CN108311099A - Ag2O/SiO2-Al2O3The method that graphene oxide composite aerogel removes thiophene sulphur in fuel oil - Google Patents
Ag2O/SiO2-Al2O3The method that graphene oxide composite aerogel removes thiophene sulphur in fuel oil Download PDFInfo
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- CN108311099A CN108311099A CN201810041788.9A CN201810041788A CN108311099A CN 108311099 A CN108311099 A CN 108311099A CN 201810041788 A CN201810041788 A CN 201810041788A CN 108311099 A CN108311099 A CN 108311099A
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- graphene oxide
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 93
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 239000004964 aerogel Substances 0.000 title claims abstract description 46
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 title claims abstract description 33
- 239000000295 fuel oil Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 31
- ZQRGREQWCRSUCI-UHFFFAOYSA-N [S].C=1C=CSC=1 Chemical compound [S].C=1C=CSC=1 ZQRGREQWCRSUCI-UHFFFAOYSA-N 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000001179 sorption measurement Methods 0.000 claims abstract description 85
- 239000003502 gasoline Substances 0.000 claims abstract description 41
- 239000003463 adsorbent Substances 0.000 claims abstract description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 28
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 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 abstract description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 8
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims abstract description 4
- 229940071536 silver acetate Drugs 0.000 claims abstract description 4
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010521 absorption reaction Methods 0.000 claims abstract 3
- 239000004411 aluminium Substances 0.000 claims abstract 2
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 claims abstract 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 69
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 38
- 229930192474 thiophene Natural products 0.000 claims description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 24
- XNRNVYYTHRPBDD-UHFFFAOYSA-N [Si][Ag] Chemical compound [Si][Ag] XNRNVYYTHRPBDD-UHFFFAOYSA-N 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims 10
- 244000025254 Cannabis sativa Species 0.000 claims 1
- NPPHEVSPZGYDHP-UHFFFAOYSA-N [S].C1=CC=C2SC=CC2=C1 Chemical compound [S].C1=CC=C2SC=CC2=C1 NPPHEVSPZGYDHP-UHFFFAOYSA-N 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000004587 chromatography analysis Methods 0.000 abstract description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract 3
- 235000006408 oxalic acid Nutrition 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 43
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 42
- 238000006477 desulfuration reaction Methods 0.000 description 34
- 230000023556 desulfurization Effects 0.000 description 34
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical class S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 description 24
- 238000002474 experimental method Methods 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 14
- 239000011593 sulfur Substances 0.000 description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- 229910052709 silver Inorganic materials 0.000 description 12
- 239000004332 silver Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 10
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 7
- 229910052681 coesite Inorganic materials 0.000 description 7
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- 229910052682 stishovite Inorganic materials 0.000 description 7
- 229910052905 tridymite Inorganic materials 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 150000003568 thioethers Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- -1 transition metal salts Chemical class 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- ZCLVNIZJEKLGFA-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxalumolan-2-yl) oxalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZCLVNIZJEKLGFA-UHFFFAOYSA-H 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J20/06—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
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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
- B01J20/06—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
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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
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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
- B01J20/28—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
- B01J20/28047—Gels
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
技术领域technical field
本发明属于燃料油加工技术领域，具体涉及一种以π络合吸附的 Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶脱硫吸附剂及其制备方法和在汽油脱硫中的应用。The invention belongs to the technical field of fuel oil processing, and in particular relates to an Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite airgel desulfurization adsorbent with π complex adsorption and its preparation method and its application in gasoline desulfurization Applications.
背景技术Background technique
随着车用工业的大力发展，汽车尾气硫化物的大量排放不仅使环境污染问题日趋严重，同样也威胁着人类的身体健康。燃料电池对燃料油中的硫含量也有相当高的要求，有机硫化物的存在，会使燃料电池电极中的催化剂中毒，使燃料电池不能有效的将柴汽油中的化学能转化成电能。因此，对燃料油的深度脱硫已经成为了全球关注的焦点。With the vigorous development of the automobile industry, the large amount of sulfide emissions from automobile exhaust not only makes environmental pollution more and more serious, but also threatens human health. Fuel cells also have very high requirements on the sulfur content in fuel oil. The presence of organic sulfides will poison the catalyst in the fuel cell electrodes, making the fuel cells unable to effectively convert the chemical energy in diesel gasoline into electrical energy. Therefore, the deep desulfurization of fuel oil has become the focus of global attention.
