15g makees adhesive, warp
Kneading, extrusion (diameter 1.5mm) are dried 6 hours at 150 DEG C, are down to room temperature, and pelletizing makes 4~6mm of length, then through 450~
It is roasted 8 hours at 600 DEG C, catalyst carrier Z1 is made；
By catalyst carrier Z1 load active component: taking cobalt nitrate 34g, ammonium molybdate 67g, water 300g, be configured to aqueous solution
Catalyst carrier Z1 334g is impregnated in solution B 1 and is kept for 40 DEG C 4 hours or more, carrying active component and auxiliary agent are urged by B1
Agent is dried at 150 DEG C, then is roasted 6 hours through 400~550 DEG C, and room temperature is down to, and the first hydrodesulfurization-isocatalysis is made
Agent Cat 1.
Embodiment 2
The preparation of second hydrogenation catalyst:
The preparation of modified molecular screen: the HZSM-5 molecular sieve 534gA2 for being 58 with silica alumina ratio, by dehydrogenation modified component Zn
(NO3) 76g, auxiliary agent ammonium phosphate 27g are dissolved in 320g water, obtain solution B 2.By molecular sieve-4 A 2 be impregnated in B2 40 DEG C 4 hours with
On, it is dried at 80~250 DEG C, then roasted 6 hours at 400~550 DEG C, modified molecular screen is made；
The preparation of catalyst carrier is raw material, nitric acid (65%) 34g with 3 167g of industrial Al (OH), modified molecular screen 334g
Make peptizing agent, sesbania powder 20g makees adhesive, adds appropriate amount of addition agent (boric acid 20g, ammonium phosphate 14g), through kneading, extrusion (diameter
1.5mm), it is dried 8 hours at 150 DEG C, is down to room temperature, pelletizing makes 4~6mm of length, then small through 450~600 DEG C of roastings 6
When, catalyst carrier Z2 is made；(3) by catalyst carrier Z2 load active component: by the salt cobalt acetate 27g of active component,
Ammonium molybdate 50g is configured to aqueous solution B3, and catalyst carrier Z2 334g is impregnated in solution B 3, is kept for 40 DEG C 4 hours or more.
The catalyst of carrying active component and modified molecular screen is dried at 80~150 DEG C, then through roasting 8 hours at 400~600 DEG C,
It is down to room temperature, the second hydrodesulfurization isomery-aromatization catalyst Cat 2 is made.
Embodiment 3
The preparation of absorbing desulfurization catalyst
Referring to the preparation method of this team authorization patent of invention CN103789038B embodiment 4:
(1) 100 grams of nickel nitrates, 200 grams of ferric nitrates, 60 grams of aluminum nitrates and 147 grams of zinc nitrates are weighed and are added to 600 milliliters
It in distilled water, is stirred well to and is completely dissolved, obtain solution A；0.5M/L sodium carbonate liquor is added, is sufficiently stirred；It is to PH preparation method
8-10 is precipitated, is stood, and filtering, deionized water washing obtain wet cake, then at 80-120 DEG C of drying, obtains dry sample F1；
(2) above-mentioned dry sample is crushed to less than 100 mesh, is sufficiently mixed with aluminium dry glue, the aqueous solution that dust technology is added fills
Point kneading, extrusion forming, in 80-120 DEG C of drying, 500 DEG C of roastings 4-8 hours are to get to adsorbent Cat3.Consisting of NiO
15.97wt%-FeO 49.10wt%-ZnO 24.79wt%-Al2O310.12wt%.
Embodiment 4-8
First method: hydrodesulfurization of whole-distillate gasoline-raising octane number test
In the experimental provision of process flow according to the invention installation, the full fraction for the use of total sulfur content being 2010 μ g/g
FCC gasoline is that raw material carries out hydrodesulfurization raising octane number experiment, examines the experimental result of different technology conditions, as a result
It is shown in Table 1 embodiment 4-8.
