CN111085261A - Modified molecular sieve for hydrodesulphurization and preparation and application thereof - Google Patents
Modified molecular sieve for hydrodesulphurization and preparation and application thereof Download PDFInfo
- Publication number
- CN111085261A CN111085261A CN201811245967.0A CN201811245967A CN111085261A CN 111085261 A CN111085261 A CN 111085261A CN 201811245967 A CN201811245967 A CN 201811245967A CN 111085261 A CN111085261 A CN 111085261A
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- CN
- China
- Prior art keywords
- molecular sieve
- modified
- metal
- zeolite
- suspension
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 131
- 239000002184 metal Substances 0.000 claims abstract description 131
- 239000002808 molecular sieve Substances 0.000 claims abstract description 88
- 239000000725 suspension Substances 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 56
- 239000002904 solvent Substances 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 48
- 239000003502 gasoline Substances 0.000 claims abstract description 39
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 36
- 239000011593 sulfur Substances 0.000 claims abstract description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 34
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 30
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 29
- 230000023556 desulfurization Effects 0.000 claims abstract description 29
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 28
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 28
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 25
- 239000004094 surface-active agent Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000004108 freeze drying Methods 0.000 claims abstract description 16
- 239000012528 membrane Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- 229910052745 lead Inorganic materials 0.000 claims abstract description 4
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 60
- 229910021536 Zeolite Inorganic materials 0.000 claims description 57
- 239000010457 zeolite Substances 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 35
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 238000007710 freezing Methods 0.000 claims description 19
- 230000008014 freezing Effects 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000852 hydrogen donor Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- -1 fatty acid amine Chemical class 0.000 claims description 9
- 229910008759 Sn—Sb—Bi Inorganic materials 0.000 claims description 8
- 229910001152 Bi alloy Inorganic materials 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002283 diesel fuel Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- OABYVIYXWMZFFJ-ZUHYDKSRSA-M sodium glycocholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 OABYVIYXWMZFFJ-ZUHYDKSRSA-M 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 229910020830 Sn-Bi Inorganic materials 0.000 claims description 4
- 229910018728 Sn—Bi Inorganic materials 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- 150000003464 sulfur compounds Chemical class 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 2
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 235000021313 oleic acid Nutrition 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002002 slurry Substances 0.000 description 23
- 239000003054 catalyst Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 150000001336 alkenes Chemical class 0.000 description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000012467 final product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000004506 ultrasonic cleaning Methods 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- 229910052815 sulfur oxide Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000003921 particle size analysis Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
-
- 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
- C10G45/12—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 containing crystalline alumino-silicates, e.g. molecular sieves
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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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
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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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
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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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- 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
- C10G2300/70—Catalyst aspects
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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Abstract
A modified molecular sieve for hydrodesulphurization and preparation and application thereof, the modified molecular sieve comprises a molecular sieve and a modified metal membrane, wherein the modified metal membrane is positioned on the outer surface of molecular sieve particles; the modified metal film contains modified metal, the modified metal comprises first metal and optional second metal, wherein the first metal is one or more of Ge, Sn and Pb, and the second metal is Bi and/or Sb and/or Ga. The preparation method comprises the following steps: forming a mixture of metal powder, a hydroxyl-containing solvent and a surfactant, and then treating under ultrasonic waves to obtain an ultrasonic mixed solution; separating the mixed solution after ultrasonic treatment to obtain suspension, mixing the suspension with the molecular sieve, and freeze-drying to obtain the modified molecular sieve. The modified molecular sieve can be used for hydrodesulfurization of sulfur-containing hydrocarbon, has the characteristics of high desulfurization activity, high stability and good selectivity, is used for gasoline desulfurization, and can improve the octane number of gasoline.
Description
Technical Field
The invention relates to a modified molecular sieve for hydrodesulphurization and a preparation method and an application method thereof.
Background
Sulfur oxides are generated after sulfur in hydrocarbon fuel is combusted, sulfur oxides generated by vehicle fuel can inhibit the activity of a noble metal catalyst in an automobile exhaust converter and can cause irreversible poisoning, and the effect of catalytic conversion of toxic gases in automobile exhaust cannot be realized, so that the discharged automobile exhaust contains unburned oxides of non-methane hydrocarbon and nitrogen and carbon monoxide, the toxic gases are catalyzed by sunlight to easily form photochemical smog to cause acid rain, and the sulfur oxides are one of main reasons for forming the acid rain.
Reducing the sulfur content in gasoline and diesel is considered to be one of the most important measures to improve air quality. With the increasing attention of people on environmental protection, environmental regulations are becoming stricter, and the sulfur content of the European V gasoline standard implemented in 2010 of the European Union is less than 10 mug/g by taking gasoline as an example. The current gasoline product standard GB 17930-2013 'automotive gasoline' in China requires that the sulfur content in gasoline must be reduced to 10 mu g/g. But also the future gasoline quality standards will be more stringent.
At present, the main methods for desulfurizing fuel oil are hydrodesulfurization and adsorption desulfurization. Hydrodesulfurization reacts sulfur-containing hydrocarbon oils, such as gasoline, by contacting them with hydrogen in the presence of a hydrogenation catalyst, which, with increasingly stringent fuel oil standards, requires more severe hydrogenation conditions, such as higher reaction pressure or temperature, to achieve lower sulfur content, but due to the large amount of olefins in gasoline, increased hydrogenation severity results in higher octane number loss. The adsorption desulfurization is usually carried out by contacting an adsorbent with sulfur-containing hydrocarbon under the hydrogen condition, wherein the sulfur-containing hydrocarbon in the oil product is captured on the adsorbent, and hydrogen sulfide is generated by hydrogenation and then is combined with zinc oxide to generate a zinc sulfide compound, which can also cause the octane number of the gasoline product to be reduced; in addition, when the sulfur combined on the zinc oxide is saturated, the desulfurization activity is reduced, the sulfur must be removed through oxidation regeneration, and in the frequent oxidation regeneration-reduction process, the deactivation rate of the adsorbent is high, which affects the implementation effect of sulfur-containing hydrocarbon desulfurization.
The existing adsorption desulfurization and hydrodesulfurization are all desulfurized in the presence of hydrogen, and in order to achieve the purpose of deep desulfurization, the operation needs to be carried out under more severe conditions.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a modified molecular sieve for hydrodesulphurization, which has higher desulphurization activity. The invention also aims to provide a preparation method and a using method of the modified molecular sieve.
