CN113842948A - Nano phenolic resin-based desulfurization catalyst and preparation method thereof - Google Patents
Nano phenolic resin-based desulfurization catalyst and preparation method thereof Download PDFInfo
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- CN113842948A CN113842948A CN202111119368.6A CN202111119368A CN113842948A CN 113842948 A CN113842948 A CN 113842948A CN 202111119368 A CN202111119368 A CN 202111119368A CN 113842948 A CN113842948 A CN 113842948A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 145
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 85
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 85
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 82
- 230000023556 desulfurization Effects 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 239000002077 nanosphere Substances 0.000 claims abstract description 59
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 39
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 26
- 238000002425 crystallisation Methods 0.000 claims description 22
- 230000008025 crystallization Effects 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 16
- 125000003277 amino group Chemical group 0.000 claims description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 150000001555 benzenes Chemical class 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 9
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229920001400 block copolymer Polymers 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 7
- 235000011164 potassium chloride Nutrition 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910020881 PMo12O40 Inorganic materials 0.000 claims description 4
- 229910020628 SiW12O40 Inorganic materials 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 31
- 230000008569 process Effects 0.000 abstract description 12
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- -1 aromatic sulfides Chemical class 0.000 abstract description 5
- 230000009977 dual effect Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000004904 shortening Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 81
- 238000006243 chemical reaction Methods 0.000 description 36
- 230000003197 catalytic effect Effects 0.000 description 18
- 239000003921 oil Substances 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 238000003917 TEM image Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 238000013507 mapping Methods 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- NJSVDVPGINTNGX-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethanamine Chemical compound CCC[Si](OC)(OC)OCN NJSVDVPGINTNGX-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- NGDPCAMPVQYGCW-UHFFFAOYSA-N dibenzothiophene 5-oxide Chemical compound C1=CC=C2S(=O)C3=CC=CC=C3C2=C1 NGDPCAMPVQYGCW-UHFFFAOYSA-N 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 150000003462 sulfoxides Chemical class 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical group C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000013585 weight reducing agent 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- B01J35/394—
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a nano phenolic resin based desulfurization catalyst and a preparation method thereof. Firstly, preparing fingerprint-shaped phenolic resin nanospheres, taking the fingerprint-shaped phenolic resin nanospheres as a carrier, grafting amino on the fingerprint-shaped phenolic resin nanospheres to obtain amino-fingerprint-shaped phenolic resin nanospheres, and dispersing heteropoly acid on the surfaces of the amino-fingerprint-shaped phenolic resin nanospheres in a molecular form by taking heteropoly acid as an active component to prepare the heteropoly acid immobilized amino-grafted fingerprint-shaped phenolic resin nanospheres. The preparation method has mild preparation conditions, low cost of used raw materials, high dispersion of active components on the surface of the catalyst carrier, more active sites of the catalyst, high-efficiency removal of refractory aromatic sulfides, reaction time shortening, catalyst consumption reduction and good cycle stability; the catalyst has the dual functions of catalysis and adsorption, omits an extracting agent, reduces the desulfurization process, reduces the cost of industrial application, and has the beneficial effects of good application prospect.
Description
Technical Field
The invention relates to a desulfurization catalyst, in particular to a nano phenolic resin-based desulfurization catalyst and a preparation method thereof.
Background
With the development of global industrialization, the problem of atmospheric pollution is becoming more severe, and the living environment of human beings is also seriously threatened. Harmful gas SO in atmospheric pollution2The direct influence on the life, work and property safety of people is caused, for example, acid rain causes serious acid corrosion to trees, steel buildings, human skin, and the like, and serious pollution to water bodies is caused. SO (SO)2One of the main sources of (a) is automobile exhaust emissions. The main components of the vehicle fuels such as gasoline, diesel oil and the like are hydrocarbon, carbon dioxide is generated by full combustion, carbon monoxide and smoke are generated by insufficient combustion, the carbon monoxide and the smoke can pollute air, and the emission of harmful sulfur oxides in automobile exhaust can seriously affect the ecological balance. Therefore, the method is very significant in how to treat the polluted exhaust gas discharged after the fuel oil is combusted. Wherein, the SO generated by fuel oil combustion is effectively reduced2One of the methods of the gas is to reduce the content of sulfur element in the fuel oil through different desulfurization technologies, thereby fundamentally solving the problem of SO generated by the combustion of the fuel oil2To a problem of (a).
The traditional desulfurization technology is hydrodesulfurization, and the technology is mainly used for removing sulfides with good desulfurization performance in fuel, but the technology has high energy consumption and high operation cost, and difficultly-degraded aromatic sulfides (such as Dibenzothiophene (DBT)) are difficult to remove.Therefore, alternative desulfurization techniques have been studied, mainly: biological desulfurization, adsorptive desulfurization, extractive desulfurization and Oxidative Desulfurization (ODS). The ODS technique has mild operating conditions and low energy consumption, and can efficiently remove refractory aromatic sulfides, so the ODS technique is widely applied. In the ODS process, sulfides are oxidized to the corresponding sulfoxides or sulfones, which are then removed by extraction or adsorption. Oxidants play a key role in ODS technology, including hydrogen peroxide, organic hydroperoxides, ozone and molecular oxygen (O)2) And the like, with hydrogen peroxide being the most widely used oxidizing agent in oxidative desulfurization systems. The extraction is often closely connected with a catalytic oxidation desulfurization process, ionic liquid, deep eutectic solvent, acetonitrile and the like are adopted in the extraction process, and sulfide in oil is firstly extracted into a polar solvent and then oxidized into corresponding sulfoxide and sulfone by an oxidant. This makes the desulfurization process complicated and the equipment and raw material costs high. Research has shown that ODS systems can achieve one-step catalytic Oxidation Adsorption Desulfurization (OADS) by increasing the polarity of the catalyst and omitting the extraction step.
