CN114950341A - Binder-free arene adsorbent and preparation method thereof - Google Patents
Binder-free arene adsorbent and preparation method thereof Download PDFInfo
- Publication number
- CN114950341A CN114950341A CN202210468545.XA CN202210468545A CN114950341A CN 114950341 A CN114950341 A CN 114950341A CN 202210468545 A CN202210468545 A CN 202210468545A CN 114950341 A CN114950341 A CN 114950341A
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- China
- Prior art keywords
- active
- sol
- aromatic hydrocarbon
- filter cake
- metal composite
- Prior art date
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- Granted
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 75
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000012065 filter cake Substances 0.000 claims abstract description 62
- 238000002156 mixing Methods 0.000 claims abstract description 54
- 238000001179 sorption measurement Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002905 metal composite material Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000004094 surface-active agent Substances 0.000 claims abstract description 24
- 239000003513 alkali Substances 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 19
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 18
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000012778 molding material Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 45
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 235000019353 potassium silicate Nutrition 0.000 claims description 8
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000007529 inorganic bases Chemical class 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000693 micelle Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 4
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 230000000274 adsorptive effect Effects 0.000 claims 1
- 238000000748 compression moulding Methods 0.000 claims 1
- 229910052732 germanium Inorganic materials 0.000 claims 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 238000011156 evaluation Methods 0.000 description 22
- 239000011959 amorphous silica alumina Substances 0.000 description 20
- 239000002808 molecular sieve Substances 0.000 description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 238000005096 rolling process Methods 0.000 description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- LYEWAIRXZWODSJ-UHFFFAOYSA-M [OH-].[K+].CCCCN Chemical compound [OH-].[K+].CCCCN LYEWAIRXZWODSJ-UHFFFAOYSA-M 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 3
- NWEKXBVHVALDOL-UHFFFAOYSA-N butylazanium;hydroxide Chemical compound [OH-].CCCC[NH3+] NWEKXBVHVALDOL-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 238000009718 spray deposition Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- XGFABUPTUPKRQI-UHFFFAOYSA-M potassium;n,n-diethylethanamine;hydroxide Chemical compound [OH-].[K+].CCN(CC)CC XGFABUPTUPKRQI-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- ZGMWRQIARRVYDR-UHFFFAOYSA-M sodium;n,n-diethylethanamine;hydroxide Chemical compound [OH-].[Na+].CCN(CC)CC ZGMWRQIARRVYDR-UHFFFAOYSA-M 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J20/103—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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
Abstract
The invention discloses a binderless aromatic hydrocarbon adsorbent and a preparation method thereof, wherein the adsorbent consists of 80-99% of active oxide and 1-20% of active gel by mass percent, and the preparation method of the adsorbent comprises the following steps: 1) synthesizing metal composite silica sol by using a silicon source, a metal salt, inorganic acid, a surfactant and water as raw materials or synthesizing metal composite amorphous silica sol by using the silicon source, an aluminum source, the metal salt, the inorganic acid, the surfactant and the water as raw materials; 2) carrying out hydrothermal aging, washing and filtering on the metal composite silica sol or the metal composite amorphous silicon-aluminum sol to obtain a filter cake; 3) mixing the filter cake with inorganic and organic composite alkali to obtain active sol; 4) uniformly mixing the filter cake and the active sol to obtain a molding material; 5) and (3) molding, drying and roasting the molded material to obtain the binder-free aromatic hydrocarbon adsorbent. The adsorbent is applied to a simulated moving bed aromatic hydrocarbon adsorption separation process, and can reduce the separation energy consumption by 20 percent compared with the aromatic hydrocarbon adsorbent with a binder.
Description
Technical Field
The invention relates to an aromatic hydrocarbon adsorbent without adhesion and a preparation method thereof
Background
Through the continuous development in recent years, although the refining industry in China has become the national economic life line and safe pillar industry, the refining industry has become the problem to be solved urgently by the refining enterprise, facing a plurality of challenges of surplus productivity, serious product homogenization, insufficient enterprise development innovation, large environmental protection pressure, severe foreign market competition and the like, how to improve quality and efficiency, increase production of high-quality products and realize sustainable development of the enterprise. The 'oil, alkene and arene are preferably used as arene' which are the targets pursued by various large refining enterprises, but the overall technical level is still not high, the innovation capability is poor, the technical content and the additional value of the product are low, and the maximization and the reasonable utilization of the oil value are not really realized.
