CN113980702B - Environment-friendly process method for producing gasoline for vehicles from naphtha - Google Patents
Environment-friendly process method for producing gasoline for vehicles from naphtha Download PDFInfo
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- CN113980702B CN113980702B CN202111613140.2A CN202111613140A CN113980702B CN 113980702 B CN113980702 B CN 113980702B CN 202111613140 A CN202111613140 A CN 202111613140A CN 113980702 B CN113980702 B CN 113980702B
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- catalyst
- reaction
- component
- naphtha
- oil
- Prior art date
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- 239000003502 gasoline Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 81
- 230000008569 process Effects 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- 239000003921 oil Substances 0.000 claims abstract description 56
- 238000002156 mixing Methods 0.000 claims abstract description 29
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010692 aromatic oil Substances 0.000 claims abstract description 24
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 20
- 239000003245 coal Substances 0.000 claims abstract description 19
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 16
- 238000002407 reforming Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims description 164
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 113
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 103
- 238000002360 preparation method Methods 0.000 claims description 83
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 75
- 229910052621 halloysite Inorganic materials 0.000 claims description 75
- 239000007787 solid Substances 0.000 claims description 62
- 229910052739 hydrogen Inorganic materials 0.000 claims description 58
- 239000001257 hydrogen Substances 0.000 claims description 58
- 239000002071 nanotube Substances 0.000 claims description 56
- 229910052593 corundum Inorganic materials 0.000 claims description 54
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 54
- 239000002253 acid Substances 0.000 claims description 53
- 230000002829 reductive effect Effects 0.000 claims description 50
- 238000010438 heat treatment Methods 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 238000001833 catalytic reforming Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 28
- 150000002431 hydrogen Chemical class 0.000 claims description 27
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 26
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 23
- 238000006317 isomerization reaction Methods 0.000 claims description 23
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 230000009471 action Effects 0.000 claims description 18
- 230000000087 stabilizing effect Effects 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 13
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000006057 reforming reaction Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 53
- 239000000047 product Substances 0.000 description 35
- 239000007864 aqueous solution Substances 0.000 description 16
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- 230000008021 deposition Effects 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- -1 hydrogen alkane Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention provides an environment-friendly process method for producing gasoline for vehicles from naphtha, belonging to the technical field of coal chemical industry. Catalytic hydrogenation is carried out on coal indirect liquefied naphtha, and C is obtained by classification4‑Component C5/C6Component (A) and (C)7+Component (B) in which5/C6The component is subjected to hydroisomerization reaction to obtain an isomeric alkane oil C7+Reforming the components to obtain aromatic oil, and proportionally mixing C4‑The components, the isomeric alkane oil and the aromatic oil are mixed evenly to obtain the motor gasoline. The environment-friendly process method for producing the ultra-low sulfur and olefin-free high-octane number clean motor gasoline has the advantages of simple method, mild reaction conditions, low cost, capability of obviously improving the octane number of the motor gasoline and the like, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of coal chemical industry, in particular to an environment-friendly process method for producing gasoline for vehicles from naphtha.
Background
Clean fuel production has been one of the major tasks of oil refinery enterprises. However, with the shortage of petroleum resources, the price of crude oil is continuously rising, and how to utilize limited resources to produce products required by the market to the maximum extent is a challenge for oil refining enterprises. The main components in the gasoline pool are catalytic cracking gasoline, catalytic reforming gasoline, alkylated gasoline and C5/C6Isomerizing gasoline. Except that catalytically cracked gasoline is obtained from heavier feedstocks, it is obtained by conversion from naphtha or light hydrocarbons.
The coal-based naphtha is classified into a direct coal-liquefied naphtha and an indirect coal-liquefied naphtha. Because a large amount of single and double olefins are generated in the coal indirect liquefaction process, the part of olefins are converted into normal paraffin after hydrogenation saturation, and the normal paraffin content in the coal indirect liquefied naphtha synthesized by the product is generally about 85 percent. Lower octane number of n-alkanes, nC6Has an octane number (RON) of 26, nC7Has an octane number (RON) of 0. The existence of a large amount of normal paraffin affects the octane number of the synthetic naphtha to be lower than 40, and the synthetic naphtha cannot be delivered as a gasoline product, thereby having negative influence on coal-to-liquid production enterprises.
The proportion of catalytic cracking gasoline in gasoline pools in China is high, and the proportion of alkylate and isomerized oil is low, so that the contents of olefin and aromatic hydrocarbon in the gasoline are high, and the octane number is low. With the upgrading of the quality standard of the motor gasoline, many enterprises consider converting straight-run light naphtha with low octane number into high-octane light naphtha rich in isomeric hydrocarbon to improve the blending proportion of the isomeric light naphtha in the gasoline pool of the whole plant, thereby improving the octane number of the gasoline pool of the whole plant and improving the octane number distribution of the gasoline pool.
CN101570698A proposes a catalytic conversion method of naphtha, which cuts naphtha raw material into light fraction, middle fraction and heavy fraction, and performs light hydrocarbon isomerization reaction on the light fraction, performs staged reforming on the middle fraction, and performs light-conversion reaction on the heavy fraction to generate light aromatic hydrocarbon and high octane gasoline component. Wherein, the sectional reforming subdivides the middle distillate and then carries out aromatization reaction, reforming reaction and non-hydrogenation modification reaction respectively.
CN108192666A discloses a method for preparing high-octane gasoline by naphtha hydrocracking. The naphtha is pretreated to remove impurities, then the naphtha is primarily fractionated to obtain light naphtha fraction and heavy naphtha fraction, the heavy naphtha fraction is subjected to hydrogenation isomerization cracking reaction treatment, and the high-octane gasoline is obtained after gas-liquid separation.
US6338791B1 discloses a process for producing high octane gasoline by a process combining hydroisomerization and separation of a C5-C8 naphtha fraction, which increases the branch degree of the isomerized hydrocarbons by separating normal isomerized hydrocarbons and performing multistage isomerization to increase the octane number of the naphtha.
When the technology is used for improving the octane number of naphtha, naphtha raw materials are usually required to be pretreated, and fractions are divided into different fractions to be respectively treated, and in addition, in the prior art, a noble metal catalyst is mostly adopted to carry out hydroisomerization treatment on light distillate oil, and hydrocracking or catalytic reforming treatment is carried out on heavy fraction oil, so that the defects of complex flow and high energy consumption are caused.
Disclosure of Invention
The invention aims to provide an environment-friendly process method for producing the automotive gasoline from naphtha, an environment-friendly process method for producing ultra-low sulfur and olefin-free high-octane number clean automotive gasoline, and the method has the advantages of simplicity, mild reaction conditions, low cost, capability of obviously improving the octane number of the automotive gasoline and the like, and has wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides an environment-friendly process method for producing gasoline for vehicles from naphtha, which is characterized in that coal indirect liquefied naphtha is subjected to catalytic hydrogenation and then is graded to obtain C4-Component C5/C6Component (A) and (C)7+Component (B) in which5/C6The component is subjected to hydroisomerization reaction to obtain an isomeric alkane oil C7+Reforming the components to obtain aromatic oil, and proportionally mixing C4-The components, the isomeric alkane oil and the aromatic oil are mixed evenly to obtain the motor gasoline.
As a further improvement of the invention, the method specifically comprises the following steps:
s1, pretreatment of raw materials: subjecting coal indirect liquefied naphtha to catalytic hydrogenation process, and fractionating by a fractionating tower to obtain C4-Component C5/C6Component (A) and (C)7+Preparing components;
s2, hydroisomerization process: c is to be5/C6Mixing the components with hydrogen, carrying out isomerization reaction under the action of a first catalyst, separating the product after passing through a first stabilizing tower, and partially separating the non-isomerized C5/C6The component is subjected to hydroisomerization process again to obtain the isomerized C5/C6The components are combined to obtain isomeric alkane oil;
s3, reforming process: c is to be7+After the components are mixed with hydrogen, performing multi-stage catalytic reforming reaction under the action of a second catalyst, and separating a product by a second stabilizing tower to obtain aromatic oil;
s4, preparation of the motor gasoline: 50-60 parts by weight of aromatic oil obtained in step S3, 30-40 parts by weight of isoparaffin oil obtained in step S2 and 3-7 parts by weight of C obtained in step S14-The components are mixed to obtain the motor gasoline.