Disclosure of Invention
The invention aims to provide a nano phenolic resin-based desulfurization catalyst and a preparation method thereof. The preparation method has the advantages of mild preparation conditions, low cost of used raw materials, high dispersion of active components on the surface of a catalyst carrier, more active sites of the catalyst, capability of efficiently removing refractory aromatic sulfides (such as Dibenzothiophene (DBT)), shortening of reaction time, reduction of catalyst dosage and good cycle stability; the catalyst has the dual functions of catalysis and adsorption, omits an extracting agent, reduces the desulfurization process, reduces the cost of industrial application, and has the characteristic of good application prospect in the aspect of catalytic oxidation adsorption desulfurization of fuel oil.
The technical scheme of the invention is as follows: a nanometer phenolic resin based desulfurization catalyst is characterized in that firstly, fingerprint-shaped phenolic resin nanospheres are prepared, the fingerprint-shaped phenolic resin nanospheres are used as carriers, amino groups are grafted on the fingerprint-shaped phenolic resin nanospheres through a silane coupling agent with amino groups to obtain amino-fingerprint-shaped phenolic resin nanospheres, then heteropoly acid is used as an active component, and the heteropoly acid is dispersed on the surfaces of the amino-fingerprint-shaped phenolic resin nanospheres in a molecular form to prepare the heteropoly acid immobilized amino-grafted fingerprint-shaped phenolic resin nanospheres.
In the nanometer phenolic resin-based desulfurization catalyst, the heteropoly acid accounts for 1-50% of the total weight of the heteropoly acid solid-supported amino grafted fingerprint-shaped phenolic resin nanospheres, and the weight ratio of the silane coupling agent with amino to the fingerprint-shaped phenolic resin nanospheres is 0.05-2: 1.
In the nanometer phenolic resin-based desulfurization catalyst, the heteropoly acid accounts for 10-50% of the total weight of the heteropoly acid solid-supported amino grafted fingerprint-shaped phenolic resin nanospheres, and the weight ratio of the silane coupling agent with amino to the fingerprint-shaped phenolic resin nanospheres is 0.25-1.5: 1.
In the nanometer phenolic resin-based desulfurization catalyst, the heteropoly acid accounts for 20% of the total weight of the heteropoly acid solid-supported amino grafted fingerprint-shaped phenolic resin nanospheres, and the weight ratio of the silane coupling agent with amino to the fingerprint-shaped phenolic resin nanospheres is 1: 1.
In the nanometer phenolic resin-based desulfurization catalyst, the heteropoly acid is H3PW12O40、H3PMo12O40、H4SiW12O40、H4PMo11VO40、H5PMo10V2O40Or/and H6PMo9V3O40One or a mixture of several of them.
The preparation method of the nanometer phenolic resin-based desulfurization catalyst comprises the following steps:
(1) dissolving the block copolymer, the surfactant and potassium chloride in a sulfuric acid solution, adding benzene series, absolute ethyl alcohol, resorcinol and formaldehyde, mixing and stirring, performing hydrothermal crystallization, performing suction filtration, washing and drying to obtain the fingerprint-shaped phenolic resin nanospheres;
(2) adding the fingerprint phenolic resin nanospheres into toluene, then dropwise adding a silane coupling agent with amino, refluxing, centrifuging, washing and drying to obtain a product A;
(3) and adding the heteropoly acid into absolute ethyl alcohol, adding the product A, performing ultrasonic mixing, refluxing, centrifuging, drying and calcining to obtain the heteropoly acid immobilized amino grafted fingerprint phenolic resin nanosphere.
In the preparation method of the nanometer phenolic resin-based desulfurization catalyst, in the step (1), 1-3g of the block copolymer, 0.2-0.6g of the surfactant and 1-3g of the potassium chloride are dissolved in 140mL of 6-10% sulfuric acid solution according to the proportion, and then 1-3mL of the benzene series, 20-30mL of absolute ethyl alcohol, 0.4-1.2g of resorcinol and 0.8-1.2mL of formaldehyde are sequentially added; the benzene series is one of benzene, toluene, xylene or trimethylbenzene.
In the preparation method of the nanometer phenolic resin-based desulfurization catalyst, in the step (1), 2g of the block copolymer, 0.4g of the surfactant and 2g of the potassium chloride are dissolved in 120mL of 7-9% sulfuric acid solution according to the proportion, and then 2mL of the benzene series, 24mL of anhydrous ethanol, 0.8g of resorcinol and 1.12mL of formaldehyde are sequentially added.
In the preparation method of the nanometer phenolic resin-based desulfurization catalyst, in the step (1), the mixture is stirred for 12-48 hours at the temperature of 25-35 ℃, the mixture is divided into two gradients to carry out hydrothermal crystallization, the first gradient crystallization temperature is 60-140 ℃, the crystallization time is 1-72 hours, the second gradient crystallization temperature is 140-.
In the preparation method of the nanometer phenolic resin-based desulfurization catalyst, in the step (1), hydrothermal crystallization is carried out in two gradients, wherein the first gradient crystallization temperature is 90-110 ℃, the crystallization time is 8-72 hours, the second gradient crystallization temperature is 160-180 ℃, and the crystallization time is 12-72 hours.
In the preparation method of the nanometer phenolic resin-based desulfurization catalyst, in the step (2), 1g of fingerprint-shaped phenolic resin nanospheres are added into 50-200mL of toluene according to the proportion, and then 0.25-1.5mL of silane coupling agent with amino groups is dropwise added;
in the step (2), the reflux time is 1-48h, the reflux temperature is 80-130 ℃, centrifugation is carried out, absolute ethyl alcohol is adopted for washing for 2-3 times, and drying is carried out for 6-9h at the temperature of 60-120 ℃.