The gasoline and diesel are subjected to adsorption separation through a Simulated Moving Bed (SMB) to obtain high-purity aromatic hydrocarbon and high-purity non-aromatic hydrocarbon components, molecular management of the gasoline and diesel components can be realized, market demand changes can be responded in a more targeted manner, subsequent aromatic hydrocarbon and non-aromatic hydrocarbon conversion processes can be coupled, directional conversion of the gasoline and diesel to chemical products is realized, and economic benefits are improved. The SMB adsorption separation process needs spherical particle adsorbent in a certain size range, and the formed adsorbent contains a large amount of binder, which causes the problems of small adsorption capacity, low adsorption and desorption rate and poor adsorption effect of the adsorbent.
Patent CN101524637B discloses a preparation method of an LSX molecular sieve-rich binder-free adsorbent, comprising mixing KNaLSX with a binder, adding a silicon source, an alkali source and a pore-expanding agent for molding, and carrying out in-situ crystallization on the binder through sodium hydroxide treatment to realize the preparation of the binder-free adsorbent. Patent CN109647329A discloses a method for preparing a binderless composite molecular sieve, which comprises mixing the formed molecular sieve raw powder, a template agent, sodium silicate and water, and carrying out hydrothermal crystallization in a crystallization kettle to obtain the binderless composite molecular sieve, thereby solving the problem of a large amount of Al in the formed molecular sieve 2 O 3 Resulting in a problem of low adsorption desulfurization rate. Patent CN107159105A discloses a binderless 13X molecular sieve adsorbent and its preparation method, which comprises adding molecular sieve into a formed adsorbent as seed crystal, controlling the alkaline environment suitable for molecular sieve growth, so that the binderless molecular sieve adsorbent has a binderless binder content of 5% or less, a large adsorption capacity and a high molecular sieve strength, and the binderless molecular sieve adsorbent is obtained by transforming the binderless adsorbent into the molecular sieve effective components through nucleation and growth.
The above patent adopts the secondary in-situ crystallization technology in the process of preparing the binderless adsorbent, i.e. the formed adsorbent is crystallized, the binder is converted into the molecular sieve component, the process is complex, the loss of the adsorbent can be caused in the secondary in-situ crystallization process, and the production yield is reduced.
Disclosure of Invention
The invention relates to a binderless aromatic hydrocarbon adsorbent and a preparation method thereof, and aims to solve the technical problems that a binder is used in the forming process of the aromatic hydrocarbon adsorbent, and the binder has no adsorption activity, so that the adsorption-desorption speed of the adsorbent is slowed, the consumption of a desorbent is increased, and the energy consumption is higher; the second technical problem to be solved by the invention is that no binder is added in the aromatic hydrocarbon adsorbent forming process, and the adsorbent strength can not meet the use requirement of an adsorption separation device (the 200N crushing rate is less than or equal to 3%).
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention provides a binder-free arene adsorbent, which consists of 80-99% of active oxide and 1-20% of active gel in mass fraction, wherein the active oxide and the active gel are both one of metal composite silicon oxide or metal composite amorphous silicon aluminum, the metal is one of germanium oxide, tin oxide, titanium oxide, zirconium oxide, manganese oxide and vanadium oxide, and the mass content of the metal in the active oxide and the active gel is 0.5-40%.
In the technical scheme, the binderless aromatic hydrocarbon adsorbent is prepared by the following steps:
(1) mixing a silicon source, a metal salt, an inorganic acid, a surfactant and water to obtain metal composite silica sol, wherein the total molar composition of the mixture is SiO 2 : metal salt: h + : surfactant (b): h 2 O ═ 1 (0.05: 0.15): (0.05-1): (0.05-0.2): (20-60), or mixing a silicon source, an aluminum source, a metal salt: inorganic alkali, surfactant and water are mixed to obtain the metal composite amorphous silicon-aluminum sol, and the total molar composition of the mixture is SiO 2 ：Al 2 O 3 : metal salt: OH (OH) - : surfactant (B): h 2 O＝1:(0.2-1):(0.05:0.15)：(0.05-1)：(0.05-0.2)：(20-60)；
(2) Carrying out hydrothermal aging, washing and filtering on one of the metal composite silica sol or the metal composite amorphous silicon-aluminum sol obtained in the step (1) to obtain a filter cake of a micelle filling pore channel structure formed by water and a surfactant, wherein the pore channel structure is one of metal composite silica or metal composite amorphous silicon-aluminum, the metal is one of germanium oxide, tin oxide, titanium oxide, zirconium oxide, manganese oxide and vanadium oxide, and the dry basis of the filter cake is 15-50 wt%;
(3) mixing the filter cake obtained in the step (2) with organic-inorganic composite alkali liquor, adjusting the pH to be more than 10, dissolving to obtain active sol with adsorption performance, wherein the dry basis is 5-30 wt%, and roasting to obtain active gel;
(4) uniformly mixing the filter cake obtained in the step (2) with the active sol obtained in the step (3) to obtain a formed material;
(5) and (4) molding, drying and roasting the molding material obtained in the step (4) to obtain the binder-free aromatic hydrocarbon adsorbent.