Seen from table 1, when reaction temperature is 270 DEG C, gasoline total sulfur is down to 267ppm by 2010ppm, and desulfurization degree reaches
86%, alkene reduces by 33% (calculating according to bromine valency), and aromatic hydrocarbons improves 24.13%.When reaction temperature be 300 DEG C, gasoline total sulfur by
2010ppm is down to 22.4ppm, and desulfurization degree reaches 98.9%, and alkene reduces by 62.3% (calculating according to bromine valency), and aromatic hydrocarbons improves
44.50%.The boiling range and variable density very little of gasoline.Show catalyst desulfurizing significant effect, the effect that alkene reduces, aromatic hydrocarbons improves
Fruit is good.
Embodiment 9-14
Second method is the first step by whole-distillate gasoline progress hydrodesulfurization-isomery aromatisation processing, and second step adds hydrogen
Gasoline carries out distillation cutting, removes H2S is simultaneously cut into light petrol A and heavy petrol B, and it is de- that third step heavy petrol B carries out deep hydrogenation
The hydrogenation products of third step are stripped de- H by sulphur-raising octane number processing, the 4th step2S obtains the high-octane heavy petrol of low-sulfur
C；5th step light petrol A and heavy petrol C blending is used as product or gasoline blending component.Test result is as shown in table 2, table 3.
As can be seen from Table 2, the method for carrying out hydrodesulfurization isomery aromatisation using full fraction, is 260-300 in reaction temperature
Under conditions of DEG C, total sulfur is down to 85.2-45.0ppm by 658ppm, and desulfurization degree reaches 87.1%-93.2%, the aromatic hydrocarbons in gasoline
Increase 22.4%-33.1%；Alkene reduces 19.4%-28.3%, and saturated hydrocarbons, boiling range and variable density are seldom.
Seen from table 3, by sulfur content be 76.2ppm hydrogasoline with 112 DEG C for cut-point, < 112 DEG C of light petrol evaporates
Part accounts for 70w%, total sulfur 8.0ppm, and > 112 DEG C of heavy gasoline fractions account for 30w%, total sulfur 241.2ppm, and aromatic hydrocarbons is
60.78w%, by two step hydrotreatings, total sulfur can be down to 6.0ppm, and aromatic hydrocarbons reaches 62.18%.By light petrol and heavy petrol tune
It closes, total sulfur 7.4ppm, is better than VI standard of state.
Embodiment 14-19 adsorbs desulfurization test, the results are shown in Table 4.
By table 4 as it can be seen that using homemade absorbing desulfurization catalyst in reaction pressure 1.0MPa, 350-400 DEG C of reaction temperature,
Reaction velocity 1.5-3.0h-1, under conditions of hydrogen-oil ratio 20-60, the total sulfur of hydrogasoline can be down to 2.15- by 73ppm
6.18ppm, better than the requirement of VI gasoline standard of state.
Embodiment 20-21
The third method: a step adds hydrogen-fractionation-absorption desulfurization aromatisation experiment, the results are shown in Table 5.
By 5 embodiment 20 of table as it can be seen that adding hydrogen by a step, in reaction pressure 1.7MPa, 290 DEG C of reaction temperature, reaction is empty
Fast 2.0h-1, react hydrogen-oil ratio 200v/v technique under, gasoline total sulfur is down to 43.1ppm by 618ppm, and desulfurization degree reaches
93.0%, alkene reduces by 6%, and aromatic hydrocarbons improves 8.5v%.
This example demonstrates that the Hydrobon catalyst and technology of independent research, have good selective hydrogenation de-
The function of sulfur functional and preferable alkene aromatisation.
By 5 embodiment 21 of table as it can be seen that by being cut to hydrogasoline embodiment 20, be cut into < 100 DEG C fraction and
>100 DEG C of fraction is carried out absorption desulfurization aromatisation processing, then reconciled with<100 DEG C of light petrol by>100 DEG C of fraction, is reconciled
The sulfur content of oil is 6.3ppm, arene content 32.2v%, olefin(e) centent 22.2V%.
Compared with raw material, total sulfur reduces by 98.98%, and aromatic hydrocarbons improves 21.14%, and alkene reduces by 20.71%, the boiling range of gasoline
It is substantially unchanged with density, it is a kind of good super-low sulfur high-octane rating blend component.
Above-described embodiment shows that the present invention improves octane number for the catalytic gasoline desulfurization of the high alkene of gasoline especially high-sulfur
Producing super-low sulfur clean gasoline has good effect.