In the preparation method of the nanometer phenolic resin-based desulfurization catalyst, in the step (3), 0.1-1g of heteropolyacid is added into 20-150mL of absolute ethyl alcohol according to the proportion, and then 1g of product A is added;
in the step (3), ultrasonic mixing is carried out for 15-20min, the reflux time is 2-10h, the reflux temperature is 60-100 ℃, centrifugation is carried out, ethanol is used for washing for 1-2 times, drying is carried out for 12-15h at 80-110 ℃, and calcination is carried out for 2-4h at 200-400 ℃ in a nitrogen atmosphere.
Note: the heteropoly acid (HPA) is [ H ]3PW12O40(HPW)、H3PMo12O40(HPM)、H4SiW12O40(HSW)、H4PMo11VO40(HPMV)、H5PMo10V2O40(HPMV2) and H6PMo9V3O40(HPMV3) the silane coupling agent with amino is APTMS, the fingerprint phenolic resin nanospheres are CRFSNS, and the amino-fingerprint phenolic resin nanospheres are NH2the-CRFSNSs and heteropoly acid immobilized amino grafted fingerprint phenolic resin nanospheres are HPA-NH2-CRFNSs。
Compared with the prior art, the invention grows heteropoly acid small particles highly dispersed in molecular form on the fingerprint-shaped phenolic resin nanospheres CRFSNs by an impregnation method to obtain the composite HPA-NH2CRFSNSs catalyst, which has a small particle size (around 150 nm). The catalyst prepared by the invention has the advantages of low cost of raw materials, mild preparation conditions, high dispersion of active components on the surface of a catalyst carrier, more active sites, good circulation stability and DBT conversion rate reaching 98.9% within 90min at 60 ℃. The surface of the catalyst prepared by the invention has a large number of polar groups (hydroxyl and amino), and the catalyst can effectively adsorb oxidized large-polarity sulfur-containing compounds (sulfones and sulfoxides), so that the catalyst has dual functions of catalysis and adsorption, and an extracting agent is omitted.
In conclusion, the nano-scale catalyst prepared by the invention has good cycle stability and catalytic activity, and has dual functions of catalysis and adsorption.
Experiments prove that:
first, the catalysts prepared in examples 1 to 4 of the present invention were subjected to the following experiments:
0.431g of dibenzothiophene was placed in a 100mL beaker, 30mL of n-octane was added and dissolved by stirring, the solution was transferred to a dry and clean 250mL volumetric flask, and n-octane was added to the scale line to obtain a simulated oil with a concentration of 300 ppm.
The performance of the catalysts prepared in examples 1 to 4 of the present invention in catalytic oxidation adsorption desulfurization was investigated, and the reaction was carried out in a total reflux three-necked flask system under conditions of a temperature of 60 ℃ and a catalyst amount of 70mg (sulfur content of 300ppm as a mock oil, an oxidant of hydrogen peroxide, [ O ]/[ S ]: 6:1, and a reaction time of 90min), and the conversion of dibenzothiophene was determined as shown in table 1:
TABLE 1 dibenzothiophene conversion
| Catalyst and process for preparing same | Dibenzothiophene conversion (%) |
| Example 1 | 11.9 |
| Example 2 | 37.05 |
| Example 3 | 98.9 |
| Example 4 | 6.26 |
By comparison, it can be seen that: when the mass ratio of APTMS to CRFSNS is 1:1, the polarity of the catalyst is most suitable, and the separation efficiency is highest.
The prior art is as follows: phosphotungstic acid immobilized amino grafted MCM-41 molecular sieve (HPW-NH)2-MCM-41), the particle size of the catalyst is larger than 1 micron, the desulfurization time is 180 minutes, the oxygen-sulfur ratio is 8:1, the extractant is methanol, and the desulfurization efficiency reaches 100%.
The invention has the following patent technologies: HPA-NH2In CRFSNSs, with HPW-NH2CRFSNSs are examples. HPW-NH2The particle size of the CRFSNSs catalyst is 150 nanometers, the desulfurization time is 90 minutes, the oxygen-sulfur ratio is 6:1, no extractant is used, and the desulfurization efficiency is 98.9 percent.
Through comparison, the catalyst disclosed by the invention is nano-particles and has a special structure with a fingerprint-shaped outer surface, so that the catalysis speed is greatly improved and is shortened from 180 minutes to 90 minutes, the desulfurization efficiency reaches 98.9%, and the time of the whole desulfurization process is greatly shortened; meanwhile, the consumption of hydrogen peroxide is reduced from 8:1 to 6:1, so that the cost of the desulfurization process is reduced; the catalyst is rich in large polar groups, can adsorb oxidized sulfur-containing compounds, saves an extracting agent, simplifies a desulfurization process and greatly reduces industrial application cost.
Secondly, the inventor aims at the HPW-NH prepared in the example 3 and having the mass ratio of APTMS to CRFSNS of 1:12CRFSNS (1:1) catalysts the following experiments and analyses were carried out:
1. FIGS. 1(a) and (b) are HPW-NH2Scanning Electron Microscopy (SEM) images of a CRFSNSs (1:1) catalyst, (c) and (d) are HPW-NH2-Transmission Electron Microscopy (TEM) image of CRFNSs (1:1) catalyst;
FIG. 1 shows HPW-NH2SEM and TEM images of a CRFSNS (1:1) catalyst. From the SEM images (fig. 1(a) and (b)), we can see that the catalyst has a particle size of about 150nm and has a spherical structure and a special fingerprint-like outer surface. TEM images [ FIGS. 1(c) and (d) ] also demonstrate HPW-NH2The CRFSS (1:1) catalyst has potential channels, and the catalyst Carrier (CRFSS) of the present invention has virtually no channels since our catalyst is calcined at 350 ℃ (the templating agent is not completely burned off), but the TEM image shows the striations of the templating agent distributionAnd (4) a way. In HPW-NH2No large, aggregated HPW particles were observed in TEM images of CRFNSs (1:1) catalysts, indicating that HPW was uniformly dispersed on the surface of CRFNSs.