The invention also provides a preparation method of the adsorbent, which comprises the following steps:
(1) mixing a silicon source, a metal salt, an inorganic acid, a surfactant and water to obtain metal composite silica sol, wherein the total molar composition of the mixture is SiO 2 : metal salt: h + : surfactant (b): h 2 O ═ 1 (0.05-0.15): (0.05-1): (0.05-0.2): (20-60), or mixing a silicon source, an aluminum source, a metal salt: inorganic alkali, surfactant and water are mixed to obtain the metal composite amorphous silicon-aluminum sol, and the total molar composition of the mixture is SiO 2 ：Al 2 O 3 : metal salt: OH group - : surfactant (B): h 2 O＝1:(0.2-1):(0.05:0.15)：(0.05-1)：(0.05-0.2)：(20-60)；
(2) Carrying out hydrothermal aging, washing and filtering on one of the metal composite silica sol or the metal composite amorphous silicon-aluminum sol obtained in the step (1) to obtain a filter cake of a micelle filling pore channel structure formed by water and a surfactant, wherein the pore channel structure is one of metal composite silica or metal composite amorphous silicon-aluminum, the metal is one of germanium oxide, tin oxide, titanium oxide, zirconium oxide, manganese oxide and vanadium oxide, and the dry basis of the filter cake is 15-50 wt%;
(3) mixing the filter cake obtained in the step (2) with organic-inorganic composite alkali liquor, adjusting the pH to be more than 10, dissolving to obtain active sol with adsorption performance, wherein the dry basis is 5-30 wt%, and roasting to obtain active gel;
(4) uniformly mixing the filter cake obtained in the step (2) with the active sol obtained in the step (3) to obtain a formed material;
(5) and (4) molding, drying and roasting the molding material obtained in the step (4) to obtain the binder-free aromatic hydrocarbon adsorbent.
In the preparation method of the adhesive-free aromatic hydrocarbon adsorbent, the silicon source in the step (1) is one of water glass and silica sol; the aluminum source is one of aluminum sulfate, aluminum nitrate, aluminum chloride and sodium metaaluminate; the metal salt is one of germanium chloride, stannic chloride, stannous sulfate, titanium chloride, titanium nitrate, titanium sulfate, zirconium chloride, zirconium nitrate and zirconium sulfate; the inorganic acid is one of sulfuric acid, nitric acid and hydrochloric acid; the inorganic base is one of sodium hydroxide and potassium hydroxide; the surfactant is one of sodium dodecyl benzene sulfonate, fatty alcohol ether sodium sulfate and isooctyl alcohol phosphate.
In the preparation method of the adhesive-free aromatic hydrocarbon adsorbent, the aging temperature in the step (2) is 30-90 ℃, and the aging time is 1-24 h.
In the preparation method of the adhesive-free aromatic hydrocarbon adsorbent, in the step (3), the organic-inorganic composite alkali accounts for 5-20% by mass, the inorganic alkali is one of sodium hydroxide and potassium hydroxide, the organic alkali is one of triethylamine and n-butylamine, and the mass ratio of the inorganic alkali to the inorganic alkali is as follows: organic base ═ 1: (0.1-5).
In the preparation method of the adhesive-free aromatic hydrocarbon adsorbent, the forming material in the step (4) is composed of 80-99% of active oxide and 1-20% of active gel in percentage by mass on a dry basis.
In the preparation method of the adhesive-free aromatic hydrocarbon adsorbent, the forming method in the step (5) is one of rolling ball forming, spray forming and compression forming.
The invention further provides an application of the adhesive-free aromatic hydrocarbon adsorbent in adsorption separation of aromatic hydrocarbon in gasoline and diesel components. Preferably, the method comprises the steps of filling the binderless aromatic hydrocarbon adsorbent into a simulated moving bed, and adopting a countercurrent simulated moving bed adsorption separation process, wherein an adsorption bed layer is 8-24 layers, the adsorption separation temperature is 40-150 ℃, and a desorbent is a mixture of alkane and aromatic hydrocarbon; further preferably, in the countercurrent simulated moving bed adsorption separation process, the adsorption bed layer is preferably 8-16 layers, the adsorption separation temperature is 50-100 ℃, the resolving agents are methylcyclohexane and toluene, and the mass fraction of the toluene is 10% -50%.
