CN114870793A - Aromatic hydrocarbon adsorbent for high sulfur-nitrogen raw oil and preparation method thereof - Google Patents
Aromatic hydrocarbon adsorbent for high sulfur-nitrogen raw oil and preparation method thereof Download PDFInfo
- Publication number
- CN114870793A CN114870793A CN202210626848.XA CN202210626848A CN114870793A CN 114870793 A CN114870793 A CN 114870793A CN 202210626848 A CN202210626848 A CN 202210626848A CN 114870793 A CN114870793 A CN 114870793A
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- aromatic hydrocarbon
- sulfur
- raw oil
- nitrogen
- Prior art date
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- Granted
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 72
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 55
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 28
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 239000003921 oil Substances 0.000 claims description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 24
- 239000003502 gasoline Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000002283 diesel fuel Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 239000012065 filter cake Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000011282 treatment Methods 0.000 claims description 15
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 10
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 239000000693 micelle Substances 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 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 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 claims description 5
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 5
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 5
- 150000003464 sulfur compounds Chemical class 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 claims description 3
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims 2
- 238000003795 desorption Methods 0.000 abstract 1
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 238000011156 evaluation Methods 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000005303 weighing Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 238000011161 development Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 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 1
- -1 monocyclic aromatic hydrocarbon Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0211—Compounds of Ti, Zr, Hf
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0251—Compounds of Si, Ge, Sn, Pb
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/06—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil
- C10G25/08—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil according to the "moving bed" method
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
Abstract
The invention discloses an aromatic hydrocarbon adsorbent for high sulfur-nitrogen raw oil and a preparation method thereof. The adsorbent is applied to a simulated moving bed adsorption separation process, has selective adsorption effect on aromatic hydrocarbon in high sulfur-nitrogen raw oil, and can be repeatedly used after desorption and regeneration of a desorbent, so that the purity of aromatic hydrocarbon components is more than 99 percent, and the purity of non-aromatic hydrocarbon components is more than 99 percent.
Description
Technical Field
The invention relates to an aromatic adsorbent for high sulfur-nitrogen raw oil and a preparation method thereof.
Background
At present, China is still in a middle-high-speed development stage, and as one of the pillar industries for guaranteeing the national economic development, the refining industry still has great development potential. The refining industry is based on the processing and utilization of fossil energy, has large industrial scale, large energy consumption and large total carbon emission, aims at realizing the aim of 'double carbon', and urgently needs to implement new development concepts and explore new development modes so as to realize low-carbon transformation development. Under the policy of 'double carbon' and 'double control' in China, the oil refining chemical industry faces a severe development situation, and the whole situation shows that a large number of basic products are excessive and high-end chemicals are in short supply. And the fuel can be further subdivided into surplus finished oil, shortage of new materials and special chemicals, saturation of diesel consumption, small increase of gasoline market and larger space for aviation kerosene and high-quality ship combustion.
The high sulfur-nitrogen raw oil generally comprises straight-run distillate oil and coking raw oil, and because of sulfur-nitrogen compounds with higher content, pretreatment is usually needed in the processing process to remove sulfur-nitrogen compounds, and then the high sulfur-nitrogen raw oil enters the subsequent processing flow. The straight-run gasoline is gasoline obtained by directly fractionating crude oil, mainly contains C4-C12 saturated hydrocarbon, less unsaturated hydrocarbon and a small amount of sulfur compounds, has low octane number, and is usually used as a blending component of the gasoline or subjected to catalytic reforming, wherein the catalytic reforming refers to that the gasoline component is subjected to a series of reactions such as aromatization, cyclization, isomerization, cracking, superposition and the like under certain reaction conditions and the action of a catalyst, so that the octane number of the gasoline is improved. The straight-run diesel oil is a diesel oil component directly obtained by distilling crude oil, the composition of the straight-run diesel oil component mainly comprises saturated hydrocarbon, the aromatic hydrocarbon component mainly comprises monocyclic aromatic hydrocarbon, the straight-run diesel oil component is generally used for secondary processing raw materials or blending raw materials, is rarely directly used, and can be used for producing jet fuel, olefin, high aromatic hydrocarbon reforming raw materials and light aromatic hydrocarbon raw materials.