In order to solve the technical problems, the invention provides the following technical scheme:
the technical scheme 1 is a modified molecular sieve for hydrodesulphurization, which comprises a molecular sieve and a modified metal membrane, wherein the modified metal membrane is positioned on the outer surface of molecular sieve particles; the modified metal film contains modified metal, the modified metal comprises first metal (also called first modified metal) and optional second metal (also called second modified metal), wherein the first metal is one or more of Ge, Sn and Pb, the second metal is Bi and/or Sb and/or Ga, and the preferred second modified metal is Bi.
Technical scheme 2. the modified molecular sieve according to technical scheme 1, wherein the thickness of the modified metal film is 5-30 nm, preferably 5-20 nm.
Technical solution 3. the modified molecular sieve according to technical solution 1 or 2, wherein the particle diameter D of the modified molecular sieve901 to 8 microns, preferably 2 to 6 microns,such as 3 to 5 microns.
Technical scheme 4. the modified molecular sieve according to technical scheme 1, 2 or 3, wherein the modified molecular sieve comprises 85-98 wt% of the molecular sieve and 2-15 wt% of the modified metal on a dry basis. Wherein the weight ratio of the first metal to the second metal is preferably 0.4-10: 1, for example, the weight ratio of the first metal to Bi is 0.4-7: 1, or 0.5-5: 1, or 1.2-7.5: 1. Wherein the dry basis is a solid product obtained after roasting for 1 hour at 800 ℃.
Technical scheme 5. a preparation method of a modified molecular sieve comprises the following steps: forming a mixture of metal powder, a hydroxyl-containing solvent and a surfactant, and then treating under ultrasonic waves to obtain an ultrasonic mixed solution; separating the mixed solution after ultrasonic treatment to obtain suspension, mixing the suspension with the molecular sieve, and freeze-drying to obtain the modified molecular sieve.
Technical scheme 6. according to any one of the technical schemes 1 to 5, the molecular sieve is one or more of a large-pore zeolite, a medium-pore zeolite and a non-zeolite molecular sieve; the large-pore zeolite refers to zeolite with a pore structure ring opening of at least 0.7 nanometer, and can be one or more selected from L zeolite, Beta zeolite, mordenite and ZSM-18 zeolite, and is preferably Beta zeolite; the medium pore zeolite is zeolite with pore structure opening of 0.56-0.70 nm, and can be selected from one or more of ZSM-5 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite and MCM-56 zeolite, preferably ZSM-5 zeolite; the non-zeolitic molecular sieve is selected from one or more of silicates having different silicon to metal ratios (e.g. metallosilicates, titanosilicates), metalloaluminates (e.g. germano-aluminates), metallophosphates, aluminophosphate-aluminophosphates, metalloaluminophosphate-aluminophosphates, metal-bonded silicoaluminophosphate-silicophosphates (mesoso and ELAPSO), silicoaluminophosphate-alumino-phosphates (SAPO), gallium germanates (gallogermanates), for example one or more of SAPO-11, SAPO-34, SAPO-31, preferably SAPO-11 molecular sieve.D of the molecular sieve90The diameter is preferably 1 to 8 micrometers, for example, 2 to 6 micrometers or 3 to 5 micrometers; the modified metal forms a metal film to cover the outer surface of the molecular sieve with high silica-alumina ratio; when the molecular sieve is a silicon-aluminum molecular sieve, the molecular sieve is preferably a molecular sieve with a high silicon-aluminum ratio, and the silicon-aluminum ratio of the molecular sieve with the high silicon-aluminum ratio is (SiO)2/Al2O3A molar ratio) of more than 50, for example 50 to 500 or 100 to 500; preferably 50 to 150 or 150 to 300. When the molecular sieve is a phosphorus-aluminum molecular sieve, the silicon-aluminum ratio is (SiO)2/Al2O3Molar ratio) of 0.1 to 1.5, for example 0.1-1.5: 1; preferably 0.2 to 0.8.
Technical scheme 7. according to the preparation method of the modified molecular sieve of technical scheme 5 or 6, wherein the concentration of the modified metal in the suspension is 5-45 g/Kg, for example, 8-40 g/Kg or 10-35 mass per thousand, preferably 10-25 g/Kg.
Technical scheme 8. the preparation method of the modified molecular sieve according to technical scheme 5, 6 or 7, wherein the particle size D of the particles in the suspension90Is 20nm or less, for example, 3 to 20nm or 4 to 10nm or 4 to 8nm, preferably 10nm or less, more preferably 5nm or less.
Technical scheme 9. the preparation method of the modified molecular sieve according to any one of technical schemes 5 to 8, wherein the suspension and the molecular sieve are mixed, and the weight ratio of the suspension to the molecular sieve is 0.5-20: 1, such as 5-18: 1, 0.5-15: 1, 1-13: 1, 1.5-12.5: 1, 2-10: 1, 2.5-6: 1, or 3-9: 1. Usually, the weight ratio of the modified metal to the molecular sieve in the suspension is 2-15: 85-98.
Technical scheme 10. the preparation method of the modified molecular sieve according to any one of technical schemes 5 to 9, wherein the weight ratio of the hydroxyl-containing solvent to the metal powder is 2-15: 1, and the weight ratio of the hydroxyl-containing solvent to the metal powder is preferably 5-10: 1.
Technical scheme 11. the preparation method of the modified molecular sieve according to any one of technical schemes 5 to 10, wherein the ratio of the surfactant to the hydroxyl-containing solvent is 0.001 to 100mg/mL, preferably 0.01 to 10mg/mL, or 0.05 to 5mg/mL, or 0.002 to 2mg/mL, or 0.02 to 2.5mg of the surfactant per mL of the hydroxyl-containing solvent, or 0.2 to 1.5 mg/mL.
Technical scheme 12. the preparation method of the modified molecular sieve according to any one of technical schemes 5 to 11, wherein, in the ultrasonic treatment, the power of ultrasonic waves is 10 to 500W, such as 30 to 450W, 60 to 300W or 160 to 400W (i.e. the specific ultrasonic power is 1.6 to 4W/mL) relative to 100mL of solvent, and the frequency of the ultrasonic waves is 20 to 100KHz, such as 20 to 50 KHz; the ultrasonic treatment time is 3 to 15 hours, for example, 4 to 12 hours or 5 to 8 hours.
Technical scheme 13. the preparation method of the modified molecular sieve according to any one of technical schemes 5 to 12, wherein the average diameter of the metal powder is less than 20 μm, for example, 1 to 18 micrometers, or 2 to 17 micrometers, or 4 to 16 micrometers.
Technical solution 14. the method for preparing a modified molecular sieve according to any one of technical solutions 5 to 13, wherein the metal powder is one or more of Ge-Bi alloy powder, Sn-Bi alloy powder, Sb-Bi alloy powder, and Sn-Sb-Bi alloy powder; preferably, in the alloy powder, the ratio of the first metal to Bi is: 0.4-10: 1, for example, 1.2-7.5: 1.