2. FIG. 2 is a HPW-NH of the present invention2-element distribution diagram of CRFNSs (1:1) catalyst: FIG. 2(a) is HPW-NH2Scanning Transmission Electron Microscopy (STEM) image of a CRFSNSs (1:1) catalyst, FIG. 2(b) C, (C) N, (d) O, (e) P and (f) W being HPW-NH2-elemental distribution (Mapping) diagram of CRFNSs (1:1) catalyst;
HPW-NH2scanning transmission electron microscopy (1:1) and elemental mapping (FIG. 2 (a)) of the CRFSS (1:1) catalyst, FIG. 2(b) C, (C) N, (d) O, (e) P and (f) W, respectively, show a uniform distribution of N, O, P, W elements on the CRFSS, indicating that it has been successful to distribute the-NH-in the CRFSS2And HPW is immobilized on the surface of CRFSNS.
3. FIG. 3 is a HPW-NH of the present invention2-XPS profile of CRFNSs (1:1) catalyst; wherein (a) the total spectrum of the sample, (b) N1 s, (c) P2P, (d) O1s, and (e) W4 f:
HPW-NH was investigated by XPS analysis2Surface composition of CRFSNS (1:1) catalyst. The sample consisted of O, N, C, P and W as shown in FIG. 3 (a); the binding energy of N1 s was 400.24eV [ fig. 3(b) N1 s ], which correlates with the N element of APTMS, indicating that the amino group was successfully grafted onto CRFNSs; the peak for Si 2p is shown in FIG. 3(a), which illustrates the grafting of Si from APTMS onto the CRFSNS vector; the weak peak of P2P at 134.37eV corresponds to P in HPW [ fig. 3(c) P2P ]; the binding energy of O1s was 531.21eV, 532.71eV, respectively, indicating the presence of oxygen in CRFNSs and HPW, respectively [ fig. 3(d) O1s ]; furthermore, the peaks at 35.57 and 37.68eV [ FIG. 3(e) W4f ] belong to W4f, respectively7/2And W4f5/2. These results confirm that HPW is successfully immobilized on NH by virtue of chemical interaction with amino group2-on CRFNSs. These conclusions are related to HPW-NH2Mapping and TEM images of CRFSNSs remained consistent.
4. FIG. 4 is a HPW-NH of the present invention2CRFSNSs (1:1) catalyst with NH2-CRFNSs (1:1), thermogravimetric mapping of CRFNSs;
HPW-NH2CRFSNSs (1:1) catalyst, NH2TGA analysis of CRFSNS (1:1), CRFSS samples is shown in FIG. 4. Total weight loss of CRFNSs is 44% over the range of 25 ℃ to 800 ℃; the first weight loss from 25 ℃ to 400 ℃ is due to the removal of physically adsorbed water, and the second weight loss from 400 ℃ to 800 ℃ is due to the decomposition of hydroxyl groups on the surface of the phenolic resin; from 25 ℃ to 400 ℃ NH2CRFSNSs (1:1) and HPW-NH2The weight loss of CRFSNSs (1:1) is due to the removal of physically adsorbed water. From 400 ℃ to 800 ℃ NH2The weight reduction of CRFSNSs (1:1) is due to the decomposition of the polar amino group; HPW-NH from 400 ℃ to 700 DEG C2The weight loss of CRFSNSs (1:1) is attributed to the decomposition of the amino groups, and the weight loss from 700 ℃ to 800 ℃ is attributed to the decomposition of HPW. Furthermore, NH2The total weight loss of CRFSNSs (1:1) is 7% less than CRFSNSs, since silicon is introduced when the amino group is grafted, and silicon is hardly lost; HPW-NH2Total weight loss ratio NH of CRFSNSs (1:1)29% less CRFSS (1:1), indicating that HPW is firmly immobilized on amino-grafted CRFSS. Results are compared with HPW-NH2XPS analysis of CRFSNSs, Mapping and TEM images remained consistent.
5. FIG. 5 is a HPW-NH of the present invention2Comparison of catalytic Oxidation sorption desulfurization Performance and maximum adsorption Capacity plot for CRFSNS (1:1) catalyst, where FIG. 5A is HPW-NH2-comparing catalytic oxidation adsorption desulfurization performance of CRFSNS (1:1) catalyst on simulated oil with different sulfur concentration; FIG. 5B is HPW-NH2CRFSNSs (1:1) CATALYST vs. Sulfur (DBTO)2) Maximum adsorption capacity curve of (a);
as shown in FIG. 5A, to study HPW-NH2Adsorption capacity of CRFSNSs (1:1) catalyst, 70mg of catalyst was added to simulated oils containing different DBT concentrations (100-500 ppm). The experimental results show that the conversion of DBT decreases with increasing concentration. Analytically obtained due to DBTO on the catalyst2Is lower than the maximum adsorption capacity, so 300ppm reflects a high conversion of DBT within 90 min: (>98%) of the concentration of the active ingredient. DBTO of the catalyst was calculated by the following formula2Adsorption capacity of (2):
in the formula qeIs the adsorption capacity (mg g) of the catalyst-1)，C0And CeThe initial and equilibrium concentrations (ppm) of S, M being the mass of the catalyst, M being the molecular weight of the substance, M being the molar mass of the catalystSIs the molecular weight of the sulfur atom (32g mol)-1) And V is the volume of simulated oil (L). By calculation, the catalyst HPW-NH2Adsorption of DBTO by CRFSNS (1:1)2Has an adsorption capacity of about 286.12mg g-1As shown in fig. 5B.