The high sulfur nitrogen raw oil is adsorbed and separated by a Simulated Moving Bed (SMB) process to obtain high-purity aromatic hydrocarbon and high-purity non-aromatic hydrocarbon components, so that molecular management of the corresponding raw oil components can be realized, market demand changes can be dealt with more specifically, the subsequent conversion process of aromatic hydrocarbon and non-aromatic hydrocarbon can be coupled, the directional conversion of the high sulfur nitrogen raw oil to chemical products is realized, the processing flow is shortened, and the economic benefit is improved.
Patent CN1600836 discloses a method for preparing gasoline with low olefin content by modifying straight-run gasoline, which comprises mixing straight-run gasoline with carbon tetraolefin fraction, contacting and reacting with HZSM-5-containing catalyst under the conditions of 0.2-0.6MPa and 300-500 ℃, and then separating dry gas, liquefied gas and gasoline components in the product. Patent CN111303940A discloses a treatment method of straight-run diesel oil, which is to perform dearomatization treatment on straight-run diesel oil by a solvent extraction method or an adsorption separation method to obtain an aromatic-rich component and a dearomatization component, wherein an adsorbent is a metal-modified Y molecular sieve, but straight-run gasoline needs to be subjected to hydrogenation modification or hydrogenation lightening treatment before adsorption separation to remove sulfur and nitrogen compounds. Patent CN111718751A discloses a method for preparing aromatic hydrocarbon and light oil by catalytic conversion of straight-run diesel oil, which comprises pretreating straight-run diesel oil to remove alkaline nitrides to obtain straight-run diesel oil, and then carrying out catalytic conversion reaction on the straight-run diesel oil with alkaline nitrides removed by using a transition metal ion modified nano ZSM-5 molecular sieve catalyst as a reaction catalyst to obtain aromatic hydrocarbon and light oil.
The above patent mainly processes high sulfur-nitrogen raw oil such as straight-run gasoline and diesel oil by means of catalytic reaction and adsorption separation, wherein the adsorption separation process is used for processing straight-run gasoline and diesel oil, and sulfur-nitrogen compounds still need to be pretreated to remove the sulfur-nitrogen compounds, so as to prevent the sulfur-nitrogen compounds from causing deactivation of the adsorbent, and no adsorbent can not be influenced by sulfur-nitrogen compounds in the raw oil, and can realize adsorption separation of high-purity aromatic hydrocarbon.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides the aromatic hydrocarbon adsorbent, which can directly adsorb and separate the raw oil containing the sulfur-nitrogen compound by stably modifying the surface of the adsorbent, and the separation performance is not influenced by the sulfur-nitrogen compound; and the high sulfur-nitrogen raw oil is subjected to adsorption separation to obtain high-purity aromatic hydrocarbon and non-aromatic hydrocarbon components, and the high-purity aromatic hydrocarbon and non-aromatic hydrocarbon components can stably operate.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention provides a preparation method of an aromatic adsorbent for high sulfur-nitrogen raw oil, which comprises the following steps:
(1) pore channel modification: and mixing the silicon-aluminum adsorbent with the nonionic surfactant solution, and filtering to obtain a filter cake with a micelle filling pore channel structure formed by water and the nonionic surfactant.
(2) Metal activation: and (2) mixing and peptizing a stable metal compound and an organic amine solution of dihydric alcohol to obtain a metal sol, then mixing the metal sol with the filter cake obtained in the step (1), and filtering, washing and drying to obtain an adsorbent precursor.