Technical scheme 15. the preparation method of the modified molecular sieve according to any one of technical schemes 5 to 14, wherein the surfactant is an anionic surfactant, a cationic surfactant or an amphoteric surfactant; for example, one of sodium glycocholate, sodium dioctyl sulfosuccinate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium lauryl sulfate, stearic acid, oleic acid, lauric acid, fatty acid amine, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, cetyl trimethyl ammonium bromide, fatty acid methyl ester, and polyoxyethylene ether; the fatty acid amine carbon chain length is preferably between C8-C10 (carbon chain is C8, C9 or C10); the fatty acid methyl ester carbon chain length is preferably between C8-C10.
Technical solution 16. the method for preparing a modified molecular sieve according to any one of technical solutions 5 to 15, wherein the hydroxyl group-containing solvent is water and/or a hydroxyl group-containing organic solvent such as an organic solvent containing one or more hydroxyl groups in a molecule, the hydroxyl group-containing organic solvent is a monohydric alcohol, a dihydric alcohol, a trihydric alcohol or a derivative thereof, and usually the number of carbon atoms in the molecule of the hydroxyl group-containing organic solvent is not more than 6, for example, 1, 2, 3 or 4; the monohydric alcohol is one or more of methanol and ethanol; the diols and/or diol derivatives, for example: ethylene glycol, said glycol derivatives such as: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, glycol ethers, trihydric alcohols such as glycerol, and trihydric alcohol derivatives such as triethanolamine.
Technical scheme 17. the preparation method of the molecular sieve according to any one of technical schemes 5 to 16, wherein the separation is performed by slow centrifugal separation, in one embodiment, the rotation speed of the slow centrifugal separation is 1200r/min to 3000r/min or 1500 to 2500r/min, and the time of the centrifugal separation can be 8 to 50 minutes, for example, 10 to 30 minutes or 15 to 20 minutes. The container used for centrifugal separation is, for example, cylindrical or prismatic, and has a ratio of diameter to height of 0.1 to 1: 1, preferably 0.25 to 1: 1.
Technical scheme 18. the preparation method of the molecular sieve according to any one of technical schemes 5 to 17, wherein the freeze drying method is sublimation drying at low temperature and high vacuum, and the freeze drying temperature is lower than the freezing point temperature of the hydroxyl-containing solvent. Generally, the mixture formed by the molecular sieve and the suspension is cooled and solidified, and then the mixture is freeze-dried under the freezing point temperature (or freezing point temperature) of the solvent and under the vacuum condition, preferably, the temperature of the freeze-drying is-30 to 5 ℃, and the pressure (absolute pressure) is not more than 0.05MPa, such as 50000Pa to 1Pa or 2 to 20000Pa, preferably 5 to 1000Pa, such as 5 to 100Pa or 10 to 50Pa or 15 to 60 Pa. The freeze drying time is 24-48 hours, for example.
Technical scheme 19. a desulfurization method of sulfur-containing hydrocarbon oil, comprising the step of carrying out contact reaction on a hydrocarbon material containing a sulfur compound, a hydrogen donor and the modified molecular sieve of any one of technical schemes 1 to 18, wherein the reaction temperature is 150 to 350 ℃, the reaction pressure is 0.5 to 5MPa, and the weight hourly space velocity of the sulfur-containing hydrocarbon feeding is 0.1 to 100h-1The volume ratio of the hydrogen donor to the sulfur-containing hydrocarbon is 0.01 to 1000. The preferred reaction temperature is 200 deg.CThe temperature is 300 ℃, the reaction pressure is 1-3.5 MPa, and the weight hourly space velocity of the sulfur-containing hydrocarbon feeding is 1-10 h-1The volume ratio of the hydrogen donor to the sulfur-containing hydrocarbon is 0.05 to 500. The sulfur hydrocarbon containing feed weight hourly space velocity refers to the weight of sulfur hydrocarbon containing feed per hour compared to the loading weight of modified molecular sieve. The volume ratio of the hydrogen donor to the sulfur-containing hydrocarbon is the ratio of the volume of the hydrogen donor introduced into the reactor in a standard state to the volume of the hydrocarbon material at 20 ℃ under a standard atmospheric pressure, which is called the hydrogen-oil ratio for short.
The desulfurization method according to claim 19, wherein the hydrogen donor is one or a mixture of two or more selected from hydrogen gas, a hydrogen-containing gas, and a hydrogen donor; hydrogen may be introduced into the reactor using various hydrogen-containing gases or hydrogen-containing gases, typically having a hydrogen content of over 30% by volume; hydrogen-containing gas such as one or more of catalytic cracking (FCC) dry gas, coking dry gas and thermal cracking dry gas; the hydrogen donor is at least one of tetrahydronaphthalene, decahydronaphthalene and indane. The hydrocarbon material is selected from one or more of natural gas, dry gas, liquefied gas, gasoline, kerosene, diesel oil and gas oil, preferably gasoline and/or diesel oil, and can reduce the olefin content of the gasoline and keep higher octane number for the catalytic cracking gasoline. The above gasoline, kerosene, diesel oil and gas oil fractions are full fractions thereof and/or partially narrow fractions thereof.
Technical scheme 21. according to the desulfurization method of the technical scheme 19 or 20, wherein the sulfur content of the hydrocarbon oil containing sulfur compounds is 10-1000 mg/Kg, for example, the sulfur-containing compound material is catalytically cracked gasoline or catalytically cracked diesel oil. Typically, the catalytically cracked gasoline has an olefin content of 15 to 50 wt.%.
The modified molecular sieve provided by the invention has one or more of the following technical effects, preferably has a plurality of the following technical effects:
(1) can have higher desulfurization activity than the prior hydrodesulfurization catalyst and hydrodesulfurization adsorbent. For example, desulfurization at lower reaction temperatures and lower hydrogen pressures can result in higher desulfurization rates than existing desulfurization catalysts.
(2) Has better stability of desulfurization activity, is beneficial to the long-period operation of a desulfurization device, for example, has better stability compared with the prior hydrogen adsorption desulfurization, and does not need frequent regeneration.
(3) The catalyst is used for hydrodesulfurizing gasoline containing olefin and has low hydrogen consumption.
(4) The catalyst is used for hydrodesulfurizing gasoline containing olefin and has obviously lowered olefin content.
(5) The catalyst is used for hydrodesulfurizing gasoline containing olefin and has better effect of improving the octane number of the gasoline at lower reaction temperature.
(6) The catalyst is used for hydrodesulfurizing gasoline containing olefin, and compared with the existing desulfurizing technology, the content of aromatic hydrocarbon is not increased or is slightly lower.
