CN108295896B - Method for catalytically producing alkylated gasoline - Google Patents
Method for catalytically producing alkylated gasoline Download PDFInfo
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- CN108295896B CN108295896B CN201810248835.7A CN201810248835A CN108295896B CN 108295896 B CN108295896 B CN 108295896B CN 201810248835 A CN201810248835 A CN 201810248835A CN 108295896 B CN108295896 B CN 108295896B
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- 238000000034 method Methods 0.000 title claims description 15
- 239000002608 ionic liquid Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 20
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000001282 iso-butane Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 93
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 21
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 10
- 238000003828 vacuum filtration Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002159 nanocrystal Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000013067 intermediate product Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011156 evaluation Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 4
- SAWCWRKKWROPRB-UHFFFAOYSA-N 1,1-dibromohexane Chemical compound CCCCCC(Br)Br SAWCWRKKWROPRB-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
-
- B01J35/33—
-
- 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
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
- C10G2300/1092—C2-C4 olefins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Abstract
The invention discloses a method for producing alkylated gasoline by catalysis, which takes isobutane and 1-butylene as raw materials, takes supported binuclear polyacid ionic liquid as a catalyst, and is carried out at the temperature of 60 DEG CoC. The reaction pressure is 1.5MPa, and the mass space velocity is 2.5h‑1Reacting in a fixed bed reactor, wherein the molar ratio of isobutane to 1-butene is 20: 1; the invention provides a magnetic binuclear polyacid-based ionic liquid catalyst with high catalytic activity, good reaction stability, high olefin conversion rate and high TMP yield, and the magnetic binuclear polyacid-based ionic liquid catalyst is applied to preparation of alkylated gasoline by taking isobutane and butene as raw materials.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, relates to a catalyst, and particularly relates to a method for producing alkylated gasoline by catalysis.
Background
With the rapid development of the automobile industry, the demand of clean gasoline production in countries of the world is increasing, wherein C is catalyzed by strong acid4The alkylation reaction to generate the alkylated gasoline is an important process for producing clean gasoline in the field of petrochemical industry, the alkylated gasoline produced by the process has the advantages of high octane number, low vapor pressure, low sulfur content, no aromatic hydrocarbon and the like, and is an environment-friendly high-octane number gasoline blending component for replacing MTBE and ethanol. At present, the mature process of the alkylation technology comprises a sulfuric acid method and a hydrofluoric acid method, but the process has a plurality of defects, such as strong toxicity of hydrofluoric acid and great harm to human health and ecological environment; the problems of low mixing reaction and reaction efficiency, large discharge amount of waste acid and alkaline residue, serious environmental pollution and the like exist in the concentrated sulfuric acid process engineering.
The ionic liquid has the advantages of high activity, low volatility, environmental protection, easy recycling and the like, and is taken as C by a plurality of well-known companies and research institutions at home and abroad4The development and research of new alkylation processes are important. The acid strength has obvious influence on the alkylation reaction of isobutane and butene, and the ionic liquid applied to the production of alkylated gasoline at present belongs to mononuclear ionic liquid, but the reaction stability and the thermal stability of the ionic liquid need to be further enhanced and are not easy to recover. Compared with the traditional ionic liquid, the magnetic binuclear polyacid ionic liquid has the advantages of high acid density, strong structural stability, high reaction stability and the like, and no relevant report of applying the magnetic binuclear polyacid ionic liquid to the preparation of alkylated gasoline exists at present.
Disclosure of Invention
In order to overcome the technical defects in the prior art, the invention discloses a method for producing alkylated gasoline by catalysis, and aims to provide a magnetic binuclear polyacid-based ionic liquid catalyst which has high catalytic activity, good reaction stability, high olefin conversion rate and high TMP yield, and is applied to the preparation of the alkylated gasoline by taking isobutane and butene as raw materials.