目前，燃料油品的脱硫工艺主要有加氢脱硫技术、烷基化脱硫技术、生物脱硫技术、萃取脱硫技术、氧化脱硫技术、吸附脱硫技术等。现在的工业生产中，脱硫的主要工艺仍是传统的加氢脱硫，但其操作成本较高、耗氢量大、操作条件苛刻，降低汽油中辛烷值等缺点。且加氢脱硫只对于硫醇、硫醚、无机硫等有较好效果，对于热稳定性极高的噻吩类硫化物的脱硫效果很差。吸附脱硫由于其成本低廉，操作条件温和，脱硫效果好，不污染环境，其中π络合吸附脱硫相对于物理吸附脱硫是有选择性的，对于化学吸附脱硫更易于脱附再生，是目前最有前景的脱硫方法。At present, the desulfurization technology of fuel oil mainly includes hydrodesulfurization technology, alkylation desulfurization technology, biological desulfurization technology, extraction desulfurization technology, oxidation desulfurization technology, adsorption desulfurization technology, etc. In current industrial production, the main process of desulfurization is still traditional hydrodesulfurization, but its operating cost is high, hydrogen consumption is large, operating conditions are harsh, and the octane number in gasoline is reduced. Moreover, hydrodesulfurization only has a good effect on mercaptans, sulfides, inorganic sulfur, etc., and has a poor desulfurization effect on thiophene sulfides with high thermal stability. Adsorption desulfurization is due to its low cost, mild operating conditions, good desulfurization effect, and no environmental pollution. Compared with physical adsorption desulfurization, π complex adsorption desulfurization is selective, and it is easier to desorb and regenerate chemical adsorption desulfurization. Prospects for desulfurization methods.
π络合吸附脱硫的关键在于制备一种高效的π络合吸附剂。常用于制备π络合脱硫吸附剂的金属离子有Cu2+、Ag+、Ni2+、Co2+等。而制备π络合脱硫吸附剂，须将这些金属离子分散在高比表面积的载体上。根据载体的不同，π络合脱硫吸附剂可分为分子筛类、活性炭类、金属氧化物类。The key to π-complex adsorption desulfurization lies in the preparation of an efficient π-complex adsorbent. Metal ions commonly used to prepare π-complex desulfurization adsorbents include Cu 2+ , Ag + , Ni 2+ , Co 2+ , etc. To prepare π-complex desulfurization adsorbents, these metal ions must be dispersed on a carrier with a high specific surface area. According to different carriers, π-complex desulfurization adsorbents can be divided into molecular sieves, activated carbons, and metal oxides.
以分子筛为载体的π络合脱硫吸附剂。沈阳化工大学(公开号CN 103170305 A)以负载Ag离子的13X分子筛为脱硫吸附剂，用于深度脱除汽油中的噻吩及其衍生物和苯并噻吩。其中银的元素含量占吸附剂总重量的3％～5％，银元素为离子态。中国科学院(公开号CN 1511629A)制备了一种深度脱除硫化物的分子筛吸附剂，由Y型分子筛负载金属盐类组成。这类π络合吸附剂，载体价格低廉，制备方法简单，可循环再生。但微孔分子筛脱硫吸附剂所交换的过渡金属离子数目有限，对硫化物的吸附容量不大，且微孔分子筛自身的微孔结构，大分子的噻吩类硫化物由于分子尺寸效应无法进入孔道内与金属离子形成π络合作用，即无法达到深度脱硫。π-complex desulfurization adsorbent with molecular sieve as carrier. Shenyang University of Chemical Technology (publication number CN 103170305 A) uses 13X molecular sieve loaded with Ag ions as a desulfurization adsorbent for deep removal of thiophene and its derivatives and benzothiophene in gasoline. The silver element content accounts for 3% to 5% of the total weight of the adsorbent, and the silver element is in an ion state. The Chinese Academy of Sciences (publication number CN 1511629A) has prepared a molecular sieve adsorbent for deep removal of sulfide, which is composed of a Y-type molecular sieve loaded with metal salts. This type of π-complex adsorbent has a low-cost carrier, a simple preparation method, and can be recycled. However, the number of transition metal ions exchanged by the microporous molecular sieve desulfurization adsorbent is limited, the adsorption capacity for sulfide is not large, and the microporous structure of the microporous molecular sieve itself, the macromolecular thiophene sulfide cannot enter the channel due to the molecular size effect Form π complexation with metal ions, that is, deep desulfurization cannot be achieved.
