CN110951510A - 一种轻烃燃料的清洁脱硫改性方法 - Google Patents
一种轻烃燃料的清洁脱硫改性方法 Download PDFInfo
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- CN110951510A CN110951510A CN201911333266.7A CN201911333266A CN110951510A CN 110951510 A CN110951510 A CN 110951510A CN 201911333266 A CN201911333266 A CN 201911333266A CN 110951510 A CN110951510 A CN 110951510A
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- parts
- light hydrocarbon
- hours
- stirring
- hydrocarbon fuel
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 60
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 60
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 58
- 239000000446 fuel Substances 0.000 title claims abstract description 34
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 12
- 230000023556 desulfurization Effects 0.000 title claims abstract description 12
- 238000002715 modification method Methods 0.000 title claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 55
- 238000003756 stirring Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000001914 filtration Methods 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 239000003599 detergent Substances 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims description 16
- 239000010935 stainless steel Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 8
- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 235000006708 antioxidants Nutrition 0.000 claims description 8
- 239000013556 antirust agent Substances 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 8
- -1 tert-butyl methyl Chemical group 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- ANHQLUBMNSSPBV-UHFFFAOYSA-N 4h-pyrido[3,2-b][1,4]oxazin-3-one Chemical group C1=CN=C2NC(=O)COC2=C1 ANHQLUBMNSSPBV-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 230000003712 anti-aging effect Effects 0.000 claims description 5