To explore the highest DBT conversion in OADS system, different reaction conditions included the weight ratio of the silane coupling agent with amino group and the fingerprint-like phenolic resin nanospheres, H2O2the/DBT molar ratio (expressed as [ O ]]/[S]) The influence of the catalyst dosage, the reaction temperature and the phosphotungstic acid solid loading on the DBT conversion rate. (OADS is catalytic oxidation adsorption desulfurization)
Examples 1 to 4 of the present invention were investigated on HPW-NH with the weight ratio of the silane coupling agent having amino group and the phenolic resin nanospheres having fingerprint shape of 0.25:1, 0.5:1, 1:1, 1.5:12The desulfurization efficiency of CRFSNSs catalysts was constant (70mg), and the results are shown in FIG. 6 (a). The desulfurization rates of the above samples were 11.90%, 37.05%, 98.90% and 6.26%, respectively, after reacting at 60 ℃ for 90 minutes. Obviously, HPW-NH2The catalytic performance of CRFSNSs (1:1) is the best. It can be seen that the amount of amino grafting plays a crucial role in the catalytic performance of the catalyst. The DBT removal rate increases and then decreases with increasing amount of amino grafting, which is related to the polarity of the catalyst. The amount of polar groups determines the polarity of the catalyst, and the polarity of the catalyst cannot be too large or too small. According to the experimental result, when the weight ratio of the silane coupling agent with amino to the fingerprint-shaped phenolic resin nanospheres is 1:1, the polarity of the catalyst is moderate.
6. In the OADS system, the amount of oxidant used is one of the major factors affecting the DBT conversion. Using different [ O ]]/[S]A series of experiments were performed to verify the effect of the amount of oxidizing agent. As shown in FIG. 6(b), H was investigated under the same conditions2O2Effect of the/DBT molar ratios 3:1, 4:1, 5:1, 6:1 and 7:1 on DBT conversion. With following[O]/[S]Increasing the molar ratio from 3:1 to 6:1, the conversion of DBT increases dramatically and beyond this ratio the conversion decreases. The reason is that H2O2The increased amount increases the polarity of the reaction solution, resulting in the polar catalyst being extracted to H2O2Phase and not in contact with the simulated oil, eventually reducing the conversion of DBT. H2O2Is greater than stoichiometric because H2O2The oxidizing agent decomposes under heating. In conclusion, we select the best [ O ]]/[S]＝6:1。
In order to obtain the maximum OADS conversion rate, a series of fresh catalysts are used under the same conditions, and the dosage of the catalysts is 50-80 mg. As shown in FIG. 6(c), when the amount of the catalyst is 50-70 mg, the conversion rate of DBT is increased from 70% to 98.9% within 90min, and the conversion rate is increased from 73% to 99.21% after 90 min. When the dosage of the catalyst is 70-80 mg, the conversion rate of DBT is slowly increased from 98.9% to 99.06% in 90min along with the extension of the reaction time. After 90min, the removal rate of both catalysts reaches 99.21 percent. As can be seen from FIG. 6(c), increasing the amount of catalyst used increases the desulfurization rate. This is due to the increased catalytically active sites, which are related to the adsorption efficiency. However, when the mass of the catalyst was further increased to 80mg, there was no significant change in the DBT removal efficiency, indicating that the adsorption capacity of the catalyst may have exceeded the amount of sulfide adsorbed. Therefore, the catalyst dosage in the OADS system is optimized to 70 mg.
The reaction temperature is also an important factor affecting the desulfurization reaction, as shown in FIG. 6 (d). The results show that the conversion of DBT is directly related to temperature. The DBT conversion was only 55.21% at 40 ℃ over 90min and reached 98.9% at 60 ℃. This is because W (O) in the HPW active increases with temperature2)nA large amount is formed, resulting in the formation of a peroxo metal complex, which may improve the oxidizing ability to sulfide. However, high temperatures increase desulfurization costs. Therefore, the optimum reaction temperature in the OADS system is 60 ℃.
The phosphotungstic acid immobilization amount also has a certain influence on the desulfurization efficiency of the catalyst, as shown in fig. 6 (e). The result shows that the specific surface area of the catalyst is increased continuously with the increase of the proportion of the HPW in the total weight of the catalyst, but if the HPW is carried in a large amount, the specific surface area of the catalyst is reduced due to the large mass of the HPW, and the large specific surface area of the catalyst provides more catalytic active sites and adsorption sites. Therefore, the optimum phosphotungstic acid loading in the OADS system was 20%.
Specifically, the method comprises the following steps: the inventors are directed to HPW-NH2CRFSNS (1:1) catalyst the following experiment was carried out:
and (3) desulfurization application: simulated oil with a DBT concentration of 300ppm was prepared by dissolving Dibenzothiophene (DBT) in n-octane. The OADS process is carried out in a three-necked flask, and unless otherwise specified, the catalytic oxidation adsorption reaction is carried out at a temperature of 40-70 deg.C, with the addition of 10mL of a simulated oil and 50-80mg of catalyst, a quantity of 30% H2O2Aqueous solutions (oxy-sulfur ratio 3:1 to 7: 1). The three-neck flask is fixed in a water bath kettle with a magnetic stirring device for stirring. And after the desulfurization reaction is finished, centrifuging the reaction solution to obtain supernatant, namely the clean oil. And after the reaction is finished, centrifugally recovering and recycling the solid catalyst. After the supernatant was analyzed by a microcoulomb sulfur meter (WK-2D), the desulfurization rate (eta represents DBT conversion, C)0And C refers to the sulfide concentration before and after desulfurization, respectively):
η＝[(C0-C)/C0]×100％
example of desulfurization experiment: HPW-NH2CRFSNS (1:1) catalyst for Dibenzothiophene (DBT) -n-octane system:
simulated oil with a DBT concentration of 300ppm was prepared by dissolving Dibenzothiophene (DBT) in n-octane. The OADS process is carried out in a three-necked flask, the catalytic oxidation adsorption reaction is carried out at 60 ℃, 10mL of simulated oil and 70mg of catalyst are added, and a certain amount of 30% H2O2Aqueous solution (oxygen to sulfur ratio 6: 1). The three-neck flask is fixed in a water bath kettle with a magnetic stirring device for stirring. And after the desulfurization reaction is finished, centrifuging the reaction solution to obtain supernatant, namely the clean oil. After the reaction is finished, the solid catalyst is centrifugally recovered and recycled, and finally the desulfurization rate reaches 98.9 percent after 90 minutes。
7. FIG. 7 is a graph showing the catalytic activity of different catalysts in the OADS system. As shown in FIG. 7, DBT removal rate of CRFSNSs is only 2.03%, NH2DBT removal efficiency of-CRFSNSs (1:1) was 2.34% due to the absence of catalytically active sites on the sample. The DBT removal efficiency of pure HPW is 1.25% due to weak adsorption capacity of HPW to DBT, and although HPW has a plurality of catalytically active sites, its actual removal efficiency is low because HPW desulfurization process cannot remove oxidized sulfide by adsorption. HPW-NH2DBT removal rate of CRFSNSs (1:1) is 98.9%, indicating that the catalysts have high catalytic activity.