The invention is realized by the following technical scheme:
the invention discloses a method for producing alkylated gasoline by catalysis, which takes isobutane and 1-butylene as raw materials, takes magnetic dual-core polyacid ionic liquid as a catalyst and has the temperature of 60 DEG CoC. The reaction pressure is 1.5MPa, and the mass space velocity is 2.5h-1Reacting in a fixed bed reactor, wherein the molar ratio of isobutane to 1-butene is 20: 1;
the magnetic binuclear polyacid ionic liquid is prepared by the following steps:
1) magnetic core Fe3O4Preparation of
FeCl is added3·6H2Dissolving O in ethylene glycol solution, adding sodium acetate and CTAB, and performing ultrasonic treatment for 20min to disperse fully to obtain a mixture; then reacting the mixture for 24 hours in a water bath condition at 200 ℃ to obtain suspension, naturally cooling the suspension to room temperature, centrifuging, washing and drying to obtain Fe3O4Magnetic nanocrystals;
2）Fe3O4surface TiO of2Coating of
Fe obtained in the step 1)3O4Dispersing magnetic nanocrystals in a dispersed phase formed by mixing ethylene glycol and deionized water, adding ammonia water, performing ultrasound for 20min, dropwise adding tetrabutyl titanate under the condition of vigorous stirring, continuously stirring at room temperature for 1h, performing centrifugal separation, treating the centrifugally separated solid product at 105 ℃ for 12h, and roasting at 350 ℃ for 4h to obtain Fe3O4@TiO2A carrier; TiO 22The coating can obviously improve the specific surface area of the catalyst on one hand and can react with SO on the ionic liquid on the other hand4 2-The reaction forms solid super acid, so as to strengthen the reaction activity of the catalyst;
3) loading of ionic liquids
Mixing Fe3O4@TiO2Placing a carrier in an aqueous solution, adding an ionic liquid X into the aqueous solution, performing dispersion treatment for 20 min-1 h under the ultrasonic condition of 200 w-300 w, and then placing the aqueous solution in a vacuum drying oven at 70 ℃ for 12h to obtain a dry magnetic dual-core polyacid ionic liquid;
wherein the structural formula of the ionic liquid X is shown as follows:
wherein, the stirring in the technical scheme refers to the stirring speed of 400-600 r/min.
As a preferred embodiment, in step 1), FeCl3·6H2The ratio of the amounts of substances of O, sodium acetate and 2.0 mmoleCTAB was 2: 10: 1, the concentration of the sodium acetate substance in the mixture is 0.5 mol/L.
As a preferred embodiment, in the step 2), the volume ratio of the ethylene glycol to the deionized water to the ammonia water to the tetrabutyl titanate is 200:75:20:3, and Fe3O4The mass volume ratio of the magnetic nanocrystal to the glycol is 5 g/L.
As a preferred embodiment, in step 3), the ionic liquid X and Fe3O4@TiO2The mass ratio of the carrier is 20-30 wt%, and the Fe3O4@TiO2The mass-to-volume ratio of the carrier to water was 1g/20 mL.
The invention also discloses a preferable preparation method of the ionic liquid X, which is prepared by the following steps:
1) dissolving imidazole and potassium hydroxide in N-formylmorpholine, stirring at room temperature for 30min to completely dissolve the imidazole, dropwise adding 1, 6-dibromohexane, transferring the imidazole into a microwave reactor after dropwise adding, treating for 40-60 min at 30-60 ℃ under 200-400W, performing vacuum filtration, and washing for 3-5 times with absolute ethyl alcohol to obtain a white solid Y; wherein the molar ratio of imidazole to potassium hydroxide is 1: 1; the volume molar ratio of the N-formyl morpholine to the imidazole is 50mL/200mmol, and the molar ratio of the imidazole to the 1, 6-dibromohexane is 2: 3;
2) stirring and mixing 1, 4-butane sultone and white solid Y in a mass ratio of 5:2 at 60 ℃ for 5-10 min, stirring at room temperature for 40min to completely dissolve the white solid to obtain a mixture, transferring the mixture into a microwave reactor, treating at 40-80 ℃ for 60-100 min under the power of 200-300W, performing vacuum filtration, and washing with anhydrous acetone for 3-5 times to obtain a product W;
3) dropwise adding trifluoroacetic acid into a product W dropwise, wherein the mass ratio of the trifluoroacetic acid to an intermediate product W is 5:11, stirring at room temperature for 1h to fully mix the trifluoroacetic acid and the intermediate product W, transferring the mixture into a hydrothermal reaction kettle, treating the mixture at 80-100 ℃ for 6-8 h, washing the obtained product with anhydrous acetone for 4 times, and drying the product at 60 ℃ in vacuum for 2h to obtain the final ionic liquid X.