以活性炭为载体的π络合脱硫吸附剂。沈阳化工大学(公开号CN 103143322 A)制备了一种负载了Fe离子的活性炭吸附剂，对汽油中的噻吩及其衍生物有较大的吸附容量与选择性，且制备方法简单，再生容易，吸附剂使用寿命长。中国石油化工股份有限公司(公开号CN 104549143A)通过采用含Al、Zn、 Ni等金属的盐和H3PO4作为助剂对活性炭进行修饰改性，较好地解决了气体原料吸附净化脱硫技术中存在单一吸附剂不能同时有效脱除多种硫化物、硫的脱除率低以及脱硫剂的穿透硫容低等问题。但活性炭的孔结构以微孔为主，改性的活性炭对噻吩类大分子硫化物的吸附容量仍然非常小，难以满足工业生产的要求。π-complex desulfurization adsorbent with activated carbon as the carrier. Shenyang University of Chemical Technology (public number CN 103143322 A) prepared an activated carbon adsorbent loaded with Fe ions, which has a large adsorption capacity and selectivity for thiophene and its derivatives in gasoline, and the preparation method is simple and easy to regenerate. The adsorbent has a long service life. China Petrochemical Co., Ltd. (publication number CN 104549143A) modified activated carbon by using salts containing Al, Zn, Ni and other metals and H 3 PO 4 as auxiliary agents, and solved the problem of adsorption, purification and desulfurization of gas raw materials. However, there are problems such as that a single adsorbent cannot effectively remove multiple sulfides at the same time, the removal rate of sulfur is low, and the breakthrough sulfur capacity of the desulfurizer is low. However, the pore structure of activated carbon is dominated by micropores, and the adsorption capacity of modified activated carbon for thiophene macromolecular sulfides is still very small, which is difficult to meet the requirements of industrial production.
以金属氧化物为载体的π络合脱硫吸附剂。南通大学(公开号CN 10300787 A)以铜元素掺杂的介孔γ-Al2O3与含硫的燃料油接触，利用吸附法实现脱硫，操作成本低，吸附容量大，且再生方便。中国石油化工股份有限公司(公开号CN 10161923A)制备了一种脱硫吸附剂，该吸附剂包括以氧化铝为粘结剂，氧化锌为载体，再与络合剂溶液接触，然后负载金属促进剂。用于燃料油脱硫，活性高，吸附硫容量大。但在制备过程中，金属离子容易堵塞金属氧化物孔道，导致负载的活性组分在表面堆积，无法进入孔道内提供活性位，降低吸附脱硫性能，且此法较难应用于工业化生产。π-complex desulfurization adsorbent with metal oxide as carrier. Nantong University (Publication No. CN 10300787 A) contacted copper-doped mesoporous γ-Al 2 O 3 with sulfur-containing fuel oil to achieve desulfurization by adsorption method. The operation cost is low, the adsorption capacity is large, and regeneration is convenient. China Petroleum & Chemical Corporation (public number CN 10161923A) has prepared a kind of desulfurization adsorbent, and this adsorbent comprises to use aluminum oxide as binding agent, zinc oxide is carrier, contacts with complexing agent solution again, then load metal promoter . It is used for desulfurization of fuel oil, with high activity and large adsorption capacity of sulfur. However, during the preparation process, metal ions are easy to block the pores of metal oxides, resulting in the accumulation of loaded active components on the surface, which cannot enter the pores to provide active sites, reducing the adsorption and desulfurization performance, and this method is difficult to apply to industrial production.
发明内容Contents of the invention
针对现有π络合吸附剂在脱除燃料油中噻吩类硫中存在的上述问题，本发明的目的在于提供一种吸附容量大、易再生的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶为吸附剂，吸附条件温和，通过π络合吸附作用脱除燃料油中噻吩类硫的方法。In view of the above-mentioned problems existing in the existing π complex adsorbents in the removal of thiophene sulfur in fuel oil, the purpose of the present invention is to provide a Ag 2 O/SiO 2 -Al 2 O 3 - Graphene oxide composite airgel is used as an adsorbent, and the adsorption conditions are mild, and a method for removing thiophene sulfur in fuel oil through π complex adsorption.
所述的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶脱除燃料油中噻吩类硫的方法，其特征在于以Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶为吸附剂，将该吸附剂填装入固定床吸附装置，在0～100℃温度下，以1～10h-1的空速通入含有噻吩类硫的模拟汽油，经吸附后得到10ppm以下硫浓度的模拟汽油。The Ag2O/SiO2-Al2O3-graphene oxide composite airgel method for removing thiophene sulfur in fuel oil is characterized in that the Ag2O / SiO2 - Al2O3 -graphene oxide composite airgel As an adsorbent, the adsorbent is filled into a fixed bed adsorption device, and at a temperature of 0-100°C, a simulated gasoline containing thiophene sulfur is passed through at a space velocity of 1-10h -1 , and sulfur below 10ppm is obtained after adsorption. concentration of simulated gasoline.
所述的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶脱除燃料油中噻吩类硫的方法，其特征在于噻吩类硫为噻吩或苯并噻吩。The Ag2O/SiO2-Al2O3-graphene oxide composite airgel method for removing thiophene sulfur in fuel oil is characterized in that the thiophene sulfur is thiophene or benzothiophene.
所述的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶脱除燃料油中噻吩类硫的方法，其特征在于Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶吸附剂采用溶胶凝胶—常压干燥法制备而得。The Ag2O/SiO2-Al2O3-graphene oxide composite airgel method for removing thiophene sulfur in fuel oil is characterized in that the Ag2O / SiO2 - Al2O3 -graphene oxide composite airgel adsorbs The agent is prepared by sol-gel-normal pressure drying method.