8. FIG. 8 is a HPW-NH of the present invention2Desulfurization performance cycle stability test chart for CRFSNS (1:1) catalyst. Catalyst recovery is one of the most critical factors in large-scale industrial applications. The desulfurized catalyst HPW-NH2CRFSNSs (1:1) was washed with acetonitrile and recovered for reuse. The results show that after 5 cycles, HPW-NH2The desulfurization efficiency of CRFSNSs (1:1) decreased from 98.9% to 94.46%. HPW-NH2The reusability of the CRFSNSs (1:1) catalyst is attributed to-NH2And the negative charge of the HPW, thereby reducing the solubility of the HPW in polar solvents.
HPA-NH prepared by the Applicant's working-up of other examples2CRFSNSs were tested and analyzed in the experiments described in 1-8 above, and the results were comparable to the above tests and analyses.
In conclusion, the preparation conditions are mild, the cost of the used raw materials is low, the active components are highly dispersed on the surface of the catalyst carrier, the number of active sites of the catalyst is large, the refractory aromatic sulfides (such as Dibenzothiophene (DBT)) can be efficiently removed, the reaction time is shortened, the catalyst dosage is reduced, and the circulation stability is good; the catalyst has dual functions of catalysis and adsorption, an extracting agent is omitted, a desulfurization process is reduced, and the cost of industrial application is reduced.
Drawings
FIG. 1 is a HPW-NH of the present invention2-Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) images of CRFNSs (1:1) catalyst; wherein (a) and (b) are HPW-NH of the invention2-Scanning Electron Microscopy (SEM) picture of CRFNSs (1:1) catalyst; FIGS. 1(c) and (d) are HPW-NH2-Transmission Electron Microscopy (TEM) image of CRFNSs (1:1) catalyst;
FIG. 2 is a HPW-NH of the present invention2-element distribution diagram of CRFNSs (1:1) catalyst: wherein (a) is HPW-NH2Scanning Transmission Electron Microscopy (STEM) of a CRFSNSs (1:1) catalyst, (b) C, (C) N, (d) O, (e) P and (f) W are HPW-NH2-elemental distribution (Mapping) diagram of CRFNSs (1:1) catalyst;
FIG. 3 is a HPW-NH of the present invention2-XPS plot of CRFNSs (1:1) catalyst; wherein (a) the total spectrum of the sample, (b) N1 s, (c) P2P, (d) O1s, and (e) W4 f;
FIG. 4 is a HPW-NH of the present invention2CRFSNSs (1:1) catalyst with NH2-CRFNSs (1:1), thermogravimetric mapping of CRFNSs;
FIG. 5 is a HPW-NH of the present invention2-comparison of catalytic oxidation adsorption desulfurization performance and maximum adsorption capacity profile for CRFNSs (1:1) catalysts; wherein A is HPW-NH2-comparative graph of catalytic oxidation adsorption desulfurization performance of CRFNSs (1:1) catalyst for simulated oil of different sulfur concentration; b is HPW-NH2CRFSNSs (1:1) CATALYST vs. Sulfur (DBTO)2) Graph of maximum adsorption capacity of;
FIG. 6 is a HPW-NH of the present invention2-catalytic performance diagram of CRFNSs (1:1) catalyst; wherein (a) is a graph of the effect of the amount of amino grafts on desulfurization performance; (b) is H2O2the/DBT molar ratio (expressed as [ O ]]/[S]) Influence graph on desulfurization performance; (c) is a graph of the effect of catalyst dosage on desulfurization performance; (d) is a graph of the effect of reaction temperature on desulfurization performance; (e) is a graph of the influence of the solid loading of phosphotungstic acid on desulfurization performance;
FIG. 7 is a graph of the catalytic activity test of different catalysts in the OADS system;
FIG. 8 is a HPW-NH of the present invention2Desulfurization performance cycle stability test chart for CRFSNS (1:1) catalyst.
Detailed Description
The invention is further illustrated by the following figures and examples, which are not to be construed as limiting the invention.
A preparation method of a nanometer phenolic resin based desulfurization catalyst specifically comprises the following steps:
(1) dissolving 1-3g of block copolymer, 0.2-0.6g of surfactant and 1-3g of potassium chloride in 140mL of 6-10% sulfuric acid solution according to the proportion, sequentially adding 1-3mL of benzene series, 20-30mL of absolute ethyl alcohol, 0.4-1.2g of resorcinol and 0.8-1.2mL of formaldehyde, mixing and stirring at 25-35 ℃ for 12-48h, dividing into two gradients for hydrothermal crystallization, wherein the first gradient crystallization temperature is 60-140 ℃, the crystallization time is 1-72h, the second gradient crystallization temperature is 140 ℃ and 220 ℃, the crystallization time is 1-72h, carrying out suction filtration, washing with deionized water until the pH value is 6.5-7.5, and drying at 50-100 ℃ for 4-8h to obtain the fingerprint-shaped phenolic resin nanospheres (CRFSNSs). (wherein the benzene series is any one of benzene, toluene, xylene and trimethylbenzene)
(2) Proportionally adding 1g of fingerprint phenolic resin nanosphere into 50-200mL of toluene, dropwise adding 0.25-1.5mL of silane coupling agent with amino group, refluxing at 80-130 deg.C for 1-48h, centrifuging, washing with anhydrous ethanol for 2-3 times, and drying at 60-120 deg.C for 6-9h to obtain product A (NH)2-CRFNSs)。
(3) Proportionally adding 0.1-1g of heteropoly acid into 20-150mL of absolute ethyl alcohol, adding 1g of product A, ultrasonically mixing for 15-20min, refluxing for 2-10h at 60-100 ℃, centrifuging, drying for 12-15h at 80-110 ℃, drying, and calcining for 2-4h at 200-400 ℃ in a nitrogen atmosphere to obtain the HPA immobilized amino grafted fingerprint phenolic resin nanospheres (HPA-NH)2CRFSNSs catalyst).