Claims (10)
1. a kind of high olefin gasolines desulfurization of high-sulfur proposes high-octane method, which comprises the steps of:
Step 1, in the first hydrogenator, gasoline stocks are contacted with the first hydrogenation catalyst simultaneously with hydrogen, are adding hydrogen anti-
Reacted under the conditions of answering, diene hydrogenation in catalytically cracked gasoline raw material saturation, monoolefine, alkane isomery aromatisation,
Alkylation, and sulfide, nitride, the oxide in gasoline are hydroconverted into H2S, NH3And H2O；
Step 2, the logistics flowed out in the first hydrogenator of step (1) is fractionated in fractionating column, removing step (1) reaction
The H of generation2S, NH3And H2O；The logistics is divided into light gasoline fraction A and heavy naphtha B simultaneously；
Step 3, in the second hydrogenator, by step (2) light petrol A and heavy naphtha B one or two with
It is contacted after hydrogen mixing with the second hydrogenation catalyst, hydrogenation reaction is carried out under hydroconversion condition, carry out deep hydrodesulfurizationof and made
Hysomer and aromatization occur for some olefin and alkane in heavy naphtha；
Step 4, gasoline fraction step 3 obtained carries out the processing of Stripping Desulfuration hydrogen, obtains gasoline component C；
Step 5, if gasoline component A, B, C are up to standard, device can be gone out as product or blend component respectively or after blending；If
It is not up to standard, it can be mixed respectively or after reconciling with hydrogen, carry out absorption desulfurization-raising octane number processing.
2. the method according to claim 1, wherein first hydrogenation catalyst includes carrier and active group
Point, carrier is selected from porous inorganic oxide or porous carbonaceous material, and active component is selected from VI B race metallic element, VIII race
One of one or more of metallic element or VI B race metallic element and the respective compound of metallic element of VIII race
Or more than one mixture.
3. according to the method described in claim 2, it is characterized in that, the carrier of first hydrogenation catalyst is selected from oxidation
Aluminium, titanium oxide, zirconium oxide, zinc oxide, magnesia, silicon carbide, silica, silica gel, natural clay, alumina silicate, in magnesium silicate
One or more kinds of mixtures, active component is selected from cobalt, molybdenum, nickel, one or more of tungsten or its respective oxygen
Compound, sulfide, nitride, one or more of phosphide further include auxiliary agent in the first hydrogenation catalyst, be Na, K, Mg,
Ca, P, V, Cr, F, B, Mn, Fe, Cu, Zn, Zr, element therein can be one kind, can also be a variety of combinations.
4. the method according to claim 1, wherein second hydrogenation catalyst includes carrier, molecular sieve
And active component, carrier are selected from one of porous inorganic oxide or mixture, active component is selected from VI B race metal member
The respective compound of metallic element of element, one or more of metallic element of VIII race or VI B race metallic element and VIII race
One of or more than one mixture.
5. according to the method described in claim 5, it is characterized in that, the carrier of second hydrogenation catalyst is selected from oxidation
Aluminium, titanium oxide, magnesia, one of silica or more than one mixture, active component are selected from cobalt, molybdenum, nickel, in tungsten
One or more or its respective oxide, sulfide, nitride, one or more of phosphide, the molecule
Screened from phosphate aluminium molecular sieve, A type molecular sieve, X-type molecular sieve, Y type molecular sieve, super Y type molecular sieve, Beta molecular sieve, mercerising boiling
Stone, ZSM type zeolite, faujasite, SAPO-11, one of diatomite or more than one mixture, the molecular sieve
Used additives are Na, K, Mg, Ca, P, V, Cr, F, B, Mn, Fe, Cu, Zn, Zr, and it can also be a variety of that element therein, which can be one kind,
Combination.
6. according to the method described in claim 3, it is characterized in that, the molecular sieve be ZSM-5, ZSM-11, ZSM-12,
ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ZSM-58, M41-S or MCM-22 molecular sieve.
7. the method according to claim 1, wherein in step 1, reaction condition are as follows: 0.2~5.0MPa of pressure,
100 DEG C~450 DEG C of temperature, oily 0.5~15.0h of air speed-1, 50~1000v/v of hydrogen-oil ratio.
8. the method according to claim 1, wherein in step 3, reaction condition are as follows:, pressure is 0.2~
5.0MPa, temperature are 100 DEG C~450 DEG C, and oily air speed is 0.5~15.0h-1, hydrogen-oil ratio is 50~1000v/v.