The invention has the beneficial effects that: the aromatic hydrocarbon adsorbent without the binder is obtained by preparing the active sol with aromatic hydrocarbon adsorption activity and cohesiveness, and mixing and molding the active sol with the metal composite silicon oxide, wherein the 200N crushing rate is less than or equal to 3 percent.
Detailed Description
The technical solution of the present invention is further described 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: gasoline and diesel oil are used as raw materials, and the aromatic hydrocarbon content of the fraction section is 15-70%. The adsorbent is filled into a simulated moving bed, the aromatic hydrocarbon is separated by adsorption into a countercurrent simulated moving bed, the adsorption bed layer is 8-24 layers, preferably 8-16 layers, the adsorption separation temperature is 40-150 ℃, preferably 50-100 ℃, and the desorbent is a mixture of alkane and aromatic hydrocarbon, preferably methylcyclohexane and toluene, wherein 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 and desorption ratio of the two materials are analyzed.
Example 1
(1) Formation of active oxide: preparing 10kg of water glass, 1kg of germanium chloride, 3.2kg of sulfuric acid, 2.3kg of sodium dodecyl benzene sulfonate and 27kg of water, uniformly mixing, heating to 30 ℃, aging for 24 hours, then performing suction filtration, and fully washing by using deionized water to obtain an active silicon oxide filter cake.
(2) Forming an active sol: weighing 10 wt% of the active silica filter cake obtained in the step (1), and uniformly mixing with 5 wt% of sodium hydroxide-triethylamine composite base, wherein the mass ratio of sodium hydroxide: and (3) dissolving triethylamine in a ratio of 1:0.1 by adjusting the pH value to be more than 10 to obtain the active sol.
(3) Mixing the active silica filter cake obtained in the step (1) and the active sol obtained in the step (2) according to the mass ratio of silica contained in the active silica filter cake to silica contained in the active sol to be 99: 1, uniformly mixing to obtain a molding material.
(4) And (4) rolling ball forming is carried out on the formed material obtained in the step (3), drying is carried out for 12 hours at the temperature of 150 ℃, and roasting is carried out for 6 hours at the temperature of 500 ℃, so that the adhesive-free aromatic hydrocarbon adsorbent is obtained.
(5) Evaluation of adsorbent: the method comprises the steps of taking hydrogenation catalytic diesel as a raw material, filling an adsorbent into a simulated moving bed with the mass fraction of aromatic hydrocarbon components being 30.5%, carrying out adsorption separation on the aromatic hydrocarbon into a countercurrent simulated moving bed adsorption separation process, wherein an adsorption bed layer is 12 layers, the adsorption separation temperature is 60 ℃, and desorbing agents of methylcyclohexane and toluene, wherein the mass fraction of the toluene 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 and the desorption ratio of the two materials are analyzed. The evaluation results are shown in Table 1.
Example 2
(1) Formation of active oxide: preparing 10kg of water glass, 0.43kg of tin chloride, 0.16kg of sulfuric acid, 0.359kg of isooctyl alcohol phosphate and 4kg of water, uniformly mixing, heating to 90 ℃, aging for 12 hours, then carrying out suction filtration, and fully washing by using deionized water to obtain the active silicon oxide filter cake.
(2) Forming an active sol: weighing 20 wt% of the active silica filter cake obtained in the step (1), and uniformly mixing with 15 wt% of potassium hydroxide-triethylamine composite base, wherein the mass ratio of potassium hydroxide: and (3) dissolving triethylamine in the ratio of 1:1 by adjusting the pH value to be more than 10 to obtain the active sol.
(3) Mixing the active silica filter cake obtained in the step (1) with the active sol obtained in the step (2) according to the mass ratio of silica contained in the active silica filter cake to the active sol to be 4: 1, uniformly mixing to obtain a molding material.
(4) And (4) rolling ball forming is carried out on the formed material obtained in the step (3), drying is carried out for 12 hours at the temperature of 120 ℃, and roasting is carried out for 6 hours at the temperature of 550 ℃, so that the adhesive-free aromatic hydrocarbon adsorbent is obtained.
(5) Evaluation of adsorbent: the evaluation results are shown in Table 1, similarly to example 1.