The step (1) is preferably: dissolving 2g of block copolymer, 0.4g of surfactant and 2g of potassium chloride in 120mL of 7-9% sulfuric acid solution according to the proportion, then sequentially adding 2mL of benzene series, 24mL of absolute ethyl alcohol, 0.8g of resorcinol and 1.12mL of formaldehyde, mixing and stirring for 24-48h at 31 ℃, the first gradient crystallization temperature is 90-110 ℃, the crystallization time is 8-72h, the second gradient crystallization temperature is 160-180 ℃, the crystallization time is 12-72h, performing suction filtration, washing with deionized water until the pH value is 6.5-7.5, and drying at 50-100 ℃ for 4-8h to obtain the fingerprint phenolic resin nanospheres (CRFSNSs). (wherein the benzene series is any one of benzene, toluene, xylene and trimethylbenzene)
According to the experimental result, the first gradient hydrothermal crystallization is carried out at 100 ℃ for 8 hours to form uniform colloid, and the dispersed phase in the colloid is aggregated into the phenolic resin nanospheres with uniform particle size after the second gradient hydrothermal crystallization is carried out at 170 ℃ for 12 hours.
The step (2) is preferably: proportionally adding 1g of fingerprint phenolic resin nanosphere into 50-100mL of toluene, dropwise adding 0.25-1.5mL of silane coupling agent with amino group, refluxing at 80-130 deg.C for 6-48h, centrifuging, washing with anhydrous ethanol for 2-3 times, and drying at 60-120 deg.C for 6-9h to obtain product A (NH)2-CRFNSs)。
The step (3) is preferably: proportionally adding 0.1-1g of heteropoly acid into 20-80mL of absolute ethyl alcohol, and adding 1g of product A (NH)2-CRFSNSs), ultrasonic mixing for 15-20min, refluxing at 60-80 ℃ for 2-8h, centrifuging, drying at 80-110 ℃ for 12-15h, calcining at 200-400 ℃ for 3h in nitrogen atmosphere to obtain HPA immobilized amino grafted fingerprint phenolic resin nanospheres (HPA-NH)2CRFSNSs catalyst).
Examples 1 to 4 were prepared according to the above procedures, respectively, to obtain HPW-NH with the weight ratio of the silane coupling agent with amino group and the fingerprint-like phenolic resin nanospheres of 0.25:1, 0.5:1, 1:1, 1.5:12-CRFNSs；
Wherein: example 1 HPW-NH with amino silane coupling agent and nanosphere weight ratio of 1:12-a CRFNSs catalyst; example 2 HPW-NH with amino silane coupling agent and nanosphere weight ratio of 0.25:12-a CRFNSs catalyst; HPW-NH with amino silane coupling agent and nanosphere weight ratio of 0.5:1 from example 32-a CRFNSs catalyst; example 4 HPW-NH with amino silane coupling agent and nanosphere weight ratio of 1.5:12CRFSNS catalysts, as follows:
example 1: HPW-NH2Preparation of CRFSNSs (1: 1):
step (1) is carried out as described above; step (2) adding 1g of fingerprint-shaped phenolic resin nanospheres into 50mL of toluene according to the proportion, then dropwise adding 1mL of silane coupling agent with amino,refluxing at 110 deg.C for 12 hr, centrifuging, washing with anhydrous ethanol for 2 times, and drying at 80 deg.C for 6 hr to obtain product A [ NH ]2-CRFNSs (1: 1); step (3) is carried out as described above to obtain HPW-NH2CRFSNS (1:1) catalyst.
Example 2: HPW-NH2Preparation of CRFSNSs (0.25:1)
Step (1) is carried out as described above; proportionally adding 1g of fingerprint-shaped phenolic resin nanospheres into 70mL of toluene, dropwise adding 0.25mL of silane coupling agent with amino groups, refluxing for 24h at 80 ℃, centrifuging, washing for 3 times by using absolute ethyl alcohol, and drying for 9h at 60 ℃ to obtain a product A [ NH ]2-CRFNSs (0.25: 1); step (3) is carried out as described above to obtain HPW-NH2CRFSNS (0.25:1) catalyst.
Example 3: HPW-NH2Preparation of CRFSNSs (0.5:1)
Step (1) is carried out as described above; adding 1g of fingerprint-shaped phenolic resin nanospheres into 80mL of toluene according to the proportion, then dropwise adding 0.5mL of silane coupling agent with amino, refluxing for 48h at 90 ℃, centrifuging, washing for 2 times by using absolute ethyl alcohol, and drying for 7h at 110 ℃ to obtain product A [ NH ]2-CRFNSs (0.5: 1); step (3) is carried out as described above to obtain HPW-NH2CRFSNS (0.5:1) catalyst.
Example 4: HPW-NH2Preparation of CRFSNSs (1.5:1)
Step (1) is carried out as described above; proportionally adding 1g of fingerprint-shaped phenolic resin nanosphere into 100mL of toluene, dropwise adding 1.5mL of silane coupling agent with amino group, refluxing at 130 ℃ for 6h, centrifuging, washing with absolute ethanol for 2 times, and drying at 120 ℃ for 8h to obtain product A [ NH ]2-CRFNSs (1.5: 1); step (3) is carried out as described above to obtain HPW-NH2CRFSNS (1.5:1) catalyst.