所述的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶脱除燃料油中噻吩类硫的方法，其特征在于制备Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶吸附剂的硅源为正硅酸甲酯、正硅酸乙酯、硅溶胶或水玻璃；银源为硝酸银或醋酸银，铝源为硝酸铝、乙酸铝或草酸铝；优选硅源为正硅酸乙酯，银源为硝酸银，铝源为硝酸铝。The Ag2O/SiO2-Al2O3-graphene oxide composite airgel method for removing thiophene sulfur in fuel oil is characterized in that Ag2O / SiO2 - Al2O3 -graphene oxide composite airgel is prepared The silicon source of the adsorbent is methyl orthosilicate, silica sol or water glass; the silver source is silver nitrate or silver acetate, and the aluminum source is aluminum nitrate, aluminum acetate or aluminum oxalate; the preferred silicon source is positive Ethyl silicate, the silver source is silver nitrate, and the aluminum source is aluminum nitrate.
所述的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶脱除燃料油中噻吩类硫的方法，其特征在于Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶吸附剂中的硅铝摩尔比为1：1～150:1,优选75：1～125:1。The Ag2O/SiO2-Al2O3-graphene oxide composite airgel method for removing thiophene sulfur in fuel oil is characterized in that the Ag2O / SiO2 - Al2O3 -graphene oxide composite airgel adsorbs The molar ratio of silicon to aluminum in the agent is 1:1 to 150:1, preferably 75:1 to 125:1.
所述的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶脱除燃料油中噻吩类硫的方法，其特征在于Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶吸附剂中的硅银摩尔比为10：1～100:1，优选为25：1～50:1。The Ag2O/SiO2-Al2O3-graphene oxide composite airgel method for removing thiophene sulfur in fuel oil is characterized in that the Ag2O / SiO2 - Al2O3 -graphene oxide composite airgel adsorbs The silicon-silver molar ratio in the agent is 10:1-100:1, preferably 25:1-50:1.
所述的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶脱除燃料油中噻吩类硫的方法，其特征在于Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶吸附剂中在制备过程中掺入了1-10mg的氧化石墨烯，优选4mg-6mg。The Ag2O/SiO2-Al2O3-graphene oxide composite airgel method for removing thiophene sulfur in fuel oil is characterized in that the Ag2O / SiO2 - Al2O3 -graphene oxide composite airgel adsorbs In the preparation process, 1-10 mg of graphene oxide, preferably 4 mg-6 mg, is mixed into the agent.
所述的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶脱除燃料油中噻吩类硫的方法，其特征在于通入含有噻吩类硫的模拟汽油时空速为1～5h-1。The Ag2O/SiO2-Al2O3-graphene oxide composite airgel method for removing thiophene sulfur in fuel oil is characterized in that the hourly space velocity of simulated gasoline containing thiophene sulfur is 1-5h -1 .
所述的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶脱除燃料油中噻吩类硫的方法，其特征在于Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶吸附噻吩类硫的吸附温度为0～40℃。The Ag2O/SiO2-Al2O3-graphene oxide composite airgel method for removing thiophene sulfur in fuel oil is characterized in that the Ag2O / SiO2 - Al2O3 -graphene oxide composite airgel adsorbs The adsorption temperature of thiophene sulfur is 0-40°C.
所述的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶脱除燃料油中噻吩类硫的方法，其特征在于模拟汽油中噻吩或苯并噻吩硫浓度为0.1～10mgS/g，优选为 0.1～5mgS/g。The Ag2O/SiO2-Al2O3-graphene oxide composite airgel method for removing thiophene sulfur in fuel oil is characterized in that the sulfur concentration of thiophene or benzothiophene in simulated gasoline is 0.1-10 mgS/g, preferably 0.1 ~5mgS/g.