As a further improvement of the invention, the catalyst of the catalytic hydrogenation process in the step S1 is at least one of HC-110, HC-170, HC-115, HC-125 and HC-29; the tower top component of the fractionating tower is C4-Component A, a first-line component of the column is C5/C6Component (C) is the bottom component of the tower7+And (4) components.
As a further improvement of the invention, the first catalyst is WO3/ZrO2/Al2O3The preparation method of the solid strong acid loaded Mg-doped Pt/Ni bimetallic catalyst comprises the following steps: dropwise adding the ammonium metatungstate solution into a mixed solution of zirconium oxychloride and aluminum isopropoxide while stirring, adjusting the pH value of the solution to 9-10, heating to 80-90 ℃, reacting for 0.5-1h, centrifuging, washing the solid precipitate with deionized water, filtering, drying and roasting to obtain WO3/ZrO2/Al2O3A solid strong acid support; to dissolve H2PtCl6And NiCl2To the solution of (3) adding MgCl2Mixing, addingWO3/ZrO2/Al2O3Carrying out ultrasonic dispersion on a solid strong acid carrier for 0.5-1h, heating to 80-90 ℃ for reaction for 1-2h, concentrating under reduced pressure, filtering, and drying to obtain WO3/ZrO2/Al2O3A solid strong acid supported Mg doped Pt/Ni bimetallic catalyst.
As a further improvement of the invention, the mass ratio of the ammonium metatungstate to the zirconium oxychloride to the aluminum isopropoxide is 10: (4-7): (2-3); said H2PtCl6、NiCl2、MgCl2The mass ratio of (3-7): (2-3): (0.01-0.05); the roasting temperature is 300-450 ℃.
As a further improvement of the invention, the hydroisomerization reaction in step S2 is carried out in a fixed-bed hydroisomerization reactor, and C is5/C6After the components are mixed with hydrogen, the mixture is heated to the reaction temperature of 140 ℃ and 190 ℃, the pressure is 1.4-2MPa, the volume space velocity is 0.5-1.5/h, and the volume ratio of hydrogen to oil is (1-3): 1, carrying out isomerization reaction under the action of a first catalyst, separating products after the products pass through a first stabilizing tower, and partially separating non-isomerized C5/C6The component is subjected to hydroisomerization process again to obtain the isomerized C5/C6And (4) combining the components to obtain the isomeric alkane oil.
As a further improvement of the invention, the second catalyst is a gamma-alumina/halloysite nanotube-supported Sn-doped Pt/Ni bimetallic catalyst, and the preparation method is as follows: dispersing halloysite nanotubes in an ethanol aqueous solution, adding aluminum isopropoxide for dissolving, ultrasonically dispersing uniformly, heating to 60-80 ℃ for reaction, removing the solvent under reduced pressure to obtain a precursor, and roasting and grinding the precursor to obtain a gamma-alumina/halloysite nanotube carrier; h is to be2PtCl6And NiCl2Adding SnCl into the solution2And after uniformly mixing, adding a gamma-alumina/halloysite nanotube carrier, performing ultrasonic dispersion for 0.5-1h, heating to 75-85 ℃ for reaction for 1-2h, performing reduced pressure concentration, filtering and drying to obtain the gamma-alumina/halloysite nanotube loaded Sn doped Pt/Ni bimetallic catalyst.
As a further improvement of the present inventionThe mass ratio of the halloysite nanotube to the aluminum isopropoxide is (3-5): 10; said H2PtCl6、NiCl2And SnCl2The mass ratio of (A) to (B) is 10: (1-2): (0.5-1); the roasting temperature is 500-600 ℃; the ethanol content in the ethanol water solution is 50-70wt%, and the balance is water.
As a further improvement of the present invention, the multistage catalytic reforming reaction described in step S3 is carried out in a fixed bed catalytic reforming reactor, and C is7+After the components are mixed with hydrogen, the mixture is heated to the temperature of 490-510 ℃, the pressure is 1-2MPa, the volume space velocity is 2-4/h, and the volume ratio of hydrogen to oil is (500-750): 1, after entering a first-stage fixed bed catalytic reforming reactor to react under the action of a second catalyst, mixing a product with hydrogen, heating to the temperature of 420-450 ℃, wherein the pressure is 1.2-1.7MPa, the volume space velocity is 2-4/h, and the volume ratio of hydrogen to oil is (550-600): 1, entering a two-stage fixed bed catalytic reforming reactor for reaction, and separating a product by a second stabilizing tower to obtain aromatic oil.
The invention further protects the motor gasoline prepared by the environment-friendly process method for producing the motor gasoline from the naphtha, wherein the octane number of the motor gasoline is 94-96, and the density of the motor gasoline is 750-760kg/m3(20 ℃), lead content less than 0.001g/L, iron content less than 0.002g/L, manganese content less than 0.002g/L, and sulfur content less than 0.0001 g/L.
The invention has the following beneficial effects: according to the invention, firstly, the indirect coal liquefaction naphtha is subjected to a catalytic hydrogenation process, so that S, N, O, metal and other impurities in the naphtha are removed, the oil quality is improved, the catalyst poisoning in the subsequent reaction is avoided, the activity of the catalyst is reduced, and thus high-quality oil products are obtained, and the selected HC series catalyst is a non-noble metal catalyst, so that the catalyst has good effect and low cost, and is safe and environment-friendly;
after the hydroisomerization reaction is carried out in step S2, the obtained isomerized paraffin oil has high yield and low sulfur content, does not contain olefin, aromatic hydrocarbon and benzene, has obviously improved octane number and low octane number sensitivity compared with the original straight-chain paraffin, can improve the front-end octane number of the gasoline, and ensures that the distillation range and the octane number of the gasoline are reasonably distributed, thereby improving the starting performance of an engine; the invention adoptsThe first catalyst prepared by precipitation/sol-gel/impregnation method is an isomerization catalyst WO3/ZrO2/Al2O3After the solid strong acid loaded Mg-doped Pt/Ni bimetallic catalyst is coprecipitated by ammonium metatungstate and zirconium oxychloride, aluminum isopropoxide is subjected to sol-gel reaction and then is roasted to obtain WO3/ZrO2/Al2O3Solid strong acid carrier, sol-gel reaction generated Al2O3The carrier has large specific surface area, large aperture, concentrated aperture and better thermal stability, the service life of the catalyst is further prolonged, the carrier has large specific surface area, a large amount of heavy metal catalyst is impregnated and complexed to adsorb, Mg is further doped, the activity of the catalyst can be obviously improved, the catalyst is a solid strong acid type Pt/Ni loaded bimetallic catalyst, compared with the common sulfuric acid catalyst, the catalyst has good thermal stability, no component loss occurs in the oxidation reduction atmosphere, the reaction temperature of the isomerization reaction can be obviously reduced, the isomerization reaction can be completed only at 190 ℃ of 140 ℃., the octane number of the obtained product is obviously improved, the octane number is improved by more than 10 units, the isomerization rate is high and can reach 97-98%, the volume ratio of the hydrogen alkane can be effectively reduced, the cost is reduced, the isomerization reaction condition is simplified, and the catalyst has good stability, the service life is long. Compared with a single Pt catalyst or a single Ni catalyst, the Pt/Ni bimetallic catalyst has lower reaction energy barrier, so that the isomerization reaction can be catalyzed more quickly and better.