Example 3
(1) Formation of active oxide: preparing 10kg of water glass, 0.71kg of stannous sulfate, 1kg of nitric acid, 0.97kg of fatty alcohol ether sodium sulfate and 10kg of water, uniformly mixing, heating to 90 ℃, aging for 1h, then performing suction filtration, and fully washing with deionized water to obtain the active silicon oxide filter cake.
(2) Forming an active sol: weighing 1 wt% of the active silica filter cake obtained in the step (1), and uniformly mixing with 20 wt% of potassium hydroxide-n-butylamine composite alkali, wherein the mass ratio of potassium hydroxide: and (3) adjusting the pH value to be more than 10 to dissolve n-butylamine to be 1:5 to obtain the active sol.
(3) Mixing the active silica filter cake obtained in the step (1) with the active sol obtained in the step (2) according to the mass ratio of silica contained in the active silica filter cake to silica contained in the active sol to be 9: 1, uniformly mixing to obtain a molding material.
(4) And (4) rolling ball forming, drying at 150 ℃ for 12h, and roasting at 600 ℃ for 4h are carried out on the formed material obtained in the step (3), so as to obtain the binder-free arene adsorbent.
(5) Evaluation of adsorbent: the evaluation results are shown in Table 1, similarly to example 1.
Example 4
(1) Formation of active oxide: 10kg of silica sol, 0.63kg of titanium chloride, 0.61kg of hydrochloric acid, 0.72kg of isooctyl alcohol phosphate and 15kg of water are prepared, uniformly mixed, heated to 90 ℃, aged for 1h, filtered, and fully washed by deionized water to obtain the active silica filter cake.
(2) Forming an active sol: weighing 1 wt% of the active silica filter cake obtained in the step (1), and uniformly mixing with 20 wt% of potassium hydroxide-n-butylamine composite alkali, wherein the mass ratio of potassium hydroxide: dissolving n-butylamine at a pH of more than 10 at a ratio of 1:5 to obtain an active sol.
(3) And (3) uniformly mixing the active silica filter cake obtained in the step (1) with the active sol obtained in the step (2) to obtain a molding material.
(4) And (4) performing spray forming on the formed material obtained in the step (3), drying at 150 ℃ for 12h, and roasting at 500 ℃ for 4h to obtain the binder-free aromatic hydrocarbon adsorbent.
(5) Evaluation of the adsorbent: the evaluation results are shown in Table 1, similarly to example 1.
Example 5
(1) Formation of active oxide: 10kg of silica sol, 0.78kg of zirconium chloride, 0.61kg of hydrochloric acid, 1.16kg of sodium dodecyl benzene sulfonate and 22kg of water are prepared, uniformly mixed, heated to 80 ℃, aged for 6 hours, filtered, and fully washed by deionized water to obtain the active silica filter cake.
(2) Forming an active sol: weighing 5 wt% of the active silica filter cake obtained in the step (1), and uniformly mixing with 10 wt% of potassium hydroxide-n-butylamine composite alkali, wherein the mass ratio of potassium hydroxide: and (3) adjusting the pH value to be more than 10 to dissolve n-butylamine to be 1:2 to obtain the active sol.
(3) Mixing the active silica filter cake obtained in the step (1) with the active sol obtained in the step (2) according to the mass ratio of the contained silica of 19: 1, uniformly mixing to obtain a molding material.
(4) And (4) carrying out extrusion forming on the formed material obtained in the step (3), drying at 150 ℃ for 12h, and roasting at 550 ℃ for 4h to obtain the binder-free aromatic hydrocarbon adsorbent.
(5) Evaluation of adsorbent: the evaluation results are shown in Table 1, similarly to example 1.
Example 6
(1) Formation of active oxide: 10kg of water glass, 2.3kg of aluminum sulfate, 0.5kg of titanium nitrate, 0.094kg of potassium hydroxide, 0.59kg of sodium dodecyl benzene sulfonate and 4kg of water are prepared, uniformly mixed, heated to 40 ℃, aged for 24 hours, then filtered, and fully washed by deionized water to obtain the active amorphous silica-alumina filter cake.
(2) Forming an active sol: weighing 20 wt% of the activated amorphous silica-alumina filter cake obtained in the step (1), and uniformly mixing with 15 wt% of potassium hydroxide-n-butylamine complex alkali, wherein the mass ratio of potassium hydroxide: n-butylamine 1:0.5, dissolved at pH > 10 to give an active sol.