Compared with the prior art, the invention has the following advantages:
(1) compared with the conventional catalyst, the magnetic dual-core polyacid ionic liquid catalyst has the advantages of strong acid density, strong structural stability, high reaction stability, difficult loss of the catalyst and the like, and simultaneously, the conversion rate of the obtained butylene in the alkylation reaction process is high, and C is8The selectivity of trimethylpentane in the hydrocarbon is obviously improved;
(2) the magnetic dual-core polyacid ionic liquid can greatly reduce the using amount of active components, and has the advantages of good repeatability, simpler preparation and use conditions, less basic corrosion of equipment, less harm to the environment and the like;
(3) synergistic effect between acidic sites on magnetic binuclear polyacid ionic liquids and SO4 2-With TiO2The super acid formed in the process can obviously enhance the reaction rate and improve the product selectivity, thereby shortening the reaction time.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
Example 1
1) Preparation of catalyst a:
a) dissolving imidazole and potassium hydroxide in N-formylmorpholine, stirring at room temperature for 30min to completely dissolve imidazole, then dropwise adding 1, 6-dibromohexane, transferring the imidazole into a microwave reactor, treating for 40min at 60 ℃ and 400W, then carrying out vacuum filtration on the imidazole and the dibromohexane, and washing for 5 times by using absolute ethyl alcohol to obtain a white solid Y; wherein the molar ratio of imidazole to potassium hydroxide is 1: 1; the volume molar ratio of the N-formyl morpholine to the imidazole is 50mL/200mmol, and the molar ratio of the imidazole to the 1, 6-dibromohexane is 2: 3;
b) stirring and mixing 1, 4-butane sultone and a white solid Y in a mass ratio of 5:2 at 60 ℃ for 5min, stirring at room temperature for 40min to completely dissolve the white solid, transferring the white solid into a microwave reactor, treating at 80 ℃ for 60min under 300W, performing vacuum filtration on the white solid, and washing with anhydrous acetone for 5 times to obtain a product W;
c) dropwise adding trifluoroacetic acid into a product W, wherein the mass ratio of the trifluoroacetic acid to the intermediate product W is 5:11, stirring at room temperature for 1h to fully mix the trifluoroacetic acid and the intermediate product W, and then transferring the trifluoroacetic acid to a hydrothermal reaction kettle to treat at 100 ℃ for 6h to obtain an ionic liquid X;
d) magnetic core Fe3O4Preparation of
4.0 mmol of FeCl3·6H2Dissolving O in 40.0mL of glycol solution, adding 20.0mmol of sodium acetate and 2.0mmol of CTAB, and performing ultrasonic treatment for 20min to fully disperse to obtain a mixture; then reacting the mixture for 24 hours in a water bath condition at 200 ℃ to obtain suspension, naturally cooling the suspension to room temperature, centrifuging, washing and drying to obtain Fe3O4Magnetic nanocrystals;
e）Fe3O4surface TiO of2Coating of
0.1g of Fe3O4The magnetic nanocrystals were dispersed in a dispersed phase of 20mL ethylene glycol and 7.5mL deionized water, and then added2.0mL of ammonia water, dispersing for 20min under the ultrasonic condition of 300w, then dropwise adding 0.30mL of tetrabutyl titanate under the condition of vigorous stirring, continuously stirring for 1h at room temperature, then performing centrifugal separation, treating the solid product after centrifugal separation at 105 ℃ for 12h, and roasting at 350 ℃ for 4h to obtain Fe3O4@TiO2A carrier;
f) loading of ionic liquids
Weighing 1gFe3O4@TiO2Putting the carrier into 20mL of aqueous solution, adding 0.3g of the ionic liquid X into the aqueous solution, performing dispersion treatment for 20min under the ultrasonic condition of 300w, and then putting the carrier into a vacuum drying oven at 70 ℃ for treatment for 12h to obtain a catalyst A in a dry state;
2) evaluation of catalyst Activity
A 2.0g sample of the catalyst was charged into a fixed bed reactor, and the reaction temperature: 80oC, reaction pressure: 1.5MPa, mass airspeed: 2.5h-1And the reaction time is as follows: 300h, the molar ratio of isobutane/1-butene was 20: 1. After the reaction evaluation for 200 hours, the conversion rate of 1-butene of the catalyst is 99.9 percent, and C8The trimethylpentane TMP content of the hydrocarbons was 84.1%.