After the reforming reaction is carried out in the step S3, the contents of naphthenic hydrocarbon and aromatic hydrocarbon in the product oil can be obviously improved, the octane number is further improved, the two-stage method is adopted for reforming, the first-stage reaction mainly comprises the dehydrogenation of the naphthenic hydrocarbon and is a strong endothermic reaction, the reaction temperature is higher, the second-stage reaction mainly comprises the cyclization reaction of the naphthenic hydrocarbon and the hydrocracking reaction, the former is an endothermic reaction, and the latter is an exothermic reaction, therefore, the reaction can be finished at a relatively lower reaction temperature, in the process, the temperature is not too high, the polycyclic aromatic hydrocarbon is easy to generate and is changed into carbon deposition after the later combustion, and once the carbon deposition is generated, the carbon deposition stays on the surface of the catalyst permanently to intensify the coking and inactivation of the catalyst, thereby influencing the reaction process. Go further into steadyAfter the device is fixed, hydrogen and low boiling point liquefied gas are removed to obtain aromatic oil. The second catalyst prepared by the invention is a reforming reaction catalyst gamma-alumina/halloysite nanotube loaded Sn-doped Pt/Ni bimetallic catalyst, wherein the carrier halloysite nanotube is a catalyst capable of effectively inhibiting carbon deposition, and the nano-scale tubular structure of the halloysite nanotube has a good domain-limiting effect; and on the top of the halloysite nanotube, the catalyst particles are not covered by carbon and can adsorb cracked carbon atoms, so that the carbon atoms are diffused on the surface of the catalyst or penetrate through the catalyst to enter the halloysite nanotube, the carbon deposition is inhibited, and meanwhile, the gamma-alumina/halloysite nanotube is generated by sol-gel reaction, wherein gamma-Al is2O3The catalyst has the advantages of large specific surface area, large aperture, concentrated aperture, good thermal stability, further prolonged service life, large specific surface area, impregnation, complexation and adsorption of a large amount of heavy metal catalysts, formation of a large amount of ionic state, high-temperature active centers of Pt, Ni and Sn in an ultrahigh dispersion state or discrete metal state and a combined metal low-temperature active center in a common dispersion state, provision of a large amount of hydrogen reaction active centers, and efficient completion of various catalytic reforming reactions, thereby achieving an efficient catalytic effect. Compared with a single Pt catalyst or a single Ni catalyst, the Pt/Ni bimetallic catalyst has lower reaction energy barrier, so that the isomerization reaction can be catalyzed more quickly and better.
In the Sn doped Pt/Ni bimetallic catalyst, after Sn is introduced, the dispersion degree of Pt metal is improved, the number of low-temperature hydrogen adsorption centers is not changed greatly, but the high-temperature centers are increased remarkably, and under the existence of high temperature and hydrogen, on one hand, Sn is reduced into low-valence oxide, and forms an oxygen-deficient surface complex Pt- [ SnO ] with high-temperature hydrogen adsorption capacity with Ptx]At the same time, SnO2Can also be reduced to zero-valent Sn to form Pt with PtxSnyThe alloy suppresses the ability of Pt to adsorb hydrogen. On the other hand, Sn interacts with the gamma-alumina carrier to form tetravalent (SnO)2·Al2O3) And divalent (SnAl)2O5) Sn fromThereby improving the catalytic selectivity and catalytic activity and further improving the yield of the aromatic hydrocarbon.
The environment-friendly process method for producing the ultra-low sulfur and olefin-free high-octane number clean motor gasoline has the advantages of simple method, mild reaction conditions, low cost by adopting the Ni-based catalyst compared with a heavy metal catalyst, capability of obviously improving the octane number of the motor gasoline, wide application prospect and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Halloysite nanotubes are provided by processing Lingshou county Yanbo mineral products, with a product number of 15, grade 1, and SiO2 45.8%、Al2O3 37.3%、Fe2O3 0.5%、K2O 0.11%、TiO2 0.39 percent, CaO and MgO with low content, the ignition loss of 14.50 percent, white or peach-red color, the refractoriness of 1730 ℃, the hardness of 1-2 and the density of 2.0-2.2g/cm3The crystal form is 100% of all natural nano-tubular structure, the diameter is 0.1-0.4 μm, and the length is less than 0.5 μm. Other reagents are all made in China and analytically pure or chemically pure.
The main physicochemical properties of the coal-derived liquefied naphtha referred to in the present invention are shown in table 1:
TABLE 1
Preparation example 1 WO3/ZrO2/Al2O3Preparation of solid strong acid loaded Mg-doped Pt/Ni bimetallic catalyst
Dropwise adding 10g of ammonium metatungstate solution into 100mL of mixed solution of 4g of zirconium oxychloride and 2g of aluminum isopropoxide under stirring, adjusting the pH value of the solution to 9, heating to 80 ℃, reacting for 0.5h, and reacting at 3000rCentrifuging for 10min, washing the solid precipitate with deionized water, filtering, drying at 80 deg.C for 2h, and calcining at 300 deg.C for 2h to obtain WO3/ZrO2/Al2O3A solid strong acid support; to dissolve 0.6g H2PtCl6And 0.4g NiCl2To 20mL of the aqueous solution of (1) was added 0.02g of MgCl2After mixing well, 5g of WO was added3/ZrO2/Al2O3Carrying out ultrasonic dispersion on a solid strong acid carrier at 1000W for 0.5h, heating to 80 ℃, reacting for 1h, concentrating under reduced pressure to half of the original volume, filtering, and drying at 80 ℃ for 2h to obtain WO3/ZrO2/Al2O3A solid strong acid supported Mg doped Pt/Ni bimetallic catalyst.
Preparation example 2 WO3/ZrO2/Al2O3Preparation of solid strong acid loaded Mg-doped Pt/Ni bimetallic catalyst
Dropwise adding 10g of ammonium metatungstate solution into 100mL of mixed solution of 7g of zirconium oxychloride and 3g of aluminum isopropoxide while stirring, adjusting the pH value of the solution to 10, heating to 90 ℃, reacting for 1h, centrifuging at 3000r/min for 10min, washing solid precipitate with deionized water, filtering, drying at 80 ℃ for 2h, and roasting at 450 ℃ for 2h to obtain WO3/ZrO2/Al2O3A solid strong acid support; to dissolve 1.4g H2PtCl6And 0.6g NiCl2To 20mL of the aqueous solution of (1) was added 0.1g of MgCl2After mixing well, 5g of WO was added3/ZrO2/Al2O3Carrying out ultrasonic dispersion on a solid strong acid carrier at 1000W for 1h, heating to 90 ℃ for reaction for 2h, concentrating under reduced pressure to half of the original volume, filtering, and drying at 80 ℃ for 2h to obtain WO3/ZrO2/Al2O3A solid strong acid supported Mg doped Pt/Ni bimetallic catalyst.
Preparation example 3 WO3/ZrO2/Al2O3Preparation of solid strong acid loaded Mg-doped Pt/Ni bimetallic catalyst
Dropwise adding 10g of ammonium metatungstate solution into 100mL of mixed solution of 5g of zirconium oxychloride and 2.5g of aluminum isopropoxide under stirring, adjusting the pH value of the solution to 9.5, heating to 85 ℃, reacting for 1h, centrifuging at 3000r/min for 10min, washing solid precipitate with deionized waterWashing, filtering, drying at 80 deg.C for 2h, and calcining at 400 deg.C for 2h to obtain WO3/ZrO2/Al2O3A solid strong acid support; to dissolve 0.8g H2PtCl6And 0.5g NiCl2To 20mL of the aqueous solution of (1) was added 0.06g of MgCl2After mixing well, 5g of WO was added3/ZrO2/Al2O3Dispersing solid strong acid carrier with 1000W ultrasound for 1h, heating to 85 deg.C for 1.5h, concentrating under reduced pressure to half of original volume, filtering, and drying at 80 deg.C for 2h to obtain WO3/ZrO2/Al2O3A solid strong acid supported Mg doped Pt/Ni bimetallic catalyst.
Comparative preparation example 1
Compared with preparation example 3, no aluminum isopropoxide was added, and other conditions were not changed.
Dropwise adding 11.7g of ammonium metatungstate solution into 100mL of 5.8g of zirconium oxychloride aqueous solution under stirring, adjusting the pH value of the solution to 9.5, heating to 85 ℃, reacting for 1h, centrifuging at 3000r/min for 10min, washing solid precipitate with deionized water, filtering, drying, and roasting at 400 ℃ for 2h to obtain WO3/ZrO2A solid strong acid support; to dissolve 0.8g H2PtCl6And 0.5g NiCl2To 20mL of the aqueous solution of (1) was added 0.06g of MgCl2After mixing well, 5g of WO was added3/ZrO2/Al2O3Dispersing solid strong acid carrier with 1000W ultrasound for 1h, heating to 85 deg.C for 1.5h, concentrating under reduced pressure to half of original volume, filtering, and drying at 80 deg.C for 2h to obtain WO3/ZrO2A solid strong acid supported Mg doped Pt/Ni bimetallic catalyst.
Comparative preparation example 2
In contrast to preparation example 3, no MgCl was added2Other conditions are not changed.