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- 238000012986 modification Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- ZVOLCUVKHLEPEV-UHFFFAOYSA-N Quercetagetin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=C(O)C(O)=C(O)C=C2O1 ZVOLCUVKHLEPEV-UHFFFAOYSA-N 0.000 claims description 4
- HWTZYBCRDDUBJY-UHFFFAOYSA-N Rhynchosin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=CC(O)=C(O)C=C2O1 HWTZYBCRDDUBJY-UHFFFAOYSA-N 0.000 claims description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 241001122767 Theaceae Species 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 239000003831 antifriction material Substances 0.000 claims description 4
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 claims description 4
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
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- 239000012459 cleaning agent Substances 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- 235000013923 monosodium glutamate Nutrition 0.000 claims description 4
- ZKZAYPCZGZAZAG-UHFFFAOYSA-J n,n-dibutylcarbamodithioate;molybdenum(4+) Chemical compound [Mo+4].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC ZKZAYPCZGZAZAG-UHFFFAOYSA-J 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- SDKTUKJXHDZWMB-UHFFFAOYSA-N phosphoric acid zirconium Chemical compound [Zr].P(O)(O)(O)=O SDKTUKJXHDZWMB-UHFFFAOYSA-N 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 4
- 235000013824 polyphenols Nutrition 0.000 claims description 4
- 235000005875 quercetin Nutrition 0.000 claims description 4
- 229960001285 quercetin Drugs 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229940073490 sodium glutamate Drugs 0.000 claims description 4
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 102000007327 Protamines Human genes 0.000 claims description 3
- 108010007568 Protamines Proteins 0.000 claims description 3
- 229940048914 protamine Drugs 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims 2
- 230000003009 desulfurizing effect Effects 0.000 claims 2