通过采用上述技术，与现有技术相比，本发明的有益效果如下：By adopting above-mentioned technology, compared with prior art, the beneficial effect of the present invention is as follows:
1)本发明的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶具有典型介孔特征孔径(5～20nm)，高孔隙率(85～99％)，高比表面积(600～1500m2/g)等独特物理化学性质，因此噻吩类硫化物可无阻碍地进入气凝胶孔道内，且活性组分与硫化物能充分接触；1) The Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite airgel of the present invention has typical mesoporous characteristic pore diameter (5-20nm), high porosity (85-99%), and high specific surface area ( 600～1500m 2 /g) and other unique physical and chemical properties, so thiophene sulfides can enter the airgel pores without hindrance, and the active components can fully contact with the sulfides;
2)本发明的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶作为π络合脱硫吸附剂与其他π络合吸附剂相比，其结构是由纳米级骨架颗粒构成，使骨架内的活性组分可充分暴露。在气凝胶的合成过程中，可将具有π络合作用的过渡金属盐加入其中，因此其活性组分的量是可调节的；2) The Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite airgel of the present invention is used as a π-complex desulfurization adsorbent, compared with other π-complex adsorbents, its structure is composed of nanoscale skeleton particles , so that the active components in the framework can be fully exposed. During the synthesis of airgel, transition metal salts with π complexation can be added to it, so the amount of active components can be adjusted;
3)本发明的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶，与Ag2O/SiO2-氧化石墨烯气凝胶相比，它在气凝胶硅骨架结构中引入Al3+，产生L酸，噻吩类化合物中S原子上的孤对电子具有碱性，气凝胶基质SiO2-Al2O3中的L酸中心可通过酸碱作用吸附噻吩类硫化合物，π络合作用和酸碱作用的协同作用能进一步提高它对噻吩类硫的吸附性能；3) The Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite aerogel of the present invention, compared with Ag 2 O/SiO 2 -graphene oxide aerogel, it has an airgel silicon skeleton structure Al 3+ is introduced into the airgel matrix to generate L acid. The lone pair of electrons on the S atom in the thiophene compound is basic, and the L acid center in the airgel matrix SiO 2 -Al 2 O 3 can adsorb thiophene sulfur through the interaction of acid and base. Compound, the synergistic effect of π complexation and acid-base action can further improve its adsorption performance for thiophene sulfur;
4)本发明的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶，掺入石墨烯后，使其骨架结构得到进一步加强，耐高温特性进一步提升；4) The Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite airgel of the present invention, after doping with graphene, further strengthens its skeleton structure and further improves its high temperature resistance;
5)本发明的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶π络合吸附剂对噻吩类硫化物有良好的吸附性能，通过溶剂洗涤便可再生，再生后仍然有良好的吸附性能。5) The Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite airgel π-complexed adsorbent of the present invention has good adsorption properties for thiophene sulfides, and can be regenerated by solvent washing. It has good adsorption properties.
6)本发明的吸附反应在常压下进行、吸附条件温和、对吸附设备的要求低、操作方便，且对噻吩类化合物有良好的吸附效果。6) The adsorption reaction of the present invention is carried out under normal pressure, the adsorption conditions are mild, the requirements for adsorption equipment are low, the operation is convenient, and the adsorption effect on thiophene compounds is good.
具体实施方式Detailed ways
下面结合具体实施例对本发明进行进一步描述，但本发明的保护范围并不仅限于此。The present invention will be further described below in conjunction with specific examples, but the protection scope of the present invention is not limited thereto.
实施例：Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶吸附剂的制备Example: Preparation of Ag 2 O/SiO 2 -Al 2 O 3 -Graphene Oxide Composite Airgel Adsorbent
以硅银摩尔比为100的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶吸附剂为例，其制备方法如下：Taking the Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite airgel adsorbent with a silicon-silver molar ratio of 100 as an example, the preparation method is as follows:
将15mL EtOH、8mL TEOS、1mL H2O、0.135g硝酸铝和0.12g硝酸银的混合溶液在酸性条件下剧烈搅拌混合均匀，搅拌一定时间后，加入氧化石墨烯继续搅拌水解一段时间，然后加入氨水调节pH值至6.5，室温下静置约5min得 Ag2O/SiO2-Al2O3-氧化石墨烯复合醇凝胶，再在体积比为25：15的无水乙醇/正硅乙酸酯中老化16h，以增强凝胶的骨架结构，再用正己烷对凝胶进行溶剂置换，24h内更换两次溶剂，除去凝胶中的乙醇、水、酸及其他有机分子。最后 80℃～150℃下干燥2h，得硅银摩尔比50：1，硅铝摩尔比为100：1的 Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶。Stir vigorously the mixed solution of 15mL EtOH, 8mL TEOS, 1mL H 2 O, 0.135g aluminum nitrate and 0.12g silver nitrate under acidic conditions and mix evenly. After stirring for a certain period of time, add graphene oxide and continue stirring for a period of time, then add Ammonia water was used to adjust the pH value to 6.5, and it was allowed to stand at room temperature for about 5 minutes to obtain Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite alcohol gel. Aging in acid ester for 16 hours to enhance the skeleton structure of the gel, and then replace the gel with n-hexane for solvent replacement twice within 24 hours to remove ethanol, water, acid and other organic molecules in the gel. Finally, dry at 80° C. to 150° C. for 2 hours to obtain Ag2O/SiO2-Al2O3-graphene oxide composite airgel with a silicon-silver molar ratio of 50:1 and a silicon-aluminum molar ratio of 100:1.