9. the method according to claim 1, wherein the sulfur content of gasoline condition up to standard are as follows: sulfur content
Less than 10ppm, arene content is less than 35%, and olefin(e) centent is less than 15%.
10. a kind of ultra-deep desulfurization mentions high-octane device, which is characterized in that the device includes: gasoline stocks tank (1), pump
(2), hydrogen gas lines (3), the first hydrogenator (4), anti-hydrogenation products outflow line (5), heat exchanger (6), fractionating column (7),
Cooler (8), knockout drum (9), H2Line (10) are discharged in the gases such as S, overhead reflux line (11), and tower top adds hydrogen light petrol to extract out
Line (12), tower bottom heavy petrol flow out line (13), and reboiler (14) is mended hydrogen line (15), the second hydrogenator (16), and two instead add hydrogen
Product stream outlet (17), heat exchanger (18), stripper (19), overhead condenser (20), knockout drum (21), H2The gases such as S
It is discharged line (22), overhead reflux line (23), tower top light oil extracts line (24) out, and stripping tower bottom hydrogenated heavy gasoline flows out line (25)；Again
It boils device (26), adsorbs desulfurizing tower (27), product gasoline extracts line (28) out；
Wherein, head tank (1) is connected with oil pump (2), and the raw material catalytic cracking gasoline in head tank (1) is boosted through oil pump (2)
It is mixed afterwards with the hydrogen in hydrogen gas lines (3)；Hydrogen gas lines (3) are connected in the first hydrogenator (4), and by hydrogen gas lines
(3) the mixture preheating in, which enters to contact with the first hydrogenation catalyst, carries out hydrodesulfurization-isomerization reaction；First hydrogenation reaction
Device (4) is connected with heat exchanger (6), and logistics is exchanged heat laggard fractionating column (7) by heat exchanger (6), the fractionating column (7) with
Cooler (8) is connected, and cooler (8) is connected with knockout drum (9), and H is equipped with above knockout drum (9)2The discharge of the gases such as S
Line；
Part light gasoline fraction is flowed back into the top of fractionating column (7) by knockout drum (9) through overhead reflux line (11), to
Control fractionation precision；Another part light gasoline fraction adds hydrogen light petrol to extract line (12) out as the product after hydrodesulfurization through tower top
Extraction；
The fractionating column (7) is connected with reboiler (14), and fractionating column (7) passes through the heavy hydrocarbon component of the high-sulfur low octane rating of tower bottom
Reboiler (14) returns to fractionating column (7) afterwards；Fractionating column (7) bottom connects tower bottom heavy petrol outflow line (13), tower bottom heavy petrol stream
Outlet (13) is connect with hydrogen line (15) are mended, and the heavy hydrocarbon component of the high-sulfur low octane rating of fractionating column (7) tower bottom is entered second plus hydrogen
Reactor (16) is contacted with the second hydrogenation catalyst carries out deep hydrodesulfurizationof；
Second hydrogenator (16) successively flows out line (17) with two anti-hydrogenation products, heat exchanger (18), connect stripping
Tower (19) connection；
Stripper (19) tower top connects overhead condenser (20), and overhead condenser (20) connects knockout drum (21),
H in the knockout drum (21)2S, NH3The H that equal gases pass through setting above knockout drum (21)2Line is discharged in the gases such as S
Discharge, into recovery system；Part light gasoline fraction is beaten through top return wire (23) and flows back into stripping in knockout drum (21)
The top of tower (19)；Another part light gasoline fraction is as the product after hydrodesulfurization through tower top light oil in knockout drum (21)
Extract line (24) extraction out；
Described stripper (19) tower bottom is separately connected reboiler (26) and stripping tower bottom hydrogenated heavy gasoline outflow line (25)；
The stripper (19) is connect with adsorpting desulfurization device (27), and the adsorpting desulfurization device (27) and product gasoline are taken out
Outlet is connected.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113786638A (en) * | 2021-10-18 | 2021-12-14 | 浙江美福石油化工有限责任公司 | MTBE product desulphurization unit |
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