(3) Mixing the activated amorphous silica-alumina filter cake obtained in the step (1) with the activated sol obtained in the step (2) according to the mass ratio of silicon oxide contained in the activated amorphous silica-alumina filter cake to silicon oxide contained in the activated sol to silicon oxide contained in the activated silica-alumina filter cake to silicon oxide contained in the activated sol to silicon oxide mass ratio of 19: 1, uniformly mixing to obtain a molding material.
(4) And (4) rolling ball forming is carried out on the formed material obtained in the step (3), drying is carried out for 12 hours at the temperature of 150 ℃, and roasting is carried out for 6 hours at the temperature of 500 ℃, so that the adhesive-free aromatic hydrocarbon adsorbent is obtained.
(5) Evaluation of adsorbent: the evaluation results are shown in Table 1, similarly to example 1.
Example 7
(1) Formation of active oxide: 10kg of water glass, 5.4kg of sodium metaaluminate, 1.4kg of zirconium sulfate, 1.4kg of sodium hydroxide, 2.3kg of sodium dodecyl benzene sulfonate and 27kg of water are prepared, uniformly mixed, heated to 30 ℃, aged for 24 hours, filtered, fully washed by deionized water, and then the active amorphous silica-alumina filter cake is obtained.
(2) Forming an active sol: weighing 1 wt% of the active amorphous silica-alumina filter cake obtained in the step (1), and uniformly mixing with 5 wt% of potassium hydroxide-n-butylamine complex alkali, wherein the mass ratio of potassium hydroxide: and (3) adjusting the pH value to be more than 10 to dissolve n-butylamine to be 1:5 to obtain the active sol.
(3) Mixing the activated amorphous silica-alumina filter cake obtained in the step (1) with the activated sol obtained in the step (2) according to the mass ratio of silicon oxide contained in the activated amorphous silica-alumina filter cake to silicon oxide contained in the activated sol to silicon oxide contained in the activated silica-alumina filter cake to silicon oxide contained in the activated sol to silicon oxide mass ratio of 19: 1, uniformly mixing to obtain a molding material.
(4) And (4) rolling ball forming is carried out on the formed material obtained in the step (3), drying is carried out for 12h at the temperature of 150 ℃, and roasting is carried out for 4h at the temperature of 550 ℃, so that the adhesive-free aromatic hydrocarbon adsorbent is obtained.
(5) Evaluation of adsorbent: the evaluation results are shown in Table 1, similarly to example 1.
Example 8
(1) Formation of active oxide: preparing 10kg of water glass, 3.5kg of aluminum nitrate, 0.8kg of titanium sulfate, 0.7kg of sodium hydroxide, 0.7kg of isooctyl alcohol phosphate and 10kg of water, uniformly mixing, heating to 90 ℃, aging for 1h, then performing suction filtration, and fully washing by using deionized water to obtain the active amorphous silica-alumina filter cake.
(2) Forming an active sol: weighing 5 wt% of the activated amorphous silica-alumina filter cake obtained in the step (1), and uniformly mixing with 10 wt% of hydroxide-n-butylamine complex alkali, wherein the mass ratio of potassium hydroxide: and (3) adjusting the pH value to be more than 10 to dissolve n-butylamine to be 1:2 to obtain the active sol.
(3) Mixing the activated amorphous silica-alumina filter cake obtained in the step (1) with the activated sol obtained in the step (2) according to the mass ratio of silicon oxide contained in the activated amorphous silica-alumina filter cake to silicon oxide contained in the activated sol to silicon oxide contained in the activated silica-alumina filter cake to silicon oxide contained in the activated sol to silicon oxide mass ratio of 19: 1, uniformly mixing to obtain a molding material.
(4) And (4) rolling ball forming is carried out on the formed material obtained in the step (3), drying is carried out for 12h at the temperature of 150 ℃, and roasting is carried out for 4h at the temperature of 550 ℃, so that the adhesive-free aromatic hydrocarbon adsorbent is obtained.
(5) Evaluation of adsorbent: the evaluation results are shown in Table 1, similarly to example 1.
Example 9
(1) Formation of active oxide: 10kg of silica sol, 4.4kg of aluminum chloride, 0.87kg of stannic chloride, 0.7kg of sodium hydroxide, 0.7kg of isooctyl alcohol phosphate and 16kg of water are prepared, uniformly mixed, heated to 80 ℃, aged for 6 hours, filtered, fully washed by deionized water, and then the active amorphous silica-alumina filter cake is obtained.