(7) The catalyst is used for desulfurizing the gasoline containing olefin, so that the content of isomeric hydrocarbon in the desulfurized gasoline is obviously improved, and the normal paraffin is obviously reduced.
(8) The catalyst is used for hydrodesulfurizing gasoline containing olefin and has high gasoline yield.
The modified molecular sieve provided by the invention can be obtained by the preparation method, and in addition, the method is easy to implement industrially.
Compared with the existing desulfurization method, the desulfurization method for sulfur-containing hydrocarbon provided by the invention has the advantages of higher desulfurization rate, longer operation period, higher yield of desulfurization products and capability of improving the octane number of desulfurized gasoline under the same reaction temperature.
Detailed Description
The modified molecular sieve for hydrogen desulfurization provided by the invention comprises a molecular sieve and a modified metal film (metal film for short), wherein the modified metal film is positioned on the outer surface of molecular sieve particles to form a film-shaped structure. Typically, the metal film is coated on the outer surface of the molecular sieve, and may cover the entire outer surface of the molecular sieve, or cover a part of the outer surface of the molecular sieve, for example, the metal film may be a single piece on the outer surface of the molecular sieve or may be divided into a plurality of pieces, each piece being continuous or spaced apart from each other. The metal film may be measured by transmission electron microscopy. The modified metal film contains a modified metal. Preferably, the modified molecular sieve comprises 85 to 98 wt% of the molecular sieve and 2 to 15 wt%, for example 5 to 15 wt%, of the modified metal film. The thickness of the metal film is 5-30 nm, preferably 5-20 nm.
The particle diameter D of the modified molecular sieve for hydrogen desulfurization provided by the invention90Is 1 to 15 microns, preferably 1 to 8 microns or 2 to 7 microns, more preferably 2 to 6 microns, for example 3 to 5 microns or 4 to 6 microns. (D)90Also written as D90 or D90 or D90Particle diameter corresponding to 90 vol% cumulative particle size distribution)
The modified molecular sieve for hydrodesulphurization provided by the invention contains the molecular sieve, so that the corresponding modified molecular sieve has the structure of the corresponding molecular sieve, the structure of the molecular sieve can be obtained by the existing method, for example, a spectrogram of the molecular sieve is obtained by an XRD method, and the structure type of the modified molecular sieve is distinguished according to XRD characteristic peaks. The molecular sieve can be one or more of large-pore zeolite, medium-pore zeolite and non-zeolite molecular sieve, the large-pore zeolite refers to zeolite with a pore structure ring opening of at least 0.7 nanometer, and can be one or more selected from L zeolite, Beta zeolite, mordenite and ZSM-18 zeolite, and is preferably Beta zeolite; the medium pore zeolite is zeolite with pore structure opening of 0.56-0.70 nm, and can be selected from one or more of ZSM-5 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite and MCM-56 zeolite, preferably ZSM-5 zeolite; the non-zeolitic molecular sieve is selected from one or more of silicates having different silicon to metal ratios (e.g., metallosilicates, titanosilicates), metalloaluminates (e.g., germano-aluminates), metallophosphates, aluminophosphates, metalloaluminophosphates, metal-bonded silicoaluminophosphates, metal-integrated silicoaluminophosphates (MeAPSO and ELAPSO), Silicoaluminophosphates (SAPO), gallium germanates (gallogermanates), and may be, for example, one or more of SAPO-11, SAPO-34, and SAPO-31, preferably SAPO-11 molecular sieve.
The preparation method of the modified molecular sieve provided by the invention comprises the steps of preparing a suspension, and mixing the suspension with a molecular sieve raw material. The suspension preparation method comprises the following steps: forming a mixture of metal powder, a hydroxyl-containing solvent and a surfactant, and treating under ultrasonic waves to obtain an ultrasonic mixed solution; wherein, in the ultrasonic treatment process, fine metal particles stripped from the metal powder are suspended in a solvent; separating larger particles from the mixed liquid after ultrasonic treatment to obtain a suspension, wherein the suspension suspends fine particles containing the modified metal. The metal powder may be an alloy powder containing a plurality of modified metals. Wherein, there is no special requirement for the relative content of metal powder (or metal powder or metal fine powder) and hydroxyl-containing solvent, as long as the hydroxyl-containing solvent can contain the modified metal element with the required content after ultrasonic treatment. Thus, the amount of metal powder used may be excessive (exceeding the amount of metal contained in the suspension). Preferably, the weight ratio of the hydroxyl-containing solvent to the metal powder is 2-15: 1, for example 3-12: 1 or 5-10: 1. By controlling the time and power of the ultrasonic treatment, the content of the modified metal element with the required concentration in the hydroxyl-containing solvent can be achieved.
The preparation method of the modified molecular sieve provided by the invention leads metal powder to generate metal stripping in the presence of a surfactant through ultrasonic treatment to form fine particles suspended in a hydroxyl-containing solvent. Generally, there is no special requirement for the power and frequency of the ultrasonic wave, the power of the ultrasonic wave is small, and a long treatment time is required to achieve a certain concentration of the modified metal in the hydroxyl group-containing solvent. Preferably, the power of the ultrasonic wave in the ultrasonic wave treatment is 30 to 500W, such as 160 to 400W, 40 to 200W or 30 to 300W, relative to 100ml of the solvent, the frequency of the ultrasonic wave is 20 to 100KHz, such as 20 to 50KHz, and the time of the ultrasonic wave treatment is 3 to 15 hours, such as 4 to 10 hours or 5 to 8 hours. (the power of the ultrasonic waves applied to the solvent per unit volume is a specific ultrasonic power, for example, when the power applied to 100mL of solvent is 30 to 500W, the specific ultrasonic power is 0.3 to 5W/mL or 30 to 500W/100 mL).
There is no particular requirement for the particle size of the metal powder, which is generally larger, requiring longer sonication times to obtain a suspension with a certain metal concentration, preferably less than 20 μm in average diameter, e.g. 1 to 15 microns or 1 to 18 microns or 4 to 16 microns.
Particle size distribution D of modified molecular sieves90Particle diameter distribution D of molecular sieves90The average particle diameter of the molecular sieve and the average diameter of the metal powder are measured by a laser particle size instrument, and the measuring method can be found in the national standard GB/T19077-.
The preparation method of the modified molecular sieve provided by the invention is characterized in that ultrasonic treatment is carried out in the presence of a surfactant. The surfactant is introduced for the purpose of peeling off the metal, forming a stable suspension, and contributing to the formation and stabilization of the metal film and the improvement of the catalyst performance, forming a metal film having higher activity. The weight ratio of the surfactant to the hydroxyl group-containing solvent is 0.001-100mg/g, preferably 0.01-10mg/g, or 0.005-5 mg/g, or 0.002-2 mg/g, or 0.005-1 mg/g, or 0.2-1.5 mg/g.