实施例1～8：不同硅源，银源与铝源的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能Examples 1-8: Adsorption performance of Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite aerogels with different silicon sources, silver sources and aluminum sources on thiophene sulfides in simulated gasoline
在采用溶胶-凝胶法制备的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶中，所用的硅源有正硅酸甲酯、正硅酸乙酯、硅溶胶，银源有硝酸银、醋酸银，铝源为硝酸铝有机铝源。将制备完成的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶进行穿透吸附脱硫实验，具体操作如下：在固定床反应器中，最底层填装适量的脱脂棉，然后填装1g的Ag2O/SiO2-Al2O3-氧化石墨烯气凝胶与适量的石英砂。吸附实验开始前，用正庚烷充分润湿所填装的吸附剂。通入模拟汽油，在反应器的下端出口处收集吸附后的模拟汽油，进行色谱分析，当流出液中硫浓度为 0.005mgS/g时定为穿透点。所得到的噻吩与苯并噻吩的穿透吸附容量，结果见表1、表2、表3。In the Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite airgel prepared by the sol-gel method, the silicon sources used include methyl orthosilicate, ethyl orthosilicate, silica sol, The silver source includes silver nitrate and silver acetate, and the aluminum source is aluminum nitrate organic aluminum source. The prepared Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite airgel was subjected to penetration adsorption desulfurization experiment, and the specific operation was as follows: in the fixed bed reactor, the bottom layer was filled with an appropriate amount of absorbent cotton, and then Fill 1g of Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide airgel and appropriate amount of quartz sand. Before the adsorption experiment started, the packed adsorbent was fully wetted with n-heptane. Feed simulated gasoline, collect the adsorbed simulated gasoline at the outlet of the lower end of the reactor, and carry out chromatographic analysis. When the sulfur concentration in the effluent is 0.005mgS/g, it is defined as the breakthrough point. The obtained breakthrough adsorption capacities of thiophene and benzothiophene are shown in Table 1, Table 2 and Table 3.
表1 不同硅源的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能Table 1 Adsorption performance of Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite aerogels with different silicon sources on thiophene sulfides in simulated gasoline
表2 不同银源的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能Table 2 Adsorption performance of Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite aerogels with different silver sources on thiophene sulfides in simulated gasoline
表3 不同铝源的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能Table 3 Adsorption performance of Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite aerogels with different aluminum sources on thiophene sulfides in simulated gasoline
从表1、表2、表3可以看出，在合成Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶所用的硅源、银源、铝源中，当硅源选用正硅酸乙酯，银源选用硝酸银，铝源选用硝酸铝时，所合成的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶在穿透吸附实验中，对噻吩与苯并噻吩有最大的穿透吸附容量。因此优选硅源为正硅酸乙酯，银源为硝酸银，铝源为硝酸铝。It can be seen from Table 1, Table 2, and Table 3 that among the silicon, silver, and aluminum sources used in the synthesis of Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite airgel, when the silicon source is selected Ethyl orthosilicate, silver nitrate as the silver source, and aluminum nitrate as the aluminum source, the synthesized Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite aerogel has a good adsorption effect on thiophene in the penetration adsorption experiment. It has the largest breakthrough adsorption capacity with benzothiophene. Therefore, it is preferred that the silicon source is tetraethyl orthosilicate, the silver source is silver nitrate, and the aluminum source is aluminum nitrate.
实施例9～14：不同硅铝摩尔比的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能Examples 9-14: Adsorption performance of Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite aerogels with different molar ratios of silicon to aluminum on thiophene sulfides in simulated gasoline
选用硅银摩尔比50：1，硅铝摩尔比分别25、50、75、100、125、150的 Ag2O/SiO2-Al2O3-氧化石墨烯气凝胶，对模拟汽油中噻吩类硫化物进行穿透吸附实验。其穿透吸附实验操作同实施例1～8，吸附结果见表4。The Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide aerogels with a silicon-silver molar ratio of 50:1 and a silicon-aluminum molar ratio of 25, 50, 75, 100, 125, and 150 were selected to simulate thiophene in gasoline. Sulfide-like compounds were subjected to breakthrough adsorption experiments. The operation of the breakthrough adsorption experiment is the same as in Examples 1-8, and the adsorption results are shown in Table 4.
表4 不同硅铝摩尔比的Ag2O/SiO2-Al2O3氧化石墨烯复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能Table 4 Adsorption properties of Ag 2 O/SiO 2 -Al 2 O 3 graphene oxide composite aerogels with different molar ratios of silicon to aluminum on thiophene sulfides in simulated gasoline
从表4可以看出，不同硅铝摩尔比的Ag2O/SiO2-Al2O3-氧化石墨烯气凝胶随着硅铝摩尔比的减少即铝含量的增加，对噻吩与苯并噻吩的穿透吸附容量先增后降。在硅铝摩尔比为100：1时，噻吩与苯并噻吩的穿透吸附容量达到最大，因此优选硅铝摩尔比为75：1～150：1的Ag2O/SiO2-Al2O3-氧化石墨烯气凝胶。It can be seen from Table 4 that Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide aerogels with different molar ratios of silicon to aluminum are more sensitive to thiophene and benzo The breakthrough adsorption capacity of thiophene increases first and then decreases. When the silicon-aluminum molar ratio is 100:1, the breakthrough adsorption capacity of thiophene and benzothiophene reaches the maximum, so Ag 2 O/SiO 2 -Al 2 O 3 with a silicon-aluminum molar ratio of 75:1-150:1 is preferred. - Graphene oxide airgel.