Dropwise adding 10g of ammonium metatungstate solution into 100mL of mixed solution of 5g of zirconium oxychloride and 2.5g of aluminum isopropoxide while stirring, adjusting the pH value of the solution to 9.5, heating to 85 ℃ for reaction for 1h, centrifuging at 3000r/min for 10min, washing solid precipitate with deionized water, filtering, drying at 80 ℃ for 2h, and roasting at 400 ℃ for 2h to obtain WO3/ZrO2/Al2O3A solid strong acid support;will dissolve 0.8g H2PtCl6And 0.56g of NiCl2After mixing well with 20mL of the aqueous solution, 5g of WO was added3/ZrO2/Al2O3Dispersing solid strong acid carrier with 1000W ultrasound for 1h, heating to 85 deg.C for 1.5h, concentrating under reduced pressure to half of original volume, filtering, and drying at 80 deg.C for 2h to obtain WO3/ZrO2/Al2O3A solid strong acid supported Pt/Ni bimetallic catalyst.
Comparative preparation example 3
In contrast to preparation example 3, no NiCl was added2Other conditions are not changed.
Dropwise adding 10g of ammonium metatungstate solution into 100mL of mixed solution of 5g of zirconium oxychloride and 2.5g of aluminum isopropoxide while stirring, adjusting the pH value of the solution to 9.5, heating to 85 ℃ for reaction for 1h, centrifuging at 3000r/min for 10min, washing solid precipitate with deionized water, filtering, drying at 80 ℃ for 2h, and roasting at 400 ℃ for 2h to obtain WO3/ZrO2/Al2O3A solid strong acid support; to dissolve 0.8g H2PtCl6To 20mL of the aqueous solution of (1) was added 0.56g of MgCl2After mixing well, 5g of WO was added3/ZrO2/Al2O3Dispersing solid strong acid carrier with 1000W ultrasound for 1h, heating to 85 deg.C for 1.5h, concentrating under reduced pressure to half of original volume, filtering, and drying at 80 deg.C for 2h to obtain WO3/ZrO2/Al2O3Solid strong acid supported Mg doped Pt catalyst.
Comparative preparation example 4
In contrast to preparation example 3, no MgCl was added2And NiCl2Other conditions are not changed.
Dropwise adding 10g of ammonium metatungstate solution into 100mL of mixed solution of 5g of zirconium oxychloride and 2.5g of aluminum isopropoxide while stirring, adjusting the pH value of the solution to 9.5, heating to 85 ℃ for reaction for 1h, centrifuging at 3000r/min for 10min, washing solid precipitate with deionized water, filtering, drying at 80 ℃ for 2h, and roasting at 400 ℃ for 2h to obtain WO3/ZrO2/Al2O3A solid strong acid support; to dissolve 1.36g H2PtCl620mL of the aqueous solution of (2) was added 5g of WO3/ZrO2/Al2O3Dispersing solid strong acid carrier with 1000W ultrasound for 1h, heating to 85 deg.C for 1.5h, concentrating under reduced pressure to half of original volume, filtering, and drying at 80 deg.C for 2h to obtain WO3/ZrO2/Al2O3A solid strong acid supported Pt catalyst.
Preparation example 4 preparation of a gamma-alumina/halloysite nanotube-supported Sn doped Pt/Ni bimetallic catalyst
Dispersing 3g of halloysite nanotubes in 100mL of 50wt% ethanol aqueous solution, adding 10g of aluminum isopropoxide for dissolving, ultrasonically dispersing for 30min at 1000W, heating to 60 ℃ for reaction, removing the solvent under reduced pressure to obtain a precursor, roasting the precursor at 500 ℃ for 3h, and grinding to obtain a gamma-alumina/halloysite nanotube carrier; will dissolve 1g H2PtCl6And 0.1g NiCl220mL of the solution of (1) was added 0.05g of SnCl2And after uniformly mixing, adding 5g of gamma-alumina/halloysite nanotube carrier, ultrasonically dispersing for 0.5h at 1000W, heating to 75 ℃ for reaction for 1h, concentrating under reduced pressure to half of the original volume, filtering, and drying at 80 ℃ for 2h to obtain the gamma-alumina/halloysite nanotube loaded Sn doped Pt/Ni bimetallic catalyst.
Preparation example 5 preparation of a gamma-alumina/halloysite nanotube-supported Sn doped Pt/Ni bimetallic catalyst
Dispersing 5g of halloysite nanotubes in 100mL of 70wt% ethanol aqueous solution, adding 10g of aluminum isopropoxide for dissolving, ultrasonically dispersing for 30min at 1000W, heating to 80 ℃ for reaction, removing the solvent under reduced pressure to obtain a precursor, roasting the precursor at 600 ℃ for 3h, and grinding to obtain a gamma-alumina/halloysite nanotube carrier; will dissolve 1g H2PtCl6And 0.2g of NiCl220mL of the solution of (1) was added 0.1g of SnCl2And after uniformly mixing, adding 5g of gamma-alumina/halloysite nanotube carrier, ultrasonically dispersing for 1h at 1000W, heating to 85 ℃ for reaction for 2h, concentrating under reduced pressure to half of the original volume, filtering, and drying at 80 ℃ for 2h to obtain the gamma-alumina/halloysite nanotube loaded Sn doped Pt/Ni bimetallic catalyst.
Preparation example 6 preparation of a gamma-alumina/halloysite nanotube-supported Sn doped Pt/Ni bimetallic catalyst
Dispersing 4g of halloysite nanotubes in 100mL of 60wt% ethanol aqueous solution, adding 10g of aluminum isopropoxide for dissolving, ultrasonically dispersing for 30min at 1000W, heating to 70 ℃ for reaction, removing the solvent under reduced pressure to obtain a precursor, roasting the precursor at 550 ℃ for 3h, and grinding to obtain a gamma-alumina/halloysite nanotube carrier; will dissolve 1g H2PtCl6And 0.15g NiCl220mL of the solution of (1) was added 0.07g of SnCl2And after uniformly mixing, adding 5g of gamma-alumina/halloysite nanotube carrier, ultrasonically dispersing for 1h at 1000W, heating to 80 ℃ for reaction for 1.5h, concentrating under reduced pressure to half of the original volume, filtering, and drying at 80 ℃ for 2h to obtain the gamma-alumina/halloysite nanotube loaded Sn doped Pt/Ni bimetallic catalyst.
Comparative preparation example 5
Compared with preparation example 6, no halloysite nanotube was added, and other conditions were not changed.
Adding 14g of aluminum isopropoxide into 100mL of 60wt% ethanol aqueous solution, dissolving, ultrasonically dispersing for 30min at 1000W, heating to 70 ℃ for reaction, decompressing and removing the solvent to obtain a precursor, roasting the precursor at 550 ℃ for 3h, and grinding to obtain the gamma-alumina carrier; will dissolve 1g H2PtCl6And 0.15g NiCl220mL of the solution of (1) was added 0.07g of SnCl2And after uniformly mixing, adding 5g of gamma-alumina carrier, ultrasonically dispersing for 1h at 1000W, heating to 80 ℃, reacting for 1.5h, concentrating under reduced pressure to half of the original volume, filtering, and drying for 2h at 80 ℃ to obtain the gamma-alumina-loaded Sn-doped Pt/Ni bimetallic catalyst.
Comparative preparation example 6
Compared with preparation example 6, aluminum isopropoxide was not added, and other conditions were not changed.
Dispersing 14g of halloysite nanotubes in 100mL of 60wt% ethanol aqueous solution, performing ultrasonic dispersion at 1000W for 30min, heating to 70 ℃ for reaction, removing the solvent under reduced pressure to obtain a precursor, roasting the precursor at 550 ℃ for 3h, and grinding to obtain a halloysite nanotube carrier; will dissolve 1g H2PtCl6And 0.15g NiCl220mL of the solution of (1) was added 0.07g of SnCl2After being mixed evenly, 5g of halloysite nanotube carrier is added and 1000W ultrasonic dispersion is carried outHeating to 80 ℃ for reaction for 1.5h, concentrating under reduced pressure to half of the original volume, filtering, and drying at 80 ℃ for 2h to obtain the halloysite nanotube-loaded Sn-doped Pt/Ni bimetallic catalyst.
Comparative preparation example 7
In comparison with preparation example 6, no SnCl was added2Other conditions are not changed.
Dispersing 4g of halloysite nanotubes in 100mL of 60wt% ethanol aqueous solution, adding 10g of aluminum isopropoxide for dissolving, ultrasonically dispersing for 30min at 1000W, heating to 70 ℃ for reaction, removing the solvent under reduced pressure to obtain a precursor, roasting the precursor at 550 ℃ for 3h, and grinding to obtain a gamma-alumina/halloysite nanotube carrier; will dissolve 1g H2PtCl6And 0.22g NiCl2After uniformly mixing the solution of 20mL, adding 5g of gamma-alumina/halloysite nanotube carrier, ultrasonically dispersing for 1h at 1000W, heating to 80 ℃ for reaction for 1.5h, concentrating under reduced pressure to half of the original volume, filtering, and drying for 2h at 80 ℃ to obtain the gamma-alumina/halloysite nanotube supported Pt/Ni bimetallic catalyst.