(3) And (3) stability regulation: placing the adsorbent precursor obtained in the step (2) into a high-pressure kettle for sulfur-nitrogen compound solvent treatment, and filtering, drying and roasting after the treatment is finished to obtain the aromatic adsorbent;
wherein the silicon-aluminum adsorbent is at least one of silicon oxide, amorphous silicon-aluminum, aluminum oxide, X molecular sieve and Y molecular sieve; the metal is at least one of Al, Ti, Zr and Sn, and the mass content of the silicon-aluminum adsorbent in the aromatic hydrocarbon adsorbent is 80-99%.
In the preparation method of the aromatic hydrocarbon adsorbent for high sulfur-nitrogen raw oil, the solid-liquid mass ratio in the step (1) is 1: (5-10), the nonionic surfactant is at least one of dodecyl phenol polyoxyethylene ether OP-10 and nonylphenol polyoxyethylene ether TX-10, the concentration of the nonionic surfactant is 0.5% -1.5%, and the treatment conditions are 40-100 ℃ and 2-12 h.
In the preparation method of the aromatic hydrocarbon adsorbent for high sulfur-nitrogen raw oil, in the step (2), the stable metal compound is at least one of aluminum isopropoxide, tetrabutyl titanate, tetraethyl titanate, tetrabutyl zirconate, zirconium acetate and trimethyl tin chloride, the dihydric alcohol is at least one of ethylene glycol, 2-propylene glycol, 1, 4-butanediol and 1, 6-hexanediol, the mass concentration of the dihydric alcohol is 30-60%, the organic amine is at least one of ethylenediamine, n-butylamine and triethylamine, the mass concentration of the organic amine is 5-20%, and the treatment condition is 60-120 ℃ and 4-24 hours.
In the preparation method of the aromatic hydrocarbon adsorbent for high sulfur-nitrogen raw oil, the sulfur compound in the step (3) is at least one of benzothiophene, benzylmercaptan and diphenyl sulfide, the nitrogen compound is at least one of pyridine, quinoline and acridine, the mass ratio of the sulfur compound to the nitrogen compound is 5-30, the treatment condition is 120-200 ℃, the treatment time is 2-12 hours, the roasting temperature is 500-700 ℃, and the roasting time is 2-12 hours.
The invention also provides a molding method of the high sulfur-nitrogen raw oil aromatic adsorbent, the adsorbent and the binder are mixed, granulated and molded, particles with the particle size range of 0.3-2mm are screened, and then the molded adsorbent is obtained by drying and roasting; the binder is at least one of silica sol, alumina sol, kaolin and attapulgite, the roasting temperature is 500-700 ℃, and the roasting time is 2-12.
The invention also provides the high sulfur-nitrogen raw oil aromatic adsorbent prepared by the preparation method.
The invention further provides application of the aromatic hydrocarbon adsorbent for high sulfur-nitrogen raw oil in adsorption separation of aromatic hydrocarbon in high sulfur-nitrogen raw oil, wherein the process for adsorption separation of aromatic hydrocarbon in high sulfur-nitrogen raw oil is a simulated moving bed process, and the purity of aromatic hydrocarbon components is more than 99%, and the purity of non-aromatic hydrocarbon components is more than 99%.
In the above application technical scheme of the invention, the high sulfur-nitrogen raw oil preferably comprises at least one of straight-run gasoline, straight-run kerosene, straight-run diesel oil, coker gasoline, coker kerosene and coker diesel oil according to a processing mode.
In the application technical scheme of the invention, the high sulfur-nitrogen raw oil is a raw material with the carbon number of C4-C22 according to the hydrocarbon, S is less than or equal to 10000ppm, and N is less than or equal to 1000 ppm.
The aromatic adsorbent for high sulfur-nitrogen raw oil and the preparation method thereof have the beneficial effects that: according to the method, the metal salt and the silicon-aluminum adsorbent are respectively pretreated, so that the synergistic adsorption capacity between the metal salt and the silicon-aluminum adsorbent is enhanced, and the performance of the adsorbent for adsorbing and separating aromatic hydrocarbon is improved; meanwhile, the adsorbent is insensitive to sulfur and nitrogen compounds in the raw oil through stability treatment, and is applied to adsorption separation of aromatic hydrocarbon in the high sulfur and nitrogen raw oil, so that the purity of aromatic hydrocarbon components is more than 99 percent, the purity of non-aromatic hydrocarbon components is more than 99 percent, the stable operation can be realized, and the adsorption separation performance is not attenuated.