- 239000003623 enhancer Substances 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 2
- 239000004094 surface-active agent Substances 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract 1
- 239000000779 smoke Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002737 fuel gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- 238000010010 raising Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- FUSJZTVOKYJFPI-UHFFFAOYSA-N cyclopentane;iron;5-methylcyclopenta-1,3-diene Chemical compound [Fe].[CH-]1[CH-][CH-][CH-][CH-]1.C[C-]1C=CC=C1 FUSJZTVOKYJFPI-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
- C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
- C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
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- C—CHEMISTRY; METALLURGY
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
- C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/22—Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency
Abstract
本发明公开了一种轻烃燃料的清洁脱硫改性方法，本发明属于燃料技术领域。本发明公开的改性方法，可提高轻烃燃料的热效，大幅度降低燃烧废气中的一氧化碳和硫含量。由于本添加剂的组成成分均为有机物，无不能燃烧的重金属残存，可同时大大降低残液量和在燃烧炉具上的附着物，使轻烃燃料达到更加清洁卫生、符合环保要求的良好效果。有利于轻烃燃料的普及，可生产民用、工业用系列燃料品种，减少烟气对环境的污染。
Description
技术领域
本发明属燃料技术领域，尤其是一种轻烃燃料的清洁脱硫改性方法。
背景技术
轻烃的来源十分广泛，油田、气田、天然气净化厂等生产流程中的伴生气凝析油，炼油厂的拔头油、轻石脑油、溶剂油厂石油醚副产品等都是轻烃原料来源。目前我国年产轻烃近1000万吨，相当于全国汽车汽油耗量的1/6。轻烃与天然气一样都是清洁燃料，除了热值高、燃烧排放清洁外，与天然气和L相比，它在常温下呈液体，运输、贮存、分销和携带更为方便安全。但是由于种种原因，过去对轻烃的综合利用缺乏研究，以致绝大部分轻烃作为生产废料在烟囱白白烧掉，不仅浪费了宝贵资源还污染了环境。随着我国可持续发展战略的实施以及人们对资源和环境的关注和技术进步，充分利用这种宝贵资源已被提到议事日程，并成为我国政府积极鼓励的重大项目之一，目前正在积极开发和推广，把轻烃作为汽车燃料就是其中之一各种车用替代燃料特点目前主要的替代燃料有天然气、乙醇汽油、甲醇汽油和电力等。这些替代燃料具有各自的优点，也存在一系列缺点有待解决。轻烃作为燃料用于汽车开发较迟，但表现出的一系列优点，表明有很好的前景，本领域技术人员亟待开发出一种轻烃燃料的清洁脱硫改性方法。
发明内容
针对上述问题，本发明旨在提供一种轻烃燃料的清洁脱硫改性方法。
本发明通过以下技术方案实现：
一种轻烃燃料的清洁脱硫改性方法，包括以下步骤：（1）将3~5份的纯度在98％以上的轻烃放入陶罐内，然后加入0.01~0.2份清洁剂和0.01~0.2份防老剂，搅拌40分钟后得A混合液；（2）按重量份数计将轻烃37~39份、甲醇37~39份、二甲醚11~13份、2-甲基-1-丁烯5~7份、催化剂3.1~5.1份，反应温度400~425℃、反应压力为常压；甲醇的重量空速为1.8~2.2/h，轻烃的重量空速为0.22~0.36/h，高纯氮300~350ml/min，反应时间6~12小时，得低碳轻烃；（3）将49.9份低碳轻烃放在不锈钢罐内，然后向该不锈钢罐内加入5~10份的复合添加剂混合，搅拌5~8分钟得B混合液；（4）再向A混合液所在的陶罐内加入6~7份的甲基叔丁基醚，混合后搅拌5~8分钟，然后将不锈钢罐内B混合液倒入A混合液所在的陶罐内，混合后搅拌5~8分钟，密封24小时即得的清洁脱硫后的轻烃燃料。