Comparative preparation example 8
In comparison with preparation example 6, no NiCl was added2Other conditions are not changed.
Dispersing 4g of halloysite nanotubes in 100mL of 60wt% ethanol aqueous solution, adding 10g of aluminum isopropoxide for dissolving, ultrasonically dispersing for 30min at 1000W, heating to 70 ℃ for reaction, removing the solvent under reduced pressure to obtain a precursor, roasting the precursor at 550 ℃ for 3h, and grinding to obtain a gamma-alumina/halloysite nanotube carrier; will dissolve 1g H2PtCl620mL of the solution of (1) was added 0.22g of SnCl2And after uniformly mixing, adding 5g of gamma-alumina/halloysite nanotube carrier, ultrasonically dispersing for 1h at 1000W, heating to 80 ℃ for reaction for 1.5h, concentrating under reduced pressure to half of the original volume, filtering, and drying at 80 ℃ for 2h to obtain the gamma-alumina/halloysite nanotube-loaded Sn-doped Pt catalyst.
Comparative preparation example 9
In comparison with preparation example 6, no SnCl was added2And NiCl2Other conditions are not changed.
4g of halloysite nanotubes dispersed in 100mL of 6Adding 10g of aluminum isopropoxide into 0wt% ethanol water solution for dissolving, performing ultrasonic dispersion at 1000W for 30min, heating to 70 ℃ for reaction, removing the solvent under reduced pressure to obtain a precursor, roasting the precursor at 550 ℃ for 3h, and grinding to obtain the gamma-alumina/halloysite nanotube carrier; will dissolve 1.22g H2PtCl6Adding 5g of gamma-alumina/halloysite nanotube carrier into 20mL of the solution, ultrasonically dispersing for 1h at 1000W, heating to 80 ℃, reacting for 1.5h, concentrating under reduced pressure to half of the original volume, filtering, and drying for 2h at 80 ℃ to obtain the gamma-alumina/halloysite nanotube-supported Pt catalyst.
Example 1
The embodiment provides an environment-friendly process method for producing gasoline for vehicles from naphtha, which specifically comprises the following steps:
s1, pretreatment of raw materials: subjecting coal indirect liquefied naphtha to catalytic hydrogenation process of catalyst HC-170, and fractionating by fractionating tower to obtain C4-Component C5/C6Component (A) and (C)7+Component C of the top component of the fractionating tower4-Component A, a first-line component of the column is C5/C6Component (C) is the bottom component of the tower7+Preparing components;
s2, hydroisomerization process: in a fixed bed hydroisomerization reactor, feeding C5/C6After the components are mixed with hydrogen, the mixture is heated to 140 ℃ and reacts, the pressure is 1.4MPa, the volume space velocity is 0.5/h, and the volume ratio of hydrogen to oil is 1: 1, WO prepared in preparation example 13/ZrO2/Al2O3Carrying out isomerization reaction under the action of a solid strong acid loaded Mg-doped Pt/Ni bimetallic catalyst, separating a product after the product passes through a first stabilizing tower, and partially separating non-isomerized C5/C6The component is subjected to hydroisomerization process again to obtain the isomerized C5/C6The components are combined to obtain isomeric alkane oil;
s3, reforming process: in a fixed bed catalytic reforming reactor, adding C7+After the components are mixed with hydrogen, the mixture is heated to 490 ℃, the pressure is 1MPa, the volume space velocity is 2/h, and the volume ratio of hydrogen to oil is 500: 1, Gamma-alumina/halloysite nanotube Supported Sn doped Pt/Ni bimetallic prepared in preparation example 4After entering a first-stage fixed bed catalytic reforming reactor to react under the action of a catalyst, mixing a product with hydrogen, heating to 420 ℃, wherein the pressure is 1.2MPa, the volume space velocity is 2/h, and the volume ratio of hydrogen to oil is 550: 1, entering a two-stage fixed bed catalytic reforming reactor for reaction, and separating a product by a second stabilizing tower to obtain aromatic oil;
s4, preparation of the motor gasoline: 50 parts by weight of the aromatic oil obtained in step S3, 30 parts by weight of the isoparaffin oil obtained in step S2, and 3 parts by weight of C in step S14-The components are mixed to obtain the motor gasoline.
Example 2
The embodiment provides an environment-friendly process method for producing gasoline for vehicles from naphtha, which specifically comprises the following steps:
s1, pretreatment of raw materials: subjecting coal indirect liquefied naphtha to catalytic hydrogenation process of catalyst HC-110, and fractionating by fractionating tower to obtain C4-Component C5/C6Component (A) and (C)7+Component C of the top component of the fractionating tower4-Component A, a first-line component of the column is C5/C6Component (C) is the bottom component of the tower7+Preparing components;
s2, hydroisomerization process: in a fixed bed hydroisomerization reactor, feeding C5/C6After the components are mixed with hydrogen, the mixture is heated to the reaction temperature of 190 ℃, the pressure is 2MPa, the volume space velocity is 1.5/h, and the volume ratio of hydrogen to oil is 3: WO 1 prepared in preparation example 23/ZrO2/Al2O3Carrying out isomerization reaction under the action of a solid strong acid loaded Mg-doped Pt/Ni bimetallic catalyst, separating a product after the product passes through a first stabilizing tower, and partially separating non-isomerized C5/C6The component is subjected to hydroisomerization process again to obtain the isomerized C5/C6The components are combined to obtain isomeric alkane oil;
s3, reforming process: in a fixed bed catalytic reforming reactor, adding C7+After the components are mixed with hydrogen, heating to 510 ℃, wherein the pressure is 2MPa, the volume space velocity is 4/h, and the volume ratio of hydrogen to oil is 750: 1, Gamma-alumina/halloysite nanotube Supported Sn doped Pt/Ni bimetallic catalyst prepared in preparation example 5After entering a first-stage fixed bed catalytic reforming reactor to react under the action, mixing a product with hydrogen, heating to 450 ℃, wherein the pressure is 1.7MPa, the volume space velocity is 4/h, and the volume ratio of hydrogen to oil is 600: 1, entering a two-stage fixed bed catalytic reforming reactor for reaction, and separating a product by a second stabilizing tower to obtain aromatic oil;
s4, preparation of the motor gasoline: 60 parts by weight of the aromatic oil obtained in step S3, 40 parts by weight of the isoparaffin oil obtained in step S2, and 7 parts by weight of C in step S14-The components are mixed to obtain the motor gasoline.
Example 3
The embodiment provides an environment-friendly process method for producing gasoline for vehicles from naphtha, which specifically comprises the following steps:
s1, pretreatment of raw materials: subjecting coal indirect liquefied naphtha to catalytic hydrogenation process of catalyst HC-29, and fractionating by fractionating tower to obtain C4-Component C5/C6Component (A) and (C)7+Component C of the top component of the fractionating tower4-Component A, a first-line component of the column is C5/C6Component (C) is the bottom component of the tower7+Preparing components;
s2, hydroisomerization process: in a fixed bed hydroisomerization reactor, feeding C5/C6After the components are mixed with hydrogen, the mixture is heated to the reaction temperature of 160 ℃, the pressure is 1.7MPa, the volume space velocity is 1/h, and the volume ratio of hydrogen to oil is 2: WO prepared in preparation example 33/ZrO2/Al2O3Carrying out isomerization reaction under the action of a solid strong acid loaded Mg-doped Pt/Ni bimetallic catalyst, separating a product after the product passes through a first stabilizing tower, and partially separating non-isomerized C5/C6The component is subjected to hydroisomerization process again to obtain the isomerized C5/C6The components are combined to obtain isomeric alkane oil;
s3, reforming process: in a fixed bed catalytic reforming reactor, adding C7+After the components are mixed with hydrogen, the mixture is heated to 500 ℃, the pressure is 1.5MPa, the volume space velocity is 3/h, and the volume ratio of hydrogen to oil is 620: 1, under the action of Sn doped Pt/Ni bimetallic catalyst loaded by gamma-alumina/halloysite nanotubes prepared in preparation example 6After the mixture enters a first-section fixed bed catalytic reforming reactor for reaction, after the product is mixed with hydrogen, the mixture is heated to 435 ℃, the pressure is 1.5MPa, the volume space velocity is 3/h, and the volume ratio of hydrogen to oil is 570: 1, entering a two-stage fixed bed catalytic reforming reactor for reaction, and separating a product by a second stabilizing tower to obtain aromatic oil;
s4, preparation of the motor gasoline: 55 parts by weight of the aromatic oil obtained in step S3, 35 parts by weight of the isoparaffin oil obtained in step S2, and 5 parts by weight of C in step S14-The components are mixed to obtain the motor gasoline.