According to the preparation method of the modified molecular sieve, undissolved particles after ultrasonic treatment are separated through separation, so that a suspension is obtained. The suspension contains fine particles including the modifying metal. The separation method of the invention is preferably a centrifugal separation method, larger particles are settled at the bottom of the container through centrifugal separation, smaller particles which are not separated exist in the solvent, namely in the suspension, the suspension at the upper layer is led out from the separation container, and the settled metal particles can be recycled. In one embodiment, the separation is performed by slow centrifugation at a rotation speed of 1200-. In one embodiment, the vessel used for centrifugation is cylindrical and has a diameter to height ratio of 0.1 to 1: 1, such as 0.1 to 0.5: 1.
Preferably, the particle size D90 of the particles in the suspension obtained after centrifugation is 20nm or less, preferably 10nm or less, more preferably 5nm or less, for example 3 to 20nm or 3 to 10nm or 3 to 5 nm.
Particle size distribution of the suspension and D90Analysis can be performed using a nanoparticle analyzer, such as the Zetasizer NanoZSP nanoparticle analyzer from Malvern.
The preparation method of the modified molecular sieve provided by the invention comprises the steps of uniformly mixing the suspension and the molecular sieve, and then freezing and drying, wherein the suspension is usually frozen and then dried under vacuum and freezing conditions. In one embodiment of the freeze drying, the temperature of the mixture is lower than the solidification temperature of the solvent, so that the mixture is solidified into a solid, then the solvent is sublimated and volatilized under the vacuum condition of the temperature lower than the solidification point or the freezing point of the solvent, and the modified molecular sieve is obtained after the solvent on the outer surface of the molecular sieve particles is volatilized.
In order to facilitate freezing and drying, the hydroxyl-containing solvent (solvent for short) with a high freezing point is preferably selected, the freezing point of the solvent is preferably not lower than-25 ℃, and the freezing and drying are preferably carried out at the temperature of-20-5 ℃, so that the solvent with the freezing point temperature of-20-5 ℃ is preferably used. Preferably, the drying is carried out under vacuum at a pressure of 10 to 10000Pa (absolute), for example 5 to 1000Pa, or 10 to 100Pa, or 10 to 50Pa, or 15 to 35 Pa. The hydroxyl-containing solvent is preferably one or more of water, glycol, glycerol and methanol.
In a preferred embodiment, the molecular sieve is first mixed with a hydroxyl group-containing solvent (referred to as a second part solvent), preferably water, wherein the mass ratio of the second part solvent to the molecular sieve on a dry basis is, for example, 0.1 to 5: 1, or 0.2 to 4: 1, for example, 0.4 to 3.6: 1, or 0.3 to 2: 1, and then mixed with the suspension. Wherein the weight ratio of the second part solvent to the hydroxyl group-containing solvent (referred to as the first part solvent) in the suspension is 0.025-0.4: 1, for example 0.03-0.3: 1. The weight ratio of the modified metal to the molecular sieve dry basis in the suspension is 2-18: 100, for example 2.1-15: 100.
The invention provides a specific implementation mode of a preparation method of a modified molecular sieve, which comprises the following steps: uniformly mixing metal powder and a hydroxyl-containing solvent, and then performing ultrasonic treatment at a specific ultrasonic power of 50-250W/(100 g of hydroxyl-containing solvent), preferably 100-150W/(100 g of hydroxyl-containing solvent)Carrying out ultrasonic treatment for 4-10 hours under power, for example, 5-8 hours, then carrying out centrifugal separation on the mixed solution after ultrasonic treatment at the rotation speed of 1200-3000 r/min, preferably 1500-2500 r/min, and obtaining a suspension after separation; and then putting the molecular sieve solid powder or the molecular sieve slurry containing the molecular sieve solid powder into the obtained suspension for uniform dispersion, and freeze-drying to obtain the modified molecular sieve. The average particle size of the metal fine powder is less than 20 micrometers, preferably 1-15 micrometers or 3-18 micrometers; d of the molecular sieve solid powder90Is 1-20 microns, preferably 2-15 microns, or 3-12 microns, or 4-8 microns; the weight ratio of the metal powder to the solvent is 1: 2-15, preferably 1: 5-10; the ratio of the surfactant to the solvent is 0.001-100 mg: 1L. The metal powder is powder or alloy powder of a metal simple substance, the freeze drying temperature is preferably-20-5 ℃, the freeze drying is carried out in vacuum, and the freeze drying pressure is 5-1000 Pa.
In the following examples and comparative examples,
XRD analysis was carried out by measuring cell constants and relative crystallinity by means of XRD analysis on a Japanese D/Max-IIiA type X-ray diffractometer (Cu-K α target) by means of RIPP146-90 method (see "analytical methods in petrochemical industry (RIPP laboratory methods), eds of Yangroi et al, science publishers, 1990).
Analysis of the thickness of the metal film: the transmission electron microscope method is adopted, and the specific analysis method is as follows: randomly selecting 30 modified molecular sieve particles in a sample, measuring the thickness of any metal film in each particle, and then taking the average value of the thicknesses of all the metal films of the particles, namely the thickness of the metal film of the sample;
the content of the metal is calculated according to the feeding proportion;
laser particle size analysis: a Malvern Mastersizer 2000 laser particle size analyzer is adopted;
particle size analysis of the suspension: zetasizer NanoZSP Analyzer from Malvern;
motor Octane Number (MON) and Research Octane Number (RON) of gasoline: measured by GB/T503-1995 and GB/T5487-1995;
and (3) measuring the sulfur content: measuring by an off-line chromatographic analysis method, and measuring by adopting a GC6890-SCD instrument of the agilent company;
a centrifugal separator: model DT5-4B, Beijing times Beili centrifuge, Inc., container diameter and height ratio 1: 1;
an ultrasonic cleaner: model KQ-400DB, frequency 40 KHZ;
solvents, surfactants, not specified, used in the examples were purchased from national pharmaceutical group chemical agents, ltd, grades: and AR.
Example 1
This example serves to illustrate the modified molecular sieve of the invention and the process for its preparation.