Detailed Description
The technical solution of the present invention is further illustrated below with reference to the following examples, but is not limited to these examples.
The evaluation performance data of the adsorbents in the examples were measured by the following methods: the straight-run gasoline/diesel oil is used as raw material, and the aromatic hydrocarbon content of the fraction section is 10-50%. The adsorbent is filled into a simulated moving bed, the aromatic hydrocarbon adsorption separation is a countercurrent simulated moving bed adsorption separation process, the adsorption bed layer is 8-24 layers, preferably 8-16 layers, the adsorption separation temperature is 40-150 ℃, preferably 50-10 ℃, the desorbent is a mixture of alkane and aromatic hydrocarbon, preferably methylcyclohexane and toluene, and the mass fraction of the toluene is 10-50%. Two materials are extracted from the simulated moving bed, one material is rich in aromatic hydrocarbon components, the other material is rich in non-aromatic hydrocarbon components, and the purity of the two materials is analyzed.
Example 1
(1) Pore channel modification: weighing 10kg of silica gel, adding 50kg of aqueous solution containing 250g of dodecyl phenol polyoxyethylene ether OP-10, treating at 40 ℃ for 12h, and then filtering to obtain a filter cake with a micelle filling pore channel structure formed by water and OP-10.
(2) Metal activation: weighing 405g of aluminum isopropoxide and 20kg of ethylene glycol solution of n-butylamine for peptization, wherein the mass concentration of the ethylene glycol is 30% and the mass concentration of the n-butylamine is 5%, mixing with the filter cake obtained in the step (1), treating at 60 ℃ for 24h, filtering, washing and drying to obtain the adsorbent precursor.
(3) And (3) stability regulation: and (3) placing the adsorbent precursor obtained in the step (2) into a high-pressure autoclave, adding a mixed solvent of benzothiophene and pyridine with the mass ratio of 5, treating for 12h at 120 ℃, filtering, drying, and roasting for 12h at 500 ℃ to obtain the adsorbent.
(4) Evaluation of adsorbent: the method comprises the steps of taking straight-run gasoline as a raw material, enabling the sulfur and nitrogen content to be shown in table 1, enabling the mass fraction of aromatic hydrocarbon components to be 13%, loading an adsorbent into a simulated moving bed, enabling aromatic hydrocarbon adsorption and separation to be a countercurrent simulated moving bed adsorption and separation process, enabling an adsorption bed layer to be 12 layers, enabling the adsorption and separation temperature to be 60 ℃, and enabling methyl cyclohexane and methylbenzene to be desorbed, wherein the mass fraction of the methylbenzene is 20%. Two materials are extracted from the simulated moving bed, one material is rich in aromatic hydrocarbon components, the other material is rich in non-aromatic hydrocarbon components, and the purity of the two materials is analyzed after continuous operation for 30 days. The evaluation results are shown in Table 2.
Example 2
(1) Pore channel modification: weighing 10kg of amorphous silica-alumina, adding 100kg of aqueous solution containing 1500g of nonylphenol polyoxyethylene ether TX-10, treating at 100 ℃ for 2h, and then filtering to obtain a filter cake with a micelle filling pore channel structure formed by water and TX-10.
(2) Metal activation: and (2) weighing 10635g of tetrabutyl titanate and 20kg of triethylamine solution of ethylene glycol for peptizing, wherein the mass concentration of the ethylene glycol is 60% and the mass concentration of the triethylamine is 20%, mixing the tetrabutyl titanate with the filter cake obtained in the step (1), treating the mixture at 120 ℃ for 4 hours, filtering, washing and drying to obtain the adsorbent precursor.