作为进一步的方案，所述催化剂的制备方法为将质量分数85%磷酸13.83~14.89份，溶于120~130份去离子水中，搅拌均匀，向该磷酸水溶液加入二氧化锆29.12份，搅拌，使之溶解成均匀溶液，另加46~56份的正硅酸乙酯、44~58份三乙醇胺、16~18.3份二乙醇胺，在激烈搅拌下将含二氧化硅硅溶胶等物质的溶液加入到磷酸-锆溶液中胶，将凝胶放入压力为2~3MPa不锈钢高压釜中，在120℃晶化96小时，然后将反应产物过滤、洗涤，在120℃干燥2小时即得催化剂的活性组分A，再称取ZSM-5型分子筛22~25份，浸泡在质量分数1~1.5%谷氨酸钠水溶液中，50℃浸泡2~6小时，过滤用去离子水洗涤，抽滤游离水，再浸泡于质量分数0.45%的氢氧化钠水溶液中，过滤用去离子水洗涤，抽滤游离水，将上述分子筛放入一个带有过滤板的循环槽中，加入0.05M的硝酸镧溶液中，在室温下以0.02m/s流速循环浸泡12小时，升温至80℃搅拌2h，处理好的样品经过去离子水反复洗涤至中性，经抽滤，烘干后，在空气气氛中以5℃/min的速度升至550℃，焙烧4h，焙烧后的样品以质量浓度为6~8%的硝酸铵溶液在80℃交换2h后过滤，如此重复4次后在120℃下干燥并于550℃焙烧2h，即活性组分B，称取含31%二氧化硅的硅溶胶212~220份、偏铝酸钠16~18份、去离子水230~240份搅拌均匀，在激烈搅拌下加入上述制备的活性组分A 30~56份、活性组分B16~20份，经喂料机调节进料速度，喷雾干燥得到一定粒度分布催化剂。
作为进一步的方案，所述步骤（1）的防老剂为的鱼精蛋白、茶多酚、栎皮酮中的其中一种或多种。
作为进一步的方案，所述步骤（3）的复合添加剂的组成为增进剂和清净剂按重量份数比1∶1组成，增进剂成分由二茂铁基叔丁基甲醇22~33份、三甲硅氧甲基二茂铁8~13份、N-丁基二茂铁丁酰胺4~7份共溶混合组成，清净剂由占清净剂含量98~99％的主剂和占清净剂1~2％的辅助剂组成；主剂清净分散剂的成分为甲醇25~28份、二茂铁甲醇25~27份、环烷酸锌1.5~3份，辅助剂由抗氧剂2~4份、抗乳化剂1~2份、防锈剂0.5~1份、减磨剂0.2~0.4份组成，其中的抗氧剂：选用叔丁基对羟基茴香醚，抗乳化剂：烯丙氧基壬基苯氧基丙醇聚氧乙烯醚硫酸铵，防锈剂：磷酸三甲酚酯，减磨剂：二丁基二硫代氨基甲酸钼。作为进一步的方案，所述步骤（1）的清洁剂为甲基环戊二烯三羰基锰或甲基环戊二烯三羰基锰的其中一种。
本发明的有益效果：
本发明公开的轻烃燃料改性处理方法通过添加剂组分改性和催化裂解，生产成本低，原料易得，操作简便。与符合行业标准要求的轻烃燃料配伍，可提高轻烃燃料的燃烧性能，适度延缓火焰传播速度，火焰传播速度快，蒸气压力高，闪点高，从而可保持燃烧过程中的安全性、稳定性。
相比现有技术本发明具有如下优点：
与未经处理的轻烃燃料气相比较，本发明公开的改性方法处理的轻烃燃气压力小，不易泄露，不易中毒，不易爆炸，安全系数高，经济实惠，改性后的轻烃燃气价格低廉，满足居民生活及各行业对降低成本的控制需求，轻烃燃气燃气气化使用率为100%，无污染，无浪费，无残留，环保节能。
具体实施方式
下面用具体实施例说明本发明，但并不是对本发明的限制。
实施例1
一种轻烃燃料的清洁脱硫改性方法，包括以下步骤：（1）将5份的纯度在98％以上的轻烃放入陶罐内，然后加入0.2份甲基环戊二烯三羰基锰和0.2份茶多酚，搅拌40分钟后得A混合液；（2）按重量份数计将轻烃39份、甲醇39份、二甲醚13份、2-甲基-1-丁烯7份、催化剂5.1份，反应温度425℃、反应压力为常压；甲醇的重量空速为2.2/h，轻烃的重量空速为0.36/h，高纯氮350ml/min，反应时间12小时，得低碳轻烃；（3）将49.9份低碳轻烃放在不锈钢罐内，然后向该不锈钢罐内加入10份的复合添加剂混合，搅拌8分钟得B混合液；（4）再向A混合液所在的陶罐内加入7份的甲基叔丁基醚，混合后搅拌8分钟，然后将不锈钢罐内B混合液倒入A混合液所在的陶罐内，混合后搅拌8分钟，密封24小时即得的清洁脱硫后的轻烃燃料。