(2) Forming an active sol: weighing 10 wt% of the active amorphous silica-alumina filter cake obtained in the step (1), and uniformly mixing with 15 wt% of hydroxide-n-butylamine complex alkali, wherein the mass ratio of potassium hydroxide: and (3) adjusting the pH value to be more than 10 to dissolve n-butylamine to be 1:2 to obtain the active sol.
(3) Mixing the activated amorphous silica-alumina filter cake obtained in the step (1) with the activated sol obtained in the step (2) according to the mass ratio of silicon oxide contained in the activated amorphous silica-alumina filter cake to silicon oxide contained in the activated sol to silicon oxide contained in the activated silica-alumina filter cake to silicon oxide contained in the activated sol to silicon oxide mass ratio of 19: 1, uniformly mixing to obtain a molding material.
(4) And (4) carrying out extrusion forming on the formed material obtained in the step (3), drying at-150 ℃ for 12h, and roasting at 550 ℃ for 4h to obtain the binder-free aromatic hydrocarbon adsorbent.
(5) Evaluation of adsorbent: the evaluation results are shown in Table 1, similarly to example 1.
Example 10
(1) Formation of active oxide: 10kg of silica sol, 2.7kg of sodium metaaluminate, 0.71kg of stannous sulfate, 0.9kg of potassium hydroxide, 1kg of fatty alcohol ether sodium sulfate and 22kg of water are prepared, uniformly mixed, heated to 60 ℃, aged for 18h, filtered, fully washed by deionized water, and then the active amorphous silica-alumina filter cake is obtained.
(2) Forming an active sol: weighing 5 wt% of the activated amorphous silica-alumina filter cake obtained in the step (1), and uniformly mixing with 10 wt% of hydroxide-n-butylamine complex alkali, wherein the mass ratio of potassium hydroxide: n-butylamine 1:1, adjusted pH > 10 to dissolve to give an active sol.
(3) Mixing the activated amorphous silica-alumina filter cake obtained in the step (1) with the activated sol obtained in the step (2) according to the mass ratio of silicon oxide contained in the activated amorphous silica-alumina filter cake to silicon oxide contained in the activated sol to silicon oxide contained in the activated silica-alumina filter cake to silicon oxide contained in the activated sol to silicon oxide mass ratio of 19: 1, uniformly mixing to obtain a molding material.
(4) And (4) performing spray forming on the formed material obtained in the step (3), drying at 150 ℃ for 12h, and roasting at 550 ℃ for 6h to obtain the binder-free aromatic hydrocarbon adsorbent.
(5) Evaluation of adsorbent: the evaluation results are shown in Table 1, similarly to example 1.
Comparative example 1
The preparation method of the aromatic hydrocarbon adsorbent is the same as that of the aromatic hydrocarbon adsorbent in example 1, and 5% of silica sol is added in the forming process to be used as a binder.
Comparative example 2
The preparation method of the aromatic hydrocarbon adsorbent is the same as that of the aromatic hydrocarbon adsorbent in example 1, and 10% of silica sol is added in the forming process to be used as a binder.
TABLE 1 evaluation results of adsorbents
Claims (9)
1. The aromatic hydrocarbon adsorbent without the binder is characterized by comprising 80-99% of active oxide and 1-20% of active gel in percentage by mass, wherein the active oxide and the active gel are one of metal composite silicon oxide or metal composite amorphous silicon aluminum, the metal is one of germanium, tin, titanium, zirconium, manganese and vanadium, and the metal content in the active oxide and the active gel is 0.5-40% in percentage by mass;
the preparation method of the binderless aromatic hydrocarbon adsorbent comprises the following steps of:
(1) mixing a silicon source, a metal salt, an inorganic acid, a surfactant and water to obtain metal composite silica sol, wherein the total molar composition of the mixture is SiO 2 : metal salt: h + : surfactant (b): h 2 O ═ 1 (0.05: 0.15): (0.05-1): (0.05-0.2): (20-60), or mixing a silicon source, an aluminum source, a metal salt: inorganic alkali, surfactant and water are mixed to obtain the metal composite amorphous silicon-aluminum sol, and the total molar composition of the mixture is SiO 2 ：Al 2 O 3 : metal salt: OH (OH) - : surfactant (B): h 2 O＝1:(0.2-1):(0.05:0.15)：(0.05-1)：(0.05-0.2)：(20-60)；
(2) Carrying out hydrothermal aging, washing and filtering on one of the metal composite silica sol or the metal composite amorphous silicon-aluminum sol obtained in the step (1) to obtain a filter cake of a micelle filling pore channel structure formed by water and a surfactant, wherein the pore channel structure is one of metal composite silica or metal composite amorphous silicon-aluminum, and the dry basis of the filter cake is 15-50 wt%;
(3) mixing the filter cake obtained in the step (2) with inorganic organic composite alkali liquor, adjusting the pH to be more than 10, dissolving to obtain active sol with adsorption performance, wherein the dry basis is 5-30 wt%, and roasting to obtain active gel;
(4) uniformly mixing the filter cake obtained in the step (2) with the active sol obtained in the step (3) to obtain a formed material;
(5) and (4) molding, drying and roasting the molding material obtained in the step (4) to obtain the binder-free aromatic hydrocarbon adsorbent.