First, 10g of Sn-Bi alloy powder (Sn-Bi alloy powder having an average particle diameter of 10 μm and a weight ratio of Sn to Bi of 0.5: 1) and 100ml of ethylene glycol (national drug group, purity AR) were added to a 200ml jar, mixed uniformly, and 60mg of sodium glycocholate (purity AR, source: Nanjing Parls Biotech Co., Ltd.) as a surfactant was added; then, the reaction vessel (jar) was placed in an ultrasonic cleaner and sonicated at 160W power for 6h (frequency 40 KHz); centrifuging the liquid after ultrasonic treatment in a centrifugal separator at 1500r/min for 20min, taking out supernatant (suspension) with a pipette, wherein the concentration of modified metal in the suspension is 15g/Kg, and D90Is 5 nm;
14.5 g (dry basis) of SAPO-11 molecular sieve powder (Si: Al: P molar ratio 1: 9: 10, D)9014 μm, relative crystallinity 91%, industrial grade, from the company zilu, chinese petrochemical catalyst limited, the same applies hereinafter), with 10g of deionized water, wet grinding to obtain a molecular sieve slurry having a particle diameter D905 microns; adding the molecular sieve slurry into 100g of the suspension; stirring for 10 min; the obtained slurry is marked as JY-1,
and finally, pre-freezing the slurry JY-1 at the temperature of-40 ℃, and then drying for 24 hours at the temperature of-30 ℃ and under the vacuum condition of the pressure of 50Pa to obtain a final product, namely the SAPO-11 molecular sieve wrapping the modified metal membrane, which is marked as A1. The thickness of the modified metal film is 5nm, the modified metal content is 9.4 wt%, and the Sn/Bi weight ratio is as follows: 0.5: 1, D90Is 5 microns。
The properties of the modified molecular sieves prepared in the examples and comparative examples are shown in Table 1, and the preparation process parameters are shown in Table 2.
Comparative example 1
SAPO-11 slurry JY-1 (milled to D as in example 1)905 μm) was mixed and impregnated with an aqueous solution of tin nitrate and bismuth nitrate to obtain a modified molecular sieve product DB 1. The modified metal content was the same as in example 1.
Comparative example 2
1g of tin nitrate (calculated as tin) and 2 g of bismuth nitrate (calculated as bismuth) were dissolved in 100ml of ethylene glycol, and then the reaction vessel was placed in an ultrasonic cleaning machine, subjected to ultrasonic treatment at a power of 160W for 6 hours, and then ground with 29g of a ground particle diameter D90SAPO-11 (same as example 1) of 5 microns is mixed and impregnated, then dried at 120 ℃ and roasted at 450 ℃ for 2 hours to obtain a modified molecular sieve product DB 2.
Comparative example 3
In the existing S-ZORB adsorbent, nickel is a hydrogenation active component, and the composition of the S-ZORB adsorbent is that the zinc oxide content is 44.3 wt%, the expanded perlite content is 24.0 wt%, the alumina content is 13.6 wt%, and the nickel content is 18.1 wt%, which are recorded as DB 3.
Comparative example 1
A modified molecular sieve was prepared by following the procedure of example 1, except that the modified molecular sieve was dried by a drying method of drying at 120 ℃ without performing the freeze-drying as described, to obtain a modified molecular sieve defined as BJ 1.
Example 2
This example serves to illustrate the modified molecular sieve of the invention and the process for its preparation.
Adding 50gGe-Bi alloy powder (average grain diameter is 15 microns, Ge-Bi weight ratio is 1.2: 1) and 400ml ethylene glycol (analytically pure) into a 500ml wide-mouth bottle, uniformly mixing, and adding 120mg of surfactant sodium dodecyl sulfate (analytically pure, national drug group); then, placing the reaction container in an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 4h at 200W; centrifuging the liquid subjected to ultrasonic treatment for 10min at 2000r/min, and taking out the suspension; the modified metal concentration in the suspension is measured to be 25g/Kg, and the particle size D is measured9010nm, the weight ratio of Ge/Bi is 1.2: 1;
40g of the powderSAPO-11 molecular sieve powder (the same SAPO-11 molecular sieve powder used in example 1) was mixed with 40g of deionized water and wet ball milled into a slurry having a particle diameter D905 microns; then, 100g of the suspension is added into the molecular sieve slurry; stirring for 10 min;
pre-freezing the slurry at-40 ℃, and then drying the slurry for 24 hours at-30 ℃ under 20Pa vacuum, wherein the final product is the SAPO-11 molecular sieve wrapped with the modified metal membrane and marked as A2. The thickness of the metal film is 15nm, the weight ratio of Ge/Bi is 1.2: 1, and the content of the modified metal accounts for 20 wt% of the total weight of the modified molecular sieve.
Example 3
40gPb-Bi alloy powder (average particle size 5 μm, Sb-Bi weight ratio 6: 1) and 150ml ethylene glycol (same as used in example 1) were added to a 500ml jar, mixed well, and 250mg of stearic acid (purchased from national institute of medicine, purity AR) as a surfactant was added; then, putting the mixture into an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 10 hours at the power of 280W; centrifuging the liquid subjected to ultrasonic treatment at 1500r/min for 30min, and taking out the suspension; the total concentration of Pb and Bi in the suspension was measured to be 30g/Kg, and the particle size D of the modified metal particles was measured90Is 4 nm;
23.8 g of SAPO-11 molecular sieve powder (D90 ═ 14 μm, technical grade, product of the medium petrochemical catalyst, Qilu division) was mixed with 40g of deionized water, and wet-ball milled into a slurry having a particle diameter D905 microns; then 140g of the above suspension was added thereto; stirring for 10 min; pre-freezing the slurry at-40 ℃, and then drying the slurry at-30 ℃ under 50Pa for 48h to obtain the final product, namely the SAPO-11 molecular sieve wrapping the modified metal membrane, which is marked as A3. The thickness of the metal film was 10nm, and the modified metal content was 15 wt%. D of modified molecular sieve90Is 5 microns.
Example 4
Adding 10gSn-Sb-Bi alloy fine powder (from Tianjin Hainan alloy Co., Ltd., Sn-Sb-Bi weight ratio of 5: 2: 1) and 100ml deionized water into a 200ml wide-mouth bottle, mixing uniformly, and adding 60mg of surfactant sodium glycocholate (from Nanjing Paersi Biotech Co., Ltd.); then, placing the jar in an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 6h at 160W power; centrifuging the liquid after ultrasonic treatment at 1500r/min for 20min, taking out and suspendingFloating liquid; the total concentration of the metal Sn-Sb-Bi in the suspension is 15g/Kg, the weight ratio of Sn-Sb-Bi is 5: 2: 1, D90Is 5 nm;
14.5 g of SAPO-11 molecular sieve powder (D90 ═ 14 μm, technical grade, product of the medium petrochemical catalyst, Qilu division) was mixed with 10g of deionized water, and wet-ball milled into a slurry having a particle diameter D905 microns; adding 100g of the suspension into the molecular sieve slurry; stirring for 10 min; pre-freezing the mixed slurry of the molecular sieve and the suspension at the temperature of minus 10 ℃, and drying the mixed slurry at the temperature of minus 5 ℃ under the pressure of 50Pa (absolute pressure) for 24 hours to obtain a final product, namely the SAPO-11 molecular sieve wrapped with the modified metal membrane, which is marked as A4. The thickness of the modified metal film is 5nm, the total content of the modified metal Sn-Sb-Bi is 9.4 weight percent, and the weight ratio of the modified metal Sn-Sb-Bi to the modified metal Sn-Sb-Bi is 5: 2: 1.