Comparative example 1
Compared with example 3, the other conditions were not changed without the reforming process of step S3.
S1, pretreatment of raw materials: subjecting coal indirect liquefied naphtha to catalytic hydrogenation process of catalyst HC-29, and fractionating by fractionating tower to obtain C4-Component C5/C6Component (A) and (C)7+Component C of the top component of the fractionating tower4-Component A, a first-line component of the column is C5/C6Component (C) is the bottom component of the tower7+Preparing components;
s2, hydroisomerization process: in a fixed bed hydroisomerization reactor, feeding C5/C6After the components are mixed with hydrogen, the mixture is heated to the reaction temperature of 160 ℃, the pressure is 1.7MPa, the volume space velocity is 1/h, and the volume ratio of hydrogen to oil is 2: WO prepared in preparation example 33/ZrO2/Al2O3Carrying out isomerization reaction under the action of a solid strong acid loaded Mg-doped Pt/Ni bimetallic catalyst, separating a product after the product passes through a first stabilizing tower, and partially separating non-isomerized C5/C6The component is subjected to hydroisomerization process again to obtain the isomerized C5/C6The components are combined to obtain isomeric alkane oil;
s3, preparation of the motor gasoline: 90 parts by weight of the isoparaffin oil obtained in step S2, 5 parts by weight of C in step S14-The components are mixed to obtain the motor gasoline.
Comparative example 2
Compared with the example 3, the hydroisomerization process without the step S2 has no other condition change.
S1, pretreatment of raw materials: subjecting coal indirect liquefied naphtha to catalytic hydrogenation process of catalyst HC-29, and fractionating by fractionating tower to obtain C4-Component C5/C6Component (A) and (C)7+Component C of the top component of the fractionating tower4-Component A, a first-line component of the column is C5/C6Component (C) is the bottom component of the tower7+Preparing components;
s2, reforming process: in a fixed bed catalytic reforming reactor, adding C7+After the components are mixed with hydrogen, the mixture is heated to 500 ℃, the pressure is 1.5MPa, the volume space velocity is 3/h, and the volume ratio of hydrogen to oil is 620: 1, after entering a first-stage fixed bed catalytic reforming reactor to react under the action of a gamma-alumina/halloysite nanotube-loaded Sn-doped Pt/Ni bimetallic catalyst prepared in preparation example 6, mixing a product with hydrogen, heating to 435 ℃, wherein the pressure is 1.5MPa, the volume space velocity is 3/h, and the volume ratio of hydrogen to oil is 570: 1, entering a two-stage fixed bed catalytic reforming reactor for reaction, and separating a product by a second stabilizing tower to obtain aromatic oil;
s3, preparation of the motor gasoline: 90 parts by weight of the aromatic oil obtained in step S3, 5 parts by weight of C in step S14-The components are mixed to obtain the motor gasoline.
Comparative example 3
Compared with the example 3, the step S1 is not subjected to the catalytic hydrogenation process of the catalyst HC-29, and other conditions are not changed.
S1, pretreatment of raw materials: the coal indirect liquefied naphtha is graded by a fractionating tower to obtain C4-Component C5/C6Component (A) and (C)7+Component C of the top component of the fractionating tower4-Component A, a first-line component of the column is C5/C6Component (C) is the bottom component of the tower7+Preparing components;
s2, hydroisomerization process: in a fixed bed hydroisomerization reactor, feeding C5/C6After the components are mixed with hydrogen, the mixture is heated to the reaction temperature of 160 ℃, the pressure is 1.7MPa, the volume space velocity is 1/h, and the volume ratio of hydrogen to oil is 2: WO prepared in preparation example 33/ZrO2/Al2O3Solid strong acid loadingThe isomerization reaction is carried out under the action of the Pt/Ni bimetallic catalyst doped with Mg, the product is separated after passing through a first stabilizing tower, and part of the C which is not isomerized is5/C6The component is subjected to hydroisomerization process again to obtain the isomerized C5/C6The components are combined to obtain isomeric alkane oil;
s3, reforming process: in a fixed bed catalytic reforming reactor, adding C7+After the components are mixed with hydrogen, the mixture is heated to 500 ℃, the pressure is 1.5MPa, the volume space velocity is 3/h, and the volume ratio of hydrogen to oil is 620: 1, after entering a first-stage fixed bed catalytic reforming reactor to react under the action of a gamma-alumina/halloysite nanotube-loaded Sn-doped Pt/Ni bimetallic catalyst prepared in preparation example 6, mixing a product with hydrogen, heating to 435 ℃, wherein the pressure is 1.5MPa, the volume space velocity is 3/h, and the volume ratio of hydrogen to oil is 570: 1, entering a two-stage fixed bed catalytic reforming reactor for reaction, and separating a product by a second stabilizing tower to obtain aromatic oil;
s4, preparation of the motor gasoline: 55 parts by weight of the aromatic oil obtained in step S3, 35 parts by weight of the isoparaffin oil obtained in step S2, and 5 parts by weight of C in step S14-The components are mixed to obtain the motor gasoline.
Comparative example 4
WO obtained in preparation example 3 in comparison with example 33/ZrO2/Al2O3The solid strong acid supported Mg-doped Pt/Ni bimetallic catalyst is replaced by the catalyst prepared in the comparative preparation example 1, and other conditions are not changed.
Comparative example 5
WO obtained in preparation example 3 in comparison with example 33/ZrO2/Al2O3The solid strong acid supported Mg-doped Pt/Ni bimetallic catalyst is replaced by the catalyst prepared in the comparative preparation example 2, and other conditions are not changed.
Comparative example 6
WO obtained in preparation example 3 in comparison with example 33/ZrO2/Al2O3The solid strong acid supported Mg-doped Pt/Ni bimetallic catalyst is replaced by the catalyst prepared in the comparative preparation example 3, and other conditions are not changed.
Comparative example 7
WO obtained in preparation example 3 in comparison with example 33/ZrO2/Al2O3The solid strong acid loaded Mg-doped Pt/Ni bimetallic catalyst is replaced by the catalyst prepared in the comparative preparation example 4, and other conditions are not changed
Comparative example 8
Compared with example 3, the gamma-alumina/halloysite nanotube-supported Sn-doped Pt/Ni bimetallic catalyst prepared in preparation example 6 was replaced with the catalyst prepared in comparative preparation example 5, and other conditions were not changed.
Comparative example 9
Compared with example 3, the gamma-alumina/halloysite nanotube-supported Sn-doped Pt/Ni bimetallic catalyst prepared in preparation example 6 was replaced with the catalyst prepared in comparative preparation example 6, and other conditions were not changed.
Comparative example 10
Compared with example 3, the gamma-alumina/halloysite nanotube-supported Sn-doped Pt/Ni bimetallic catalyst prepared in preparation example 6 was replaced with the catalyst prepared in comparative preparation example 7, and other conditions were not changed.
Comparative example 11
Compared with example 3, the gamma-alumina/halloysite nanotube-supported Sn-doped Pt/Ni bimetallic catalyst prepared in preparation example 6 was replaced with the catalyst prepared in comparative preparation example 8, and other conditions were not changed.
Comparative example 12
Compared with example 3, the gamma-alumina/halloysite nanotube-supported Sn-doped Pt/Ni bimetallic catalyst prepared in preparation example 6 was replaced with the catalyst prepared in comparative preparation example 9, and other conditions were not changed.
Test example 1
The contents and properties in the respective reaction steps of the motor gasoline prepared in examples 1 to 3 of the present invention and comparative examples 1 to 12 were measured, and the results are shown in table 2.
TABLE 2
As can be seen from the above table, the isoparaffin oil yield is high after the step S2, and the isoparaffin oil yield is high; and (4) after the step S3, the aromatic hydrocarbon yield is high.