2. The method for preparing the binderless aromatic hydrocarbon adsorbent of claim 1, comprising the steps of:
(1) mixing a silicon source, a metal salt, an inorganic acid, a surfactant and water to obtain metal composite silica sol, wherein the total molar composition of the mixture is SiO 2 : metal salt: h + : surfactant (B): h 2 O ═ 1 (0.05: 0.15): (0.05-1): (0.05-0.2): (20-60), or mixing a silicon source, an aluminum source, a metal salt: inorganic alkali, surfactant and water are mixed to obtain the metal composite amorphous silicon-aluminum sol, and the total molar composition of the mixture is SiO 2 ：Al 2 O 3 : metal salt: OH group - : surfactant (b): h 2 O＝1:(0.2-1):(0.05:0.15)：(0.05-1)：(0.05-0.2)：(20-60)；
(2) Carrying out hydrothermal aging, washing and filtering on one of the metal composite silica sol or the metal composite amorphous silicon-aluminum sol obtained in the step (1) to obtain a filter cake of a micelle filling pore channel structure formed by water and a surfactant, wherein the pore channel structure is one of metal composite silica or metal composite amorphous silicon-aluminum, and the dry basis of the filter cake is 15-50 wt%;
(3) mixing the filter cake obtained in the step (2) with inorganic organic composite alkali liquor, adjusting the pH to be more than 10, dissolving to obtain active sol with adsorption performance, wherein the dry basis is 5-30 wt%, and roasting to obtain active gel;
(4) uniformly mixing the filter cake obtained in the step (2) with the active sol obtained in the step (3) to obtain a formed material;
(5) and (4) molding, drying and roasting the molding material obtained in the step (4) to obtain the binder-free aromatic hydrocarbon adsorbent.
3. The preparation method according to claim 2, wherein the silicon source in step (1) is one of water glass and silica sol; the aluminum source is one of aluminum sulfate, aluminum nitrate, aluminum chloride and sodium metaaluminate; the metal salt is one of germanium chloride, stannic chloride, stannous sulfate, titanium chloride, titanium nitrate, titanium sulfate, zirconium chloride, zirconium nitrate and zirconium sulfate; the inorganic acid is one of sulfuric acid, nitric acid and hydrochloric acid; the inorganic base is one of sodium hydroxide and potassium hydroxide; the surfactant is one of sodium dodecyl benzene sulfonate, fatty alcohol ether sodium sulfate and isooctyl alcohol phosphate.
4. The method according to claim 2, wherein the aging temperature in the step (2) is 30 to 90 ℃ and the aging time is 1 to 24 hours.
5. The preparation method according to claim 2, wherein the inorganic-organic composite base in step (3) has a mass fraction of 5-20%, the inorganic base is one of sodium hydroxide and potassium hydroxide, the organic base is one of triethylamine and n-butylamine, and the mass ratio of the inorganic base to the inorganic base is as follows: organic base ═ 1: (0.1-5).
6. The method as set forth in claim 2, wherein the molding method in the step (5) is one of ball molding, spray molding, and compression molding.
7. Use of the binderless aromatic hydrocarbon adsorbent of claim 1 for adsorptive separation of aromatic hydrocarbons from a gasoline and diesel component.
8. The application of claim 7, wherein the binderless aromatic hydrocarbon adsorbent is loaded into a simulated moving bed by a countercurrent simulated moving bed adsorption separation process, wherein the adsorption bed layer is 8-24 layers, the adsorption separation temperature is 40-150 ℃, and the desorbent is a mixture of alkane and aromatic hydrocarbon.
9. The application of claim 7, wherein in the countercurrent simulated moving bed adsorption separation process, the adsorption bed layer is 8-16 layers, the adsorption separation temperature is 50-100 ℃, the resolving agents are methylcyclohexane and toluene, and the mass fraction of the toluene is 10-50%.
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