作为进一步的方案，所述催化剂的制备方法为将质量分数85%磷酸14.89份，溶于30份去离子水中，搅拌均匀，向该磷酸水溶液加入二氧化锆29.12份，搅拌，使之溶解成均匀溶液，另加56份的正硅酸乙酯、58份三乙醇胺、18.3份二乙醇胺，在激烈搅拌下将含二氧化硅硅溶胶等物质的溶液加入到磷酸-锆溶液中胶，将凝胶放入压力为3MPa不锈钢高压釜中，在120℃晶化96小时，然后将反应产物过滤、洗涤，在120℃干燥2小时即得催化剂的活性组分A，再称取ZSM-5型分子筛25份，浸泡在质量分数1.5%谷氨酸钠水溶液中，50℃浸泡6小时，过滤用去离子水洗涤，抽滤游离水，再浸泡于质量分数0.45%的氢氧化钠水溶液中，过滤用去离子水洗涤，抽滤游离水，将上述分子筛放入一个带有过滤板的循环槽中，加入0.05M的硝酸镧溶液中，在室温下以0.02m/s流速循环浸泡12小时，升温至80℃搅拌2h，处理好的样品经过去离子水反复洗涤至中性，经抽滤，烘干后，在空气气氛中以5℃/min的速度升至550℃，焙烧4h，焙烧后的样品以质量浓度为8%的硝酸铵溶液在80℃交换2h后过滤，如此重复4次后在120℃下干燥并于550℃焙烧2h，即活性组分B，称取含31%二氧化硅的硅溶胶220份、偏铝酸钠18份、去离子水240份搅拌均匀，在激烈搅拌下加入上述制备的活性组分A 56份、活性组分B20份，经喂料机调节进料速度，喷雾干燥得到一定粒度分布催化剂。
作为进一步的方案，所述步骤（3）的复合添加剂的组成为增进剂和清净剂按重量份数比1∶1组成，增进剂成分由二茂铁基叔丁基甲醇33份、三甲硅氧甲基二茂铁13份、N-丁基二茂铁丁酰胺7份共溶混合组成，清净剂由占清净剂含量99％的主剂和占清净剂1％的辅助剂组成；主剂清净分散剂的成分为甲醇28份、二茂铁甲醇27、环烷酸锌3份，辅助剂由抗氧剂4份、抗乳化剂2份、防锈剂1份、减磨剂0.4份组成，其中的抗氧剂：选用叔丁基对羟基茴香醚，抗乳化剂：烯丙氧基壬基苯氧基丙醇聚氧乙烯醚硫酸铵，防锈剂：磷酸三甲酚酯，减磨剂：二丁基二硫代氨基甲酸钼。
实施例2
一种轻烃燃料的清洁脱硫改性方法，包括以下步骤：（1）将5份的纯度在98％以上的轻烃放入陶罐内，然后加入0.2份甲基环戊二烯三羰基锰和0.2份栎皮酮，搅拌40分钟后得A混合液；（2）按重量份数计将轻烃37份、甲醇37份、二甲醚11份、2-甲基-1-丁烯5份、催化剂3.1份，反应温度400℃、反应压力为常压；甲醇的重量空速为1.8/h，轻烃的重量空速为0.22/h，高纯氮300ml/min，反应时间6小时，得低碳轻烃；（3）将49.9份低碳轻烃放在不锈钢罐内，然后向该不锈钢罐内加入5份的复合添加剂混合，搅拌5分钟得B混合液；（4）再向A混合液所在的陶罐内加入6份的甲基叔丁基醚，混合后搅拌5分钟，然后将不锈钢罐内B混合液倒入A混合液所在的陶罐内，混合后搅拌5分钟，密封24小时即得的清洁脱硫后的轻烃燃料。
作为进一步的方案，所述催化剂的制备方法为将质量分数85%磷酸13.83份，溶于120份去离子水中，搅拌均匀，向该磷酸水溶液加入二氧化锆29.12份，搅拌，使之溶解成均匀溶液，另加56份的正硅酸乙酯、44份三乙醇胺、16份二乙醇胺，在激烈搅拌下将含二氧化硅硅溶胶等物质的溶液加入到磷酸-锆溶液中胶，将凝胶放入压力为2MPa不锈钢高压釜中，在120℃晶化96小时，然后将反应产物过滤、洗涤，在120℃干燥2小时即得催化剂的活性组分A，再称取ZSM-5型分子筛22份，浸泡在质量分数1%谷氨酸钠水溶液中，50℃浸泡2小时，过滤用去离子水洗涤，抽滤游离水，再浸泡于质量分数0.45%的氢氧化钠水溶液中，过滤用去离子水洗涤，抽滤游离水，将上述分子筛放入一个带有过滤板的循环槽中，加入0.05M的硝酸镧溶液中，在室温下以0.02m/s流速循环浸泡12小时，升温至80℃搅拌2h，处理好的样品经过去离子水反复洗涤至中性，经抽滤，烘干后，在空气气氛中以5℃/min的速度升至550℃，焙烧4h，焙烧后的样品以质量浓度为6%的硝酸铵溶液在80℃交换2h后过滤，如此重复4次后在120℃下干燥并于550℃焙烧2h，即活性组分B，称取含31%二氧化硅的硅溶胶220份、偏铝酸钠18份、去离子水240份搅拌均匀，在激烈搅拌下加入上述制备的活性组分A 56份、活性组分B20份，经喂料机调节进料速度，喷雾干燥得到一定粒度分布催化剂。
作为进一步的方案，所述步骤（1）的防老剂为的鱼精蛋白、茶多酚、栎皮酮中的其中一种或多种。。