Example 5
Adding 10g of lead-tin alloy fine powder (weight ratio of lead to tin is 2.5: 1, average particle size is 15 μm) and 100ml of glycerol (analytical purity) into a 200ml wide-mouth bottle, mixing uniformly, and adding 60mg of surfactant sodium glycocholate (purity AR from Nanjing Palse Biotech Co., Ltd.); then, putting the wide-mouth bottle into an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 6h at 160W power; centrifuging the liquid after ultrasonic treatment for 20min at 3000r/min, and taking out the suspension; the total concentration of metal-modified metal in the suspension was 25g/Kg, the weight ratio of Pb to Sn was 2.5: 1, D90Is 5 nm;
22.5 g of HZSM-5 molecular sieve powder (the silica-alumina ratio (Si/A1) is 100, the product of Qilu division of China petrochemical catalyst Co., Ltd., the crystallinity is 95 percent) is mixed with 20g of deionized water, and the mixture is ball-milled into slurry by a wet method, wherein the particle diameter d90 is 2 microns; then adding the whole into 100g of the suspension; stirring for 10 min; obtaining slurry JY-5;
and freezing the slurry JY-5 at-20 ℃, and drying at-15 ℃ and 30Pa (absolute pressure) for 24h to obtain a final product, namely the ZSM-5 molecular sieve coated with the modified metal membrane, which is marked as A5. The thickness of the modified metal film was 12nm, the total content of the modified metal was 18 wt%, and the weight ratio of lead and tin in the modified metal was 2.5: 1. D of modified molecular sieve A590Is 2 microns.
Example 6
Firstly, adding 50g of tin powder (with the average particle size of 18 microns) and 300ml of ethylene glycol into a 500ml wide-mouth bottle, uniformly mixing, and then adding 120mg of surfactant lauryl sodium sulfate; then, placing the reaction container in an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 4h at the power of 180W; centrifuging the liquid after ultrasonic treatment at 2000r/min for 10min, taking out suspension, wherein the concentration of tin in the suspension is 20g/Kg, and the particle size D90Is 10 nm;
20g of Beta molecular sieve powder (d90 ═ 20 μm, technical grade, product of the well petrochemical catalyst, Qilu division, hydrogen type, silica to alumina ratio 30, degree of crystallinity 90%), was mixed with 40g of deionized water, wet ball milled into slurry, particle diameter d90 ═ 5 μm; then 200g of the above suspension was added thereto; stirring for 10 min;
and finally, pre-freezing the slurry at the temperature of-40 ℃, and then drying the slurry for 24 hours at the temperature of-30 ℃ under the vacuum condition of 20Pa to obtain a final product, namely the modified Beta molecular sieve wrapping the modified metal film, which is marked as A6. The thickness of the metal film is 15nm, and the content of tin accounts for 20 wt% of the total weight of the modified molecular sieve.
Example 7
Adding 30g of lead-antimony alloy powder (average particle size of 5 microns, weight ratio of lead to antimony of 2: 1, and 150ml of ethylene glycol) into a 250ml wide-mouth bottle, mixing uniformly, adding 200mg of surfactant stearic acid, placing the reaction container in an ultrasonic cleaning machine, performing ultrasonic treatment at 200W for 10h, separating the liquid after ultrasonic treatment at 1500r/min for 30min, taking out supernatant fluid, namely suspension, wherein the total concentration of lead and antimony in the suspension is 10g/Kg, and the particle size D is90Is 4 nm;
20g of mordenite molecular sieve powder (d90 is 10 microns, industrial grade, Shanghai cloud-green new material Co., Ltd., Si/Al ratio 40, crystallinity 95%) is mixed with 34 g of deionized water, and the mixture is ball-milled into slurry by a wet method, wherein the particle diameter d90 is 5 microns; then 100g of the above suspension was added thereto; stirring for 10 min; pre-freezing the slurry at-40 deg.C, and drying at-30 deg.C under 50Pa for 48 hr to obtain the final product, i.e. mordenite coated with metal film, marked as A7. The thickness of the metal film was 10nm, and the modified metal content was 5 wt%. D of the modified molecular sieve90Is 5 microns.
Application example
The modified sub-sieves A1-A7, DB1, DB2, DB3 and BJ1 prepared according to examples 1-7, comparative examples 1-3 and comparative example 1 of the invention are subjected to desulfurization evaluation experiments by using a fixed bed micro-reaction experimental device, and the specific method comprises the following steps: filling 16g of modified molecular sieve (also called as desulfurization catalyst) in a fixed bed reactor with the inner diameter of 30mm and the length of 1m, using hydrogen as a hydrogen supply medium, and under the conditions that the reaction temperature is 300 ℃, the reaction pressure is 1.38MPa, the hydrogen flow is 6.3L/h, the gasoline feed flow is 56g/h, and the weight space velocity of the raw material hydrocarbon oil is 4h-1Under the reaction conditions of (1), a desulfurization reaction of the sulfur-containing hydrocarbon oil is carried out. The gasoline composition is shown in Table 3, and the reaction results are shown in tables 4-6.
TABLE 1
TABLE 3
| Item | Analyzing data | Item | Analyzing data |
| Density (20 ℃ C.) (kg.m)-3) | 727.3 | Induction phase (min) | 922 |
| Actual gum (mg/mL) | 0.34 | Distillation range (. degree.C.) | |
| Refractive index (20 ℃ C.) | 1.4143 | Initial boiling point | 38.5 |
| Sulfur content (ng./. mu.L) | 960.48 | 5％ | 49.0 |
| Mercaptan sulfur content (ng/. mu.L) | 10.2 | 10％ | 55.5 |
| Hydrogen sulfide content (ng/. mu.L) | 0 | 30％ | 74.7 |
| Octane number (RON/MON) | 93.7/83.6 | 50％ | 97.2 |
| Group composition volume (%) | 70％ | 124.2 | |
| Saturated hydrocarbons | 44.0 | 90％ | 155.2 |
| Olefins | 41.2 | 95％ | 165.2 |
| Aromatic hydrocarbons | 14.8 | End point of distillation | 185.0 |
TABLE 4
TABLE 5
Note: in tables 4 to 5:
1. the feed gasoline had a sulfur content of 960ppm, a RON of 93.7 and a MON of 83.6.