Test example 2
The motor gasoline prepared in examples 1 to 3 of the present invention and comparative examples 1 to 12 were subjected to performance tests, and the results are shown in Table 3.
Reference is made to GB17930-2011 national Standard for motor gasoline 93# gasoline and DB11/238 and 2012 Beijing City local Standard 92# gasoline standard.
TABLE 3
As can be seen from the table, the vehicle gasoline prepared by the embodiment of the invention has a higher RON value and extremely low impurity content, and is clean gasoline.
Comparative example 1, which did not undergo the reforming process of step S3, resulted in a significant decrease in the RON value of the car gasoline produced, compared to example 3. Therefore, after the reforming reaction is carried out in the step S3, the contents of naphthene and aromatic hydrocarbon in the product oil can be obviously improved, the octane number is further improved, the two-stage method is adopted for reforming, the first-stage reaction mainly comprises naphthene dehydrogenation and strong endothermic reaction, the reaction temperature is higher, the second-stage reaction mainly comprises alkane cyclization reaction and hydrocracking reaction, the former is endothermic reaction, and the latter is exothermic reaction, therefore, the reaction can be finished at relatively lower reaction temperature, in the process, the temperature is not too high, polycyclic aromatic hydrocarbon is easy to generate if the temperature is too high, later combustion is changed into carbon deposition, once the carbon deposition is generated, the carbon deposition stays on the surface of the catalyst permanently to intensify the coking and inactivation of the catalyst, and the reaction process is influenced. And further entering a stabilizer, and removing hydrogen and the low-boiling-point liquefied gas to obtain the aromatic oil.
Comparative example 2 compared to example 3, the RON value of the car gasoline obtained without the hydroisomerization process of step S2 was significantly decreased. Therefore, after the hydroisomerization reaction is performed in step S2, the obtained isomerized paraffin oil has high yield and very low sulfur content, does not contain olefin, aromatic hydrocarbon and benzene, has a significantly improved octane number and a low octane number sensitivity compared with the original straight-chain paraffin, and can improve the front-end octane number of the gasoline, so that the distillation range and the octane number of the gasoline are reasonably distributed, thereby improving the starting performance of the engine.
Comparative example 3 in comparison with example 3, step S1 was not subjected to the catalytic hydrogenation process of catalyst HC-29. The method has the advantages that firstly, after the indirect coal liquefaction naphtha is subjected to a catalytic hydrogenation process, S, N, O, metal and other impurities in the naphtha are removed, the oil quality is improved, the catalyst activity is reduced due to the fact that the catalyst is poisoned in the subsequent reaction, high-quality oil products are obtained, the selected HC series catalyst is a non-noble metal catalyst, the effect is good, the cost is low, and the method is safe and environment-friendly.
Comparative example 4 in comparison with example 3, WO obtained in preparation example 33/ZrO2/Al2O3Solid strong acid supported Mg doped Pt/Ni bimetallic catalyst WO prepared in comparative preparation example 13/ZrO2Solid strong acid supported Mg doped Pt/Ni bimetallic catalyst. The RON value and the yield of isomerized alkane are obviously reduced, and alumina is not contained in the carrier, so that the amount of the supported catalyst is obviously reduced, and the catalytic effect is obviously reduced. Al generated by sol-gel reaction2O3The carrier has large specific surface area, large aperture, concentrated aperture and good thermal stability, the service life of the catalyst is further prolonged, and the carrier has extremely large specific surface area and can impregnate, complex and adsorb a large amount of heavy metal catalysts.
Comparative example 5 in comparison with example 3, WO obtained in preparation example 33/ZrO2/Al2O3Solid strong acid supported Mg doped Pt/Ni bimetallic catalyst WO prepared from comparative preparation example 23/ZrO2/Al2O3Solid strong acid supported Pt/Ni bimetallic catalyst. The RON value and the yield of isomerized alkane are obviously reduced withoutThe Mg doping causes the catalytic effect to be slightly reduced, so that the Mg doping can obviously improve the catalyst activity.
Comparative example 6 in comparison with example 3, WO obtained in preparation example 33/ZrO2/Al2O3Solid strong acid supported Mg doped Pt/Ni bimetallic catalyst WO prepared in comparative preparation example 33/ZrO2/Al2O3Solid strong acid supported Mg doped Pt catalyst. The RON value and the yield of isomerized alkane are obviously reduced, and compared with a single Pt catalyst, the Pt/Ni bimetallic catalyst has lower reaction energy barrier, so that the isomerization reaction can be catalyzed more quickly and better.
Comparative example 7 in comparison with example 3, WO obtained in preparation example 33/ZrO2/Al2O3Solid strong acid supported Mg doped Pt/Ni bimetallic catalyst WO prepared in comparative preparation example 43/ZrO2/Al2O3Solid strong acid supported Pt catalyst. The RON value and the isomerized alkane yield are obviously reduced, and compared with a single Pt catalyst, the Mg-doped Pt/Ni bimetallic catalyst has lower reaction energy barrier, so that the isomerization reaction can be catalyzed more quickly and better.
Comparative example 8 in comparison with example 3, the gamma-alumina/halloysite nanotube-supported Sn-doped Pt/Ni bimetallic catalyst prepared in preparation example 6 was replaced with the gamma-alumina-supported Sn-doped Pt/Ni bimetallic catalyst prepared in comparative preparation example 5. The RON value and the aromatic hydrocarbon yield are obviously reduced, the halloysite nanotube is also of a porous structure, so that the high-efficiency loading of the metal catalyst is facilitated, and the gamma-alumina and the halloysite nanotube are used as carriers, so that more metal catalysts can be loaded, and the synergistic effect is achieved.
Comparative example 9 compared to example 3, the gamma-alumina/halloysite nanotube-supported Sn-doped Pt/Ni bimetallic catalyst prepared in preparative example 6 was replaced with the halloysite nanotube-supported Sn-doped Pt/Ni bimetallic catalyst prepared in comparative preparative example 6. The RON value and the yield of aromatic hydrocarbon are obviously reduced, and alumina is not contained in the carrier, so that the amount of the supported catalyst is obviously reduced, and the catalytic effect is obviously reduced. Sol gelAl produced by glue reaction2O3The carrier has large specific surface area, large aperture, concentrated aperture and good thermal stability, the service life of the catalyst is further prolonged, and the carrier has extremely large specific surface area and can impregnate, complex and adsorb a large amount of heavy metal catalysts.
Comparative example 10 in comparison with example 3, the gamma-alumina/halloysite nanotube-supported Sn-doped Pt/Ni bimetallic catalyst prepared in preparation example 6 was replaced with the gamma-alumina/halloysite nanotube-supported Pt/Ni bimetallic catalyst prepared in comparative preparation example 7. The RON value and the yield of aromatic hydrocarbon are obviously reduced, and therefore, in the Sn-doped Pt/Ni bimetallic catalyst, after Sn is introduced, the dispersion degree of Pt metal is improved, the number of low-temperature hydrogen adsorption centers is not changed greatly, but high-temperature centers are obviously increased, and under the existence of high temperature and hydrogen, on one hand, Sn is reduced into low-valent oxide, and forms an oxygen-deficient surface complex Pt- [ SnO & lt/EN & gt with high-temperature hydrogen adsorption capacityx]At the same time, SnO2Can also be reduced to zero-valent Sn to form Pt with PtxSnyThe alloy suppresses the ability of Pt to adsorb hydrogen. On the other hand, Sn interacts with the gamma-alumina carrier to form tetravalent (SnO)2·Al2O3) And divalent (SnAl)2O5) Sn, thereby improving the catalytic selectivity and catalytic activity and further improving the yield of aromatic hydrocarbon.
Comparative example 11 compared to example 3, the gamma-alumina/halloysite nanotube-supported Sn-doped Pt/Ni bimetallic catalyst prepared in preparative example 6 was replaced with the gamma-alumina/halloysite nanotube-supported Sn-doped Pt catalyst prepared in comparative preparative example 8. The RON value and the yield of aromatic hydrocarbon are obviously reduced, and the Pt/Ni bimetallic catalyst has lower reaction energy barrier compared with a single Pt catalyst, so that the isomerization reaction can be catalyzed more quickly and better.