(3) And (3) stability regulation: and (3) placing the adsorbent precursor obtained in the step (2) into a high-pressure autoclave, adding a mixed solvent of benzyl mercaptan and quinoline in a mass ratio of 30, treating for 2h at 200 ℃, filtering, drying, and roasting for 2h at 700 ℃ to obtain the adsorbent.
(4) Evaluation of adsorbent: the evaluation results are shown in Table 2, in the same manner as in example 1.
Example 3
(1) Pore channel modification: weighing 10kg of alumina, adding 80kg of aqueous solution containing 800g of nonylphenol polyoxyethylene ether TX-10, treating at 60 ℃ for 8h, and then filtering to obtain a filter cake with a micelle filling pore channel structure formed by water and TX-10.
(2) Metal activation: weighing 1500g of tetraethyl titanate and 20kg of ethylene diamine solution of 2-propylene glycol for peptizing, wherein the mass concentration of the 2-propylene glycol is 40% and the mass concentration of the ethylene diamine is 10%, then mixing with the filter cake obtained in the step (1), treating at 100 ℃ for 6h, filtering, washing and drying to obtain the adsorbent precursor.
(3) And (3) stability regulation: and (3) placing the adsorbent precursor obtained in the step (2) into a high-pressure kettle, adding a mixed solvent of 10 mass percent of diphenyl sulfide and acridine, treating for 8 hours at 150 ℃, filtering, drying, and roasting for 6 hours at 550 ℃ to obtain the adsorbent.
(4) Evaluation of adsorbent: the same as in example 1, the evaluation results are shown in Table 2.
Example 4
(1) Pore channel modification: weighing 10kgX molecular sieve, adding 80kg of aqueous solution containing 800g of dodecyl phenol polyoxyethylene ether OP-10, treating at 60 ℃ for 8h, and then filtering to obtain a filter cake with a micelle filling pore channel structure formed by water and OP-10.
(2) Metal activation: weighing 1639g of tetrabutyl zirconate to peptize with 20kg of 1 g of triethylamine solution of 4-butanediol, wherein the mass concentration of the 4-butanediol is 40% and the mass concentration of the triethylamine is 10%, then mixing with the filter cake obtained in the step (1), treating at 80 ℃ for 16h, filtering, washing and drying to obtain the adsorbent precursor.
(3) And (3) stability regulation: and (3) placing the adsorbent precursor obtained in the step (2) into a high-pressure kettle, adding a mixed solvent of 10 mass percent of diphenyl sulfide and acridine, treating for 8 hours at 150 ℃, filtering, drying, and roasting for 6 hours at 550 ℃ to obtain the adsorbent.
(4) Evaluation of adsorbent: the method comprises the steps of taking straight-run diesel as a raw material, enabling the sulfur and nitrogen content to be shown in table 1, enabling the mass fraction of aromatic hydrocarbon components to be 21%, loading an adsorbent into a simulated moving bed, enabling aromatic hydrocarbon adsorption and separation to be a countercurrent simulated moving bed adsorption and separation process, enabling an adsorption bed layer to be 12 layers, enabling the adsorption and separation temperature to be 60 ℃, and enabling methyl cyclohexane and methylbenzene to be desorbed, wherein the mass fraction of the methylbenzene is 20%. Two materials are extracted from the simulated moving bed, one material is rich in aromatic hydrocarbon components, the other material is rich in non-aromatic hydrocarbon components, and the purity of the two materials is analyzed after the continuous operation for 30 days. The evaluation results are shown in Table 2.
Example 5
(1) Pore channel modification: weighing 10kgY molecular sieve, adding 70kg aqueous solution containing 840g of dodecyl phenol polyoxyethylene ether OP-10, processing at 80 ℃ for 10h, and then filtering to obtain filter cake with micelle filling pore channel structure formed by water and OP-10.