Example 5: synthesis of other nano-scale heteropolyacid catalysts
According to the preparation method of the nano phenolic resin-based desulfurization catalyst, the heteropoly acid (H) is changed3PW12O40(HPA)、H3PMo12O40(HPM)、H4SiW12O40(HSW)、H4PMo11VO40(HPMV)、H5PMo10V2O40(HPMV2) and H6PMo9V3O40(HPMV3)), synthesized NH2The CRFSNS supported heteropolyacid catalyst has the following 6 types: HPA-NH2-CRFNSs、HPM-NH2-CRFNSs、HSW-NH2-CRFNSs、HPMV-NH2-CRFNSs、HPMV2-NH2CRFSNSs and HPMV3-NH2-CRFNSs。
Claims (10)
1. A nanometer phenolic resin-based desulfurization catalyst is characterized in that: firstly, preparing fingerprint-shaped phenolic resin nanospheres, taking the fingerprint-shaped phenolic resin nanospheres as a carrier, grafting amino on the fingerprint-shaped phenolic resin nanospheres through a silane coupling agent with amino to obtain amino-fingerprint-shaped phenolic resin nanospheres, and dispersing heteropoly acid on the surfaces of the amino-fingerprint-shaped phenolic resin nanospheres in a molecular form by taking heteropoly acid as an active component to prepare heteropoly acid immobilized amino-grafted fingerprint-shaped phenolic resin nanospheres.
2. The nano phenolic resin based desulfurization catalyst according to claim 1, characterized in that: the heteropolyacid accounts for 1-50% of the total weight of the heteropolyacid solid-supported amino grafted fingerprint-shaped phenolic resin nanospheres, and the weight ratio of the silane coupling agent with amino to the fingerprint-shaped phenolic resin nanospheres is 0.05-2: 1.
3. The nano phenolic resin based desulfurization catalyst according to claim 2, characterized in that: the heteropolyacid accounts for 10-50% of the total weight of the heteropolyacid solid-supported amino grafted fingerprint-shaped phenolic resin nanospheres, and the weight ratio of the silane coupling agent with amino to the fingerprint-shaped phenolic resin nanospheres is 0.25-1.5: 1.
4. The nano phenolic resin based desulfurization catalyst according to claim 1, characterized in that: the heteropoly acid is H3PW12O40、H3PMo12O40、H4SiW12O40、H4PMo11VO40、H5PMo10V2O40Or/and H6PMo9V3O40One or a mixture of several of them.
5. The method for preparing a nano phenolic resin based desulfurization catalyst as claimed in any one of claims 1 to 4, characterized in that: the method comprises the following steps:
(1) dissolving the block copolymer, the surfactant and potassium chloride in a sulfuric acid solution, adding benzene series, absolute ethyl alcohol, resorcinol and formaldehyde, mixing and stirring, performing hydrothermal crystallization, performing suction filtration, washing and drying to obtain the fingerprint-shaped phenolic resin nanospheres;
(2) adding the fingerprint phenolic resin nanospheres into toluene, then dropwise adding a silane coupling agent with amino, refluxing, centrifuging, washing and drying to obtain a product A;
(3) and adding the heteropoly acid into absolute ethyl alcohol, adding the product A, performing ultrasonic mixing, refluxing, centrifuging, drying and calcining to obtain the heteropoly acid immobilized amino grafted fingerprint phenolic resin nanosphere.
6. The method for preparing the nano phenolic resin based desulfurization catalyst according to claim 5, characterized in that: in the step (1), 1-3g of block copolymer, 0.2-0.6g of surfactant and 1-3g of potassium chloride are dissolved in 140mL of 6-10% sulfuric acid solution according to the proportion, and then 1-3mL of benzene series, 20-30mL of absolute ethyl alcohol, 0.4-1.2g of resorcinol and 0.8-1.2mL of formaldehyde are sequentially added; the benzene series is one of benzene, toluene, xylene or trimethylbenzene.
7. The method for preparing the nano phenolic resin based desulfurization catalyst according to claim 5, characterized in that: in the step (1), mixing and stirring are carried out for 12-48h at 25-35 ℃, hydrothermal crystallization is carried out in two gradients, the first gradient crystallization temperature is 60-140 ℃, the crystallization time is 1-72h, the second gradient crystallization temperature is 140-.
8. The method for preparing the nano phenolic resin based desulfurization catalyst according to claim 8, characterized in that: in the step (1), the hydrothermal crystallization is carried out by two gradients, wherein the first gradient crystallization temperature is 90-110 ℃, the crystallization time is 8-72h, the second gradient crystallization temperature is 160-180 ℃, and the crystallization time is 12-72 h.
9. The method for preparing the nano phenolic resin based desulfurization catalyst according to claim 5, characterized in that: in the step (2), 1g of fingerprint-shaped phenolic resin nanospheres are added into 50-200mL of toluene according to the proportion, and then 0.25-1.5mL of silane coupling agent with amino groups is dropwise added;
in the step (2), the reflux time is 1-48h, the reflux temperature is 80-130 ℃, centrifugation is carried out, absolute ethyl alcohol is adopted for washing for 2-3 times, and drying is carried out for 6-9h at the temperature of 60-120 ℃.
10. The method for preparing the nano phenolic resin based desulfurization catalyst according to claim 5, characterized in that: in the step (3), 0.1-1g of heteropoly acid is added into 20-150mL of absolute ethyl alcohol according to the proportion, and 1g of product A is added;
in the step (3), ultrasonic mixing is carried out for 15-20min, the reflux time is 2-10h, the reflux temperature is 60-100 ℃, centrifugation is carried out, ethanol is used for washing for 1-2 times, drying is carried out for 12-15h at 80-110 ℃, and calcination is carried out for 2-4h at 200-400 ℃ in a nitrogen atmosphere.
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