实施例15～18：不同硅银摩尔比的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能Examples 15-18: Adsorption performance of Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite aerogels with different silicon-silver molar ratios on thiophene sulfides in simulated gasoline
选用硅银摩尔比分别10、20、50、100的Ag2O/SiO2-Al2O3-氧化石墨烯气凝胶，对模拟汽油中噻吩类硫化物进行穿透吸附实验。其穿透吸附实验操作同实施例1～8，吸附结果见表5。Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide aerogels with silicon-silver molar ratios of 10, 20, 50, and 100 were selected to conduct breakthrough adsorption experiments on thiophene sulfides in simulated gasoline. The operation of the breakthrough adsorption experiment is the same as in Examples 1-8, and the adsorption results are shown in Table 5.
表5 不同硅银摩尔比的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能Table 5 Adsorption properties of Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite aerogels with different molar ratios of silicon to silver for thiophene sulfides in simulated gasoline
从表5可以看出，Ag2O/SiO2-Al2O3-氧化石墨烯气凝胶随着硅银摩尔比的减小即银含量的增加，对噻吩与苯并噻吩的穿透吸附容量先增后减。在硅银摩尔比为50：1后，噻吩与苯并噻吩的穿透吸附容量达到最大，因此优选硅银摩尔比为20：1～50：1的Ag2O/SiO2-Al2O3-氧化石墨烯气凝胶。It can be seen from Table 5 that the breakthrough adsorption of Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide aerogels on thiophene and benzothiophene increases with the decrease of silicon-silver molar ratio, that is, the increase of silver content. The capacity first increases and then decreases. When the silicon-silver molar ratio is 50:1, the breakthrough adsorption capacity of thiophene and benzothiophene reaches the maximum, so Ag 2 O/SiO 2 -Al 2 O 3 with a silicon-silver molar ratio of 20:1-50:1 is preferred. - Graphene oxide airgel.
实施案例19～23：不同空速对Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能Implementation cases 19-23: Adsorption performance of Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite aerogels for thiophene sulfides in simulated gasoline with different space velocities
掺入氧化石墨烯的量分别1mg、2mg、3mg、4mg、5mg的Ag2O/SiO2-Al2O3- 氧化石墨烯气凝胶，对模拟汽油中噻吩类硫化物进行穿透吸附实验。其穿透吸附实验操作同实施例1～8，吸附结果见表6。Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide aerogels mixed with 1 mg, 2 mg, 3 mg, 4 mg, and 5 mg of graphene oxide were used to conduct penetration adsorption experiments on thiophene sulfides in simulated gasoline . The operation of the breakthrough adsorption experiment is the same as in Examples 1-8, and the adsorption results are shown in Table 6.
表6 掺入不同氧化石墨烯的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能Table 6 Adsorption performance of Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite aerogels doped with different graphene oxides on thiophene sulfides in simulated gasoline
从表6可以看出，Ag2O/SiO2-Al2O3-氧化石墨烯气凝胶随着氧化石墨烯掺入量的增加，对噻吩与苯并噻吩的穿透吸附容量先增后减。在氧化石墨烯掺入量到达4mg时，噻吩与苯并噻吩的穿透吸附容量达到最大，因此优选氧化石墨烯掺入量为3mg-4mg的Ag2O/SiO2-Al2O3-氧化石墨烯气凝胶。It can be seen from Table 6 that the penetration adsorption capacity of Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide airgel for thiophene and benzothiophene increases first and then increases with the increase of graphene oxide doping amount. reduce. When the amount of graphene oxide added reaches 4mg, the breakthrough adsorption capacity of thiophene and benzothiophene reaches the maximum, so Ag 2 O/SiO 2 -Al 2 O 3 -oxidized Graphene airgel.
实施案例24～28：不同空速Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能Implementation Cases 24-28: Adsorption Performance of Ag 2 O/SiO 2 -Al 2 O 3 -Graphene Oxide Composite Aerogels with Different Space Velocities on Thiophene Sulfides in Simulated Gasoline
选用硅银摩尔比50：1，硅铝摩尔比为100：1的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶。在空速为1h-1、3h-1、5h-1、8h-1、10h-1下，对模拟汽油中噻吩类硫化物进行穿透吸附实验。其穿透吸附实验操作同实施例1～8，吸附结果见表7。The Ag2O/SiO2-Al2O3-graphene oxide composite airgel with a silicon-silver molar ratio of 50:1 and a silicon-aluminum molar ratio of 100:1 was selected. The breakthrough adsorption experiments were carried out on thiophene sulfides in simulated gasoline at the space velocity of 1h -1 , 3h -1 , 5h -1 , 8h -1 , 10h -1 . The operation of the breakthrough adsorption experiment is the same as in Examples 1-8, and the adsorption results are shown in Table 7.