(2) Metal activation: weighing 1395g of zirconium acetate and 20kg of 1 triethylamine solution of 6-hexanediol for peptization, wherein the mass concentration of 1, 6-hexanediol is 40%, and the mass concentration of triethylamine is 10%, then mixing with the filter cake obtained in the step (1), processing for 20h at 80 ℃, filtering, washing and drying to obtain the adsorbent precursor.
(3) And (3) stability regulation: and (3) placing the adsorbent precursor obtained in the step (2) into a high-pressure autoclave, adding a mixed solvent of benzothiophene and pyridine in a mass ratio of 10, treating for 8 hours at 150 ℃, filtering, drying, and roasting for 6 hours at 550 ℃ to obtain the adsorbent.
(4) Evaluation of adsorbent: the same as in example 4, the evaluation results are shown in Table 2.
Example 6
(1) Pore channel modification: weighing 10kg of silica gel, adding 60kg of aqueous solution containing 900g of nonylphenol polyoxyethylene ether TX-10, treating at 60 ℃ for 12h, and then filtering to obtain a filter cake with a micelle filling pore channel structure formed by water and TX-10.
(2) Metal activation: weighing 696g of trimethyl tin chloride and 20kg of n-butylamine solution of ethylene glycol for peptizing, wherein the mass concentration of the ethylene glycol is 40% and the mass concentration of the n-butylamine is 10%, then mixing with the filter cake obtained in the step (1), processing for 6h at 100 ℃, filtering, washing and drying to obtain the adsorbent precursor.
(3) And (3) stability regulation: and (3) placing the adsorbent precursor obtained in the step (2) into a high-pressure autoclave, adding a mixed solvent of benzothiophene and pyridine in a mass ratio of 10, treating for 8 hours at 150 ℃, filtering, drying, and roasting for 6 hours at 550 ℃ to obtain the adsorbent.
(5) Evaluation of adsorbent: the same as in example 4, the evaluation results are shown in Table 2.
Comparative example 1
The procedure of synthesis was the same as in example 1 except that tetrabutyl titanate as a stable metal compound was not added, and the adsorbent evaluation was the same as in example 1, and the evaluation results are shown in Table 2.
Comparative example 2
The procedure was the same as in example 5 except that tetrabutyl zirconate, a stable metal compound, was not added during the synthesis, the adsorbent evaluation was the same as in example 4, and the evaluation results are shown in Table 2.
TABLE 1 adsorption separation of raw material impurity content
TABLE 2 evaluation results of adsorbents
Claims (8)
1. The preparation method of the aromatic hydrocarbon adsorbent for the high sulfur-nitrogen raw oil is characterized by comprising the following steps of:
(1) pore channel modification: mixing the silicon-aluminum adsorbent with a non-ionic surfactant solution, and filtering to obtain a filter cake with a micelle filling pore channel structure formed by water and the non-ionic surfactant;
(2) metal activation: mixing and peptizing a stable metal compound and an organic amine solution of dihydric alcohol to obtain a metal sol, then mixing the metal sol with the filter cake obtained in the step (1), and filtering, washing and drying to obtain an adsorbent precursor;
(3) and (3) stability regulation: placing the adsorbent precursor obtained in the step (2) into a high-pressure kettle for sulfur-nitrogen compound solvent treatment, and filtering, drying and roasting after the treatment is finished to obtain the aromatic adsorbent;
wherein the silicon-aluminum adsorbent is at least one of silicon oxide, amorphous silicon-aluminum, aluminum oxide, X molecular sieve and Y molecular sieve; the metal is at least one of Al, Ti, Zr and Sn, and the mass content of the silicon-aluminum adsorbent in the aromatic hydrocarbon adsorbent is 80-99%.
2. The preparation method according to claim 1, wherein the solid-liquid mass ratio in step (1) is 1: (5-10), the nonionic surfactant is at least one of dodecyl phenol polyoxyethylene ether OP-10 and nonylphenol polyoxyethylene ether TX-10, the concentration of the nonionic surfactant is 0.5% -1.5%, and the treatment conditions are 40-100 ℃ and 2-12 h.