作为进一步的方案，所述步骤（3）的复合添加剂的组成为增进剂和清净剂按重量份数比1∶1组成，增进剂成分由二茂铁基叔丁基甲醇22份、三甲硅氧甲基二茂铁8份、N-丁基二茂铁丁酰胺4份共溶混合组成，清净剂由占清净剂含量98％的主剂和占清净剂2％的辅助剂组成；主剂清净分散剂的成分为甲醇28份、二茂铁甲醇25份、环烷酸锌1.5份，辅助剂由抗氧剂2份、抗乳化剂1份、防锈剂0.5份、减磨剂0.4份组成，其中的抗氧剂：选用叔丁基对羟基茴香醚，抗乳化剂：烯丙氧基壬基苯氧基丙醇聚氧乙烯醚硫酸铵，防锈剂：磷酸三甲酚酯，减磨剂：二丁基二硫代氨基甲酸钼。
对比例1
本对比例2与实施例2相比，在步骤（3）中省去添加复合添加剂，除此外的方法步骤均相同。
对比例2
未经改性处理的轻烃。
对实施例1~2和对比例1~2的轻烃燃料进行性能测试，测试结果见表1
表1实施例和对比例的轻烃燃料性能测定结果
对实施例1~2和对比例1~2的轻烃燃料进行抗爆性等性能测试，测试结果见表2
表2实施例和对比例的轻烃燃料抗爆性等性能测定结果
Claims (5)
1.一种轻烃燃料的清洁脱硫改性方法，其特征在于，包括以下步骤：（1）将3~5份的纯度在98％以上的轻烃放入陶罐内，然后加入0.01~0.2份清洁剂和0.01~0.2份防老剂，搅拌40分钟后得A混合液；（2）按重量份数计将轻烃37~39份、甲醇37~39份、二甲醚11~13份、2-甲基-1-丁烯5~7份、催化剂3.1~5.1份，反应温度400~425℃、反应压力为常压；甲醇的重量空速为1.8~2.2/h，轻烃的重量空速为0.22~0.36/h，高纯氮300~350ml/min，反应时间6~12小时，得低碳轻烃；（3）将49.9份低碳轻烃放在不锈钢罐内，然后向该不锈钢罐内加入5~10份的复合添加剂混合，搅拌5~8分钟得B混合液；（4）再向A混合液所在的陶罐内加入6~7份的甲基叔丁基醚，混合后搅拌5~8分钟，然后将不锈钢罐内B混合液倒入A混合液所在的陶罐内，混合后搅拌5~8分钟，密封24小时即得的清洁脱硫后的轻烃燃料。
2.根据权利要求1所述的一种轻烃燃料的清洁脱硫改性方法，其特征在于，所述催化剂的制备方法为将质量分数85%磷酸13.83~14.89份，溶于120~130份去离子水中，搅拌均匀，向该磷酸水溶液加入二氧化锆29.12份，搅拌，使之溶解成均匀溶液，另加46~56份的正硅酸乙酯、44~58份三乙醇胺、16~18.3份二乙醇胺，在激烈搅拌下将含二氧化硅硅溶胶等物质的溶液加入到磷酸-锆溶液中胶，将凝胶放入压力为2~3MPa不锈钢高压釜中，在120℃晶化96小时，然后将反应产物过滤、洗涤，在120℃干燥2小时即得催化剂的活性组分A，再称取ZSM-5型分子筛22~25份，浸泡在质量分数1~1.5%谷氨酸钠水溶液中，50℃浸泡2~6小时，过滤用去离子水洗涤，抽滤游离水，再浸泡于质量分数0.45%的氢氧化钠水溶液中，过滤用去离子水洗涤，抽滤游离水，将上述分子筛放入一个带有过滤板的循环槽中，加入0.05M的硝酸镧溶液中，在室温下以0.02m/s流速循环浸泡12小时，升温至80℃搅拌2h，处理好的样品经过去离子水反复洗涤至中性，经抽滤，烘干后，在空气气氛中以5℃/min的速度升至550℃，焙烧4h，焙烧后的样品以质量浓度为6~8%的硝酸铵溶液在80℃交换2h后过滤，如此重复4次后在120℃下干燥并于550℃焙烧2h，即活性组分B，称取含31%二氧化硅的硅溶胶212~220份、偏铝酸钠16~18份、去离子水230~240份搅拌均匀，在激烈搅拌下加入上述制备的活性组分A30~56份、活性组分B16~20份，经喂料机调节进料速度，喷雾干燥得到一定粒度分布催化剂。
3.根据权利要求1所述的一种轻烃燃料的清洁脱硫改性方法，其特征在于，所述步骤（1）的防老剂为的鱼精蛋白、茶多酚、栎皮酮中的其中一种或多种。
4.根据权利要求1所述的一种轻烃燃料的清洁脱硫改性方法，其特征在于，所述步骤（3）的复合添加剂的组成为增进剂和清净剂按重量份数比1∶1组成，增进剂成分由二茂铁基叔丁基甲醇22~33份、三甲硅氧甲基二茂铁8~13份、N-丁基二茂铁丁酰胺4~7份共溶混合组成，清净剂由占清净剂含量98~99％的主剂和占清净剂1~2％的辅助剂组成；主剂清净分散剂的成分为甲醇25~28份、二茂铁甲醇25~27份、环烷酸锌1.5~3份，辅助剂由抗氧剂2~4份、抗乳化剂1~2份、防锈剂0.5~1份、减磨剂0.2~0.4份组成，其中的抗氧剂：选用叔丁基对羟基茴香醚，抗乳化剂：烯丙氧基壬基苯氧基丙醇聚氧乙烯醚硫酸铵，防锈剂：磷酸三甲酚酯，减磨剂：二丁基二硫代氨基甲酸钼。
5.根据权利要求1所述的一种轻烃燃料的清洁脱硫改性方法，其特征在于，所述步骤（1）的清洁剂为甲基环戊二烯三羰基锰或甲基环戊二烯三羰基锰的其中一种。
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