表7 不同空速下Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能Table 7 Adsorption performance of Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite aerogels on thiophene sulfides in simulated gasoline at different space velocities
从表7可以看出，空速的减小，噻吩与苯并噻吩的穿透吸附容量会逐渐增大，当空速减小到5h-1之后，对噻吩类硫化物的穿透吸附容量变化不大，因此优选空速为1～5h-1。It can be seen from Table 7 that the breakthrough adsorption capacity of thiophene and benzothiophene will gradually increase with the decrease of space velocity. Therefore, the space velocity is preferably 1 to 5 h -1 .
实施案例29～33：不同吸附温度对Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能Implementation cases 29-33: Adsorption performance of Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite aerogels for thiophene sulfides in simulated gasoline at different adsorption temperatures
选用硅银摩尔比50：1，硅铝摩尔比为100：1的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶。吸附温度分别选为0℃、25℃、40℃、80℃、100℃，对模拟汽油中噻吩类硫化物进行穿透吸附实验。穿透吸附实验操作同实施例1～8，吸附结果见表8。Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite airgel with a silicon-silver molar ratio of 50:1 and a silicon-aluminum molar ratio of 100:1 was selected. The adsorption temperature was selected as 0°C, 25°C, 40°C, 80°C, and 100°C, respectively, and the penetration adsorption experiments were carried out on thiophene sulfides in simulated gasoline. The operation of the breakthrough adsorption experiment was the same as in Examples 1-8, and the adsorption results are shown in Table 8.
表8 不同吸附温度下Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能Table 8 Adsorption performance of Ag2O/SiO2-Al2O3-graphene oxide composite airgel on thiophene sulfides in simulated gasoline at different adsorption temperatures
从表8可以看出，随着吸附温度的升高，噻吩与苯并噻吩的穿透吸附容量逐渐减小，在80℃之后，噻吩与苯并噻吩的吸附穿透容量非常小，表明在此温度下，被Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶吸附的噻吩与苯并噻吩已脱附。因此优先吸附温度为0～40℃。It can be seen from Table 8 that as the adsorption temperature increases, the breakthrough adsorption capacity of thiophene and benzothiophene decreases gradually. After 80 °C, the adsorption breakthrough capacity of thiophene and benzothiophene is very small, indicating that At low temperature, the thiophene and benzothiophene adsorbed by the Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite airgel have been desorbed. Therefore, the preferred adsorption temperature is 0-40°C.
实施案例34～39：不同硫浓度对Ag2O/SiO2-Al2O2复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能Implementation cases 34-39: Adsorption performance of Ag 2 O/SiO 2 -Al 2 O 2 composite aerogels for thiophene sulfides in simulated gasoline with different sulfur concentrations
选用硅银摩尔比50：1，硅铝摩尔比为100：1的Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶。模拟汽油中的噻吩或苯并噻吩的硫浓度分别为0.1mgS/g、0.5 mgS/g、1mgS/g、2mgS/g、5mgS/g、10mgS/g进行穿透吸附实验。穿透吸附操作同实施例1～8，吸附结果见表9。The Ag2O/SiO2-Al2O3-graphene oxide composite airgel with a silicon-silver molar ratio of 50:1 and a silicon-aluminum molar ratio of 100:1 was selected. Sulfur concentrations of thiophene or benzothiophene in simulated gasoline were 0.1mgS/g, 0.5 mgS/g, 1mgS/g, 2mgS/g, 5mgS/g, and 10mgS/g for breakthrough adsorption experiments. The breakthrough adsorption operation is the same as in Examples 1-8, and the adsorption results are shown in Table 9.
表9 不同硫浓度对Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能Table 9 Adsorption performance of Ag 2 O/SiO 2 -Al 2 O 3 -graphene oxide composite aerogels for thiophene sulfides in simulated gasoline with different sulfur concentrations
从表9可以看出，模拟汽油中噻吩或苯并噻吩硫浓度的增大， Ag2O/SiO2-Al2O3-氧化石墨烯复合气凝胶对噻吩与苯并噻吩穿透吸附容量呈下降的趋势，因此优选模拟汽油中噻吩或苯并噻吩硫浓度为0.1～5mgS/g。It can be seen from Table 9 that the penetration adsorption capacity of Ag2O/SiO2-Al2O3-graphene oxide composite aerogels for thiophene and benzothiophene decreases with the increase of the sulfur concentration of thiophene or benzothiophene in simulated gasoline, so Preferably, the sulfur concentration of thiophene or benzothiophene in simulated gasoline is 0.1-5 mgS/g.
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