3. The preparation method according to claim 1, wherein the stable metal compound in step (2) is at least one of aluminum isopropoxide, tetrabutyl titanate, tetraethyl titanate, tetrabutyl zirconate, zirconium acetate and trimethyltin chloride, the diol is at least one of ethylene glycol, 2-propylene glycol, 1, 4-butanediol and 1, 6-hexanediol, the mass concentration of the diol is 30% -60%, the organic amine is at least one of ethylenediamine, n-butylamine and triethylamine, the mass concentration of the organic amine is 5% -20%, and the treatment conditions are 60-120 ℃ and 4-24 h.
4. The preparation method as claimed in claim 1, wherein the mass ratio of the sulfur compound in the sulfur-nitrogen compound solvent and the nitrogen compound in step (3) is 5-30, the sulfur compound is at least one of benzothiophene, benzylmercaptan and phenylsulfide, the nitrogen compound is at least one of pyridine, quinoline and acridine, the treatment conditions are 120-200 ℃ and 2-12h, the roasting temperature is 500-700 ℃ and the roasting time is 2-12 h.
5. The aromatic hydrocarbon adsorbent for high sulfur-nitrogen raw oil prepared by the preparation method of any one of claims 1 to 4.
6. The application of the aromatic hydrocarbon adsorbent for high sulfur-nitrogen raw oil in the adsorption separation of aromatic hydrocarbon in high sulfur-nitrogen raw oil according to claim 5, wherein the process for adsorption separation of aromatic hydrocarbon in high sulfur-nitrogen raw oil is a simulated moving bed process, and the purity of aromatic hydrocarbon components is more than 99%, and the purity of non-aromatic hydrocarbon components is more than 99%.
7. The use of claim 5, wherein the high sulfur-nitrogen raw oil comprises at least one of straight-run gasoline, straight-run kerosene, straight-run diesel oil, coker gasoline, coker kerosene and coker diesel oil according to a processing mode.
8. The use of claim 5, wherein the high sulfur-nitrogen raw oil is a raw material with a hydrocarbon carbon number composition of C4-C22, S is less than or equal to 10000ppm, and N is less than or equal to 1000 ppm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5220099A (en) * | 1988-08-31 | 1993-06-15 | Exxon Chemical Patents Inc. | Purification of a hydrocarbon feedstock using a zeolite adsorbent |
| US5925330A (en) * | 1998-02-13 | 1999-07-20 | Mobil Oil Corporation | Method of m41s functionalization of potentially catalytic heteroatom centers into as-synthesized m41s with concomitant surfactant extraction |
| RU2010153767A (en) * | 2010-12-28 | 2012-07-10 | Светлана Борисовна Зуева (RU) | WASTE WATER TREATMENT METHOD |
| CN104549423A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Metal modified Y zeolite and preparation method and application thereof |
| CN106187666A (en) * | 2016-06-30 | 2016-12-07 | 中国海洋石油总公司 | A kind of C10+the method that aromatics absorption separates |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5220099A (en) * | 1988-08-31 | 1993-06-15 | Exxon Chemical Patents Inc. | Purification of a hydrocarbon feedstock using a zeolite adsorbent |
| US5925330A (en) * | 1998-02-13 | 1999-07-20 | Mobil Oil Corporation | Method of m41s functionalization of potentially catalytic heteroatom centers into as-synthesized m41s with concomitant surfactant extraction |
| RU2010153767A (en) * | 2010-12-28 | 2012-07-10 | Светлана Борисовна Зуева (RU) | WASTE WATER TREATMENT METHOD |
| CN104549423A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Metal modified Y zeolite and preparation method and application thereof |
| CN106187666A (en) * | 2016-06-30 | 2016-12-07 | 中国海洋石油总公司 | A kind of C10+the method that aromatics absorption separates |
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