Comparative example 12 in comparison with example 3, the gamma-alumina/halloysite nanotube-supported Sn-doped Pt/Ni bimetallic catalyst prepared in preparation example 6 was replaced with the gamma-alumina/halloysite nanotube-supported Pt catalyst prepared in comparative preparation example 9. The RON value and the yield of aromatic hydrocarbon are obviously reduced, and the Sn-doped Pt/Ni bimetallic catalyst has lower reaction energy barrier compared with a single Pt catalyst, so that the isomerization reaction can be more quickly and better catalyzed.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. An environment-friendly process method for producing gasoline for vehicles from naphtha is characterized in that coal indirect liquefied naphtha is subjected to catalytic hydrogenation and then is graded to obtain C4-Component C5/C6Component (A) and (C)7+Component (B) in which5/C6The component is subjected to hydroisomerization reaction to obtain an isomeric alkane oil C7+Reforming the components to obtain aromatic oil, and proportionally mixing C4-Uniformly mixing the components, the isomeric alkane oil and the aromatic oil to obtain the motor gasoline;
the catalyst for the hydroisomerization reaction is a first catalyst, and the first catalyst is prepared by carrying out coprecipitation reaction and sol-gel reaction on ammonium metatungstate, zirconium oxychloride and aluminum isopropoxide to obtain WO3/ZrO2/Al2O3Solid strong acid carrier, then impregnating H2PtCl6、NiCl2And MgCl2WO obtained by supporting on the carrier3/ZrO2/Al2O3A solid strong acid-supported Mg-doped Pt/Ni bimetallic catalyst;
the catalyst of the reforming reaction is a second catalyst, the second catalyst is a gamma-alumina/halloysite nanotube carrier obtained by sol-gel reaction of a halloysite nanotube and aluminum isopropoxide, and then H is carried out by an impregnation method2PtCl6、NiCl2And SnCl2Loaded on the carrier to obtain the gamma-alumina/halloysite nanotube loaded Sn doped Pt/Ni bimetallic catalyst.
2. The environment-friendly process method for producing motor gasoline from naphtha as claimed in claim 1, which comprises the following steps:
s1, pretreatment of raw materials: subjecting coal indirect liquefied naphtha to catalytic hydrogenation process, and fractionating by a fractionating tower to obtain C4-Component C5/C6Component (A) and (C)7+Preparing components;
s2, hydroisomerization process: c is to be5/C6Mixing the components with hydrogen, carrying out isomerization reaction under the action of a first catalyst, separating the product after passing through a first stabilizing tower, and partially separating the non-isomerized C5/C6The component is subjected to hydroisomerization process again to obtain the isomerized C5/C6The components are combined to obtain isomeric alkane oil;
s3, reforming process: c is to be7+After the components are mixed with hydrogen, performing multi-stage catalytic reforming reaction under the action of a second catalyst, and separating a product by a second stabilizing tower to obtain aromatic oil;
s4, preparation of the motor gasoline: 50-60 parts by weight of aromatic oil obtained in step S3, 30-40 parts by weight of isoparaffin oil obtained in step S2 and 3-7 parts by weight of C obtained in step S14-The components are mixed to obtain the motor gasoline.
3. The environmentally friendly process for producing motor gasoline from naphtha as set forth in claim 2, wherein the catalyst of the catalytic hydrogenation process in step S1 is at least one of HC-110, HC-170, HC-115, HC-125 and HC-29; the tower top component of the fractionating tower is C4-Component A, a first-line component of the column is C5/C6Component (C) is the bottom component of the tower7+And (4) components.
4. The environmentally friendly process for producing motor gasoline from naphtha as set forth in claim 2, wherein the first catalyst is WO3/ZrO2/Al2O3The preparation method of the solid strong acid loaded Mg-doped Pt/Ni bimetallic catalyst comprises the following steps: dropwise adding ammonium metatungstate solution into mixed solution of zirconium oxychloride and aluminum isopropoxide under stirring, adjusting pH value of the solution to 9-10, heating to 80-90 deg.C, reacting for 0.5-1h, centrifuging, and precipitating solidWashing with deionized water, filtering, drying and roasting to obtain WO3/ZrO2/Al2O3A solid strong acid support; to dissolve H2PtCl6And NiCl2To the solution of (3) adding MgCl2After mixing uniformly, add WO3/ZrO2/Al2O3Carrying out ultrasonic dispersion on a solid strong acid carrier for 0.5-1h, heating to 80-90 ℃ for reaction for 1-2h, concentrating under reduced pressure, filtering, and drying to obtain WO3/ZrO2/Al2O3A solid strong acid supported Mg doped Pt/Ni bimetallic catalyst.
5. The environment-friendly process method for producing motor gasoline from naphtha as claimed in claim 4, wherein the mass ratio of the ammonium metatungstate to the zirconium oxychloride to the aluminum isopropoxide is 10: 4-7: 2-3; said H2PtCl6、NiCl2、MgCl2The mass ratio of (A) to (B) is 3-7: 2-3: 0.01-0.05; the roasting temperature is 300-450 ℃.
6. The environmentally friendly process for producing motor gasoline from naphtha as claimed in claim 2, wherein the hydroisomerization reaction in step S2 is carried out in a fixed bed hydroisomerization reactor, and C is5/C6After the components are mixed with hydrogen, the mixture is heated to the reaction temperature of 140 ℃ and 190 ℃, the pressure is 1.4-2MPa, the volume space velocity is 0.5-1.5/h, and the volume ratio of hydrogen to oil is 1-3: 1, carrying out isomerization reaction under the action of a first catalyst, separating products after the products pass through a first stabilizing tower, and partially separating non-isomerized C5/C6The component is subjected to hydroisomerization process again to obtain the isomerized C5/C6And (4) combining the components to obtain the isomeric alkane oil.
7. The environmentally friendly process for producing motor gasoline from naphtha as set forth in claim 2, wherein said second catalyst is a γ -alumina/halloysite nanotube supported Sn doped Pt/Ni bimetallic catalyst prepared by the following method: dispersing halloysite nanotubes in ethanol water solution, adding aluminum isopropoxide for dissolution, and ultrasonically separatingUniformly dispersing, heating to 60-80 ℃ for reaction, decompressing and removing a solvent to obtain a precursor, roasting and grinding the precursor to obtain the gamma-alumina/halloysite nanotube carrier; h is to be2PtCl6And NiCl2Adding SnCl into the solution2And after uniformly mixing, adding a gamma-alumina/halloysite nanotube carrier, performing ultrasonic dispersion for 0.5-1h, heating to 75-85 ℃ for reaction for 1-2h, performing reduced pressure concentration, filtering and drying to obtain the gamma-alumina/halloysite nanotube loaded Sn doped Pt/Ni bimetallic catalyst.
8. The environment-friendly process method for producing the gasoline for vehicles from naphtha as claimed in claim 7, wherein the mass ratio of the halloysite nanotube to the aluminum isopropoxide is 3-5: 10; said H2PtCl6、NiCl2And SnCl2The mass ratio of (A) to (B) is 10: 1-2: 0.5 to 1; the roasting temperature is 500-600 ℃; the ethanol content in the ethanol water solution is 50-70wt%, and the balance is water.
9. The environmentally friendly process for producing motor gasoline from naphtha as set forth in claim 2, wherein the multistage catalytic reforming reaction in step S3 is carried out in a fixed bed catalytic reforming reactor, and C is7+After the components are mixed with hydrogen, the mixture is heated to the temperature of 490-510 ℃, the pressure is 1-2MPa, the volume space velocity is 2-4/h, and the volume ratio of hydrogen to oil is 500-750: 1, after entering a first-stage fixed bed catalytic reforming reactor to react under the action of a second catalyst, mixing a product with hydrogen, heating to the temperature of 420-450 ℃, wherein the pressure is 1.2-1.7MPa, the volume space velocity is 2-4/h, and the volume ratio of hydrogen to oil is 550-600: 1, entering a two-stage fixed bed catalytic reforming reactor for reaction, and separating a product by a second stabilizing tower to obtain aromatic oil.
10. The motor gasoline prepared by the environment-friendly process for producing motor gasoline from naphtha as claimed in any one of claims 1 to 9, wherein the octane number of the motor gasoline is 94 to 96, and the density at 20 ℃ is 750-760kg/m3Lead content less than 0.001g/L, iron content less than 0.002g/L, manganese content less than 0.002g/L, sulfurThe content is less than 0.0001 g/L.
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| CN110358577B (en) * | 2018-04-10 | 2021-11-16 | 中国石油化工股份有限公司 | Method for converting naphtha into high-octane gasoline and aromatic hydrocarbon |
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