2.Δ MON represents the increase in product MON;
3.Δ RON represents the increase in product RON;
4. delta (RON + MON)/2 is the difference between the antiknock index of the product and the antiknock index of the raw material.
5. The sulfur content of the samples at each time point is the sulfur content of the samples collected within one hour before the sampling time point, and the gasoline composition and octane number are the average values of the analysis results of each sample.
From the results data of tables 4 to 5, it can be seen that:
the modified molecular sieve prepared by the invention is used as a catalyst for gasoline desulfurization treatment, the sulfur content in a gasoline product is lower than 0.5ppm (chromatographic detection limit) in the initial reaction stage, the sulfur content in the product is gradually increased along with the reaction time, but the highest sulfur content of the gasoline product can be still lower than 10ppm or even lower than 5ppm after the reaction of 240-960 h, the octane number is increased, the olefin content of the gasoline is obviously reduced, and the isoparaffin content is increased.
Claims (17)
1. The modified molecular sieve for hydrodesulphurization is characterized by comprising a molecular sieve and a modified metal membrane, wherein the modified metal membrane is positioned on the outer surface of molecular sieve particles; the modified metal film contains modified metal, the modified metal comprises first metal and optional second metal, wherein the first metal is one or more of Ge, Sn and Pb, and the second metal is Bi and/or Sb and/or Ga.
2. The modified molecular sieve of claim 1, wherein the modified metal film has a thickness of 5 to 30 nm.
3. The modified molecular sieve of claim 1 or 2, wherein the modified molecular sieve has a particle diameter D90Is 1 to 8 μm.
4. The modified molecular sieve of claim 1, 2 or 3, wherein the modified molecular sieve comprises 85 to 98 weight percent molecular sieve and 2 to 15 weight percent modified metal; wherein the weight ratio of the first metal to the second metal is preferably 0.4 to 10: 1.
5. A preparation method of a modified molecular sieve comprises the following steps: forming a mixture of metal powder, a hydroxyl-containing solvent and a surfactant, and then treating under ultrasonic waves to obtain an ultrasonic mixed solution; separating the mixed solution after ultrasonic treatment to obtain suspension, mixing the suspension with the molecular sieve, and freeze-drying to obtain the modified molecular sieve.
6. The process for preparing modified molecular sieve according to claim 5, wherein the molecular sieve is one or more of large-pore zeolite, medium-pore zeolite and non-zeolite molecular sieve; the large-pore zeolite can be one or more selected from L zeolite, Beta zeolite, mordenite and ZSM-18 zeolite; the medium pore zeolite can be one or more selected from ZSM-5 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite and MCM-56 zeolite; the non-zeolite molecular sieve can be selected from one or more of SAPO-11, SAPO-34 and SAPO-31; d of the molecular sieve90Preferably 1 to 8 microns.
7. The preparation method of the modified molecular sieve of claim 5, wherein the concentration of the modified metal in the suspension is 5-45 g/Kg, preferably 10-25 g/Kg.
8. A process for preparing a modified molecular sieve according to claim 5 or 7, wherein the particle size D of the particles in the suspension is90Is 20nm or less, for example, 3 to 20 nm.
9. The method for preparing the modified molecular sieve of claim 5 or 7, wherein the suspension and the molecular sieve are mixed, the weight ratio of the suspension to the molecular sieve is 0.5-20: 1, and preferably, the weight ratio of the modified metal in the suspension to the molecular sieve is 2-15: 85-98.
10. The method for preparing the modified molecular sieve of claim 5, wherein the weight ratio of the hydroxyl-containing solvent to the metal powder is 2-15: 1, the ratio of the surfactant to the hydroxyl group-containing solvent is 0.001 to 100 mg/mL.
11. The method for preparing the modified molecular sieve of claim 5, wherein the ultrasonic treatment is performed at a power of 10 to 500W per 100ml of the solvent; preferably, the metal powder has an average diameter of less than 20 μm.
12. The method for preparing the modified molecular sieve of claim 5 or 11, wherein the metal powder is one or more of Ge-Bi alloy powder, Sn-Bi alloy powder, Sb-Bi alloy powder, and Sn-Sb-Bi alloy powder; preferably, in the alloy powder, the ratio of the first metal to Bi is: 0.4-10: 1.
13. The method of claim 5, wherein the surfactant is one of sodium glycocholate, sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium lauryl sulfate, stearic acid, oleic acid, lauric acid, fatty acid amine, cetyl trimethylammonium bromide, sodium dodecyl sulfate, cetyl trimethylammonium bromide, fatty acid methyl ester, and polyoxyethylene ether.
14. The method of preparing a modified molecular sieve of claim 5, wherein the hydroxyl-containing solvent is water and/or a hydroxyl-containing organic solvent, and the hydroxyl-containing organic solvent is a monohydric alcohol, a dihydric alcohol, a trihydric alcohol or a derivative thereof; the monohydric alcohol is one or more of methanol and ethanol, the dihydric alcohol is ethylene glycol, the glycol derivative is one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and ethylene glycol ether, the trihydric alcohol is glycerol, and the trihydric alcohol derivative is triethanolamine.
15. The method of claim 5, wherein the separation is performed by centrifugation at a speed of 1200 to 3000 r/min.
16. The method for preparing a molecular sieve according to claim 5, wherein the freeze-drying method is sublimation-drying at a low temperature and under a high vacuum, the drying temperature being lower than the freezing point temperature of the hydroxyl group-containing solvent; for example, the temperature of freeze drying is-30 to 5 ℃, and is not more than 0.05 Mpa; the freeze-drying time is, for example, 24 to 48 hours.
17. A desulfurization method of sulfur-containing hydrocarbon oil comprises the step of carrying out contact reaction on a hydrocarbon material containing sulfur compounds, a hydrogen donor and the modified molecular sieve of any one of claims 1 to 4, wherein the reaction temperature is 150-350 ℃, the reaction pressure is 0.5-5 MPa, and the weight hourly space velocity of the sulfur-containing hydrocarbon feeding is 0.1-100 h-1The volume ratio of the hydrogen donor to the sulfur-containing hydrocarbon is 0.01-1000; the hydrogen donor is selected from one or a mixture of more than two of hydrogen, hydrogen-containing gas and hydrogen donor; the hydrocarbon material is selected from one or more of natural gas, dry gas, liquefied gas, gasoline, kerosene, diesel oil and gas oil.
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