Example 2
1) Preparation of catalyst B:
a) dissolving imidazole and potassium hydroxide in N-formylmorpholine, stirring at room temperature for 30min to completely dissolve imidazole, then dropwise adding 1, 6-dibromohexane, transferring the imidazole into a microwave reactor, treating at 30 ℃ and 200W for 60min, then carrying out vacuum filtration on the imidazole and the dibromohexane, and washing with absolute ethyl alcohol for 5 times to obtain a white solid Y; wherein the molar ratio of imidazole to potassium hydroxide is 1: 1; the volume molar ratio of the N-formyl morpholine to the imidazole is 50mL/200mmol, and the molar ratio of the imidazole to the 1, 6-dibromohexane is 2: 3;
b) stirring and mixing 1, 4-butane sultone and a white solid Y in a mass ratio of 5:2 at 60 ℃ for 10min, stirring at room temperature for 40min to completely dissolve the white solid, transferring the white solid into a microwave reactor, treating at 40 ℃ and 200W for 100min, performing vacuum filtration on the white solid, and washing with anhydrous acetone for 5 times to obtain a product W;
c) trifluoroacetic acid was added dropwise to the product W in a mass ratio of 5:11, stirred at room temperature for 1h to mix well, and then transferred to a hydrothermal reaction kettle for treatment at 80 ℃ for 8 h. After the reaction is finished, washing the obtained product with anhydrous acetone for 4 times, and carrying out vacuum drying at 60 ℃ for 2 hours to obtain the final ionic liquid X;
d) magnetic core Fe3O4Was prepared as in example 1
e）Fe3O4Surface TiO of2Coating the same as in example 1
f) Loading of ionic liquids
Weighing 1gFe3O4@TiO2Putting the carrier into 20mL of aqueous solution, adding 0.2g of the ionic liquid X into the aqueous solution, performing dispersion treatment for 1h under 200w of ultrasonic conditions, and then putting the carrier into a vacuum drying oven at 70 ℃ for treatment for 12h to obtain a catalyst B in a dry state;
2) evaluation of catalyst Activity
After the reaction evaluation for 300 hours, the conversion rate of 1-butene of the catalyst is 99.8 percent, and C is8The trimethylpentane TMP content of the hydrocarbons was 82.8%.
Example 3
1) Preparation of catalyst C:
a) dissolving imidazole and potassium hydroxide in N-formylmorpholine, stirring at room temperature for 30min to completely dissolve imidazole, then dropwise adding 1, 6-dibromohexane, transferring the imidazole into a microwave reactor, treating for 50min at 40 ℃ and 300W, then carrying out vacuum filtration on the imidazole and the dibromohexane, and washing for 4 times by using absolute ethyl alcohol to obtain a white solid Y; wherein the molar ratio of imidazole to potassium hydroxide is 1: 1; the volume molar ratio of the N-formyl morpholine to the imidazole is 50mL/200mmol, and the molar ratio of the imidazole to the 1, 6-dibromohexane is 2: 3;
b) stirring and mixing 1, 4-butane sultone and a white solid Y in a mass ratio of 5:2 at 60 ℃ for 8min, stirring at room temperature for 40min to completely dissolve the white solid, transferring the white solid into a microwave reactor, treating at 60 ℃ for 80min under 200W, performing vacuum filtration on the white solid, and washing with anhydrous acetone for 4 times to obtain a product W;
c) dropwise adding trifluoroacetic acid into a product W, wherein the mass ratio of the trifluoroacetic acid to the product W is 5:11, stirring at room temperature for 1h to fully mix the trifluoroacetic acid and the product W, then transferring the product into a hydrothermal reaction kettle to treat at 90 ℃ for 7h, washing the obtained product with anhydrous acetone for 4 times after the reaction is finished, and performing vacuum drying at 60 ℃ for 2h to obtain the final ionic liquid X;
d) magnetic core Fe3O4Was prepared as in example 1
e）Fe3O4Surface TiO of2Coating the same as in example 1
f) Loading of ionic liquids
Weighing 1gFe3O4@TiO2Putting the carrier into 20mL of aqueous solution, adding 0.2g of the ionic liquid X into the aqueous solution, performing dispersion treatment for 1h under 200w of ultrasonic conditions, and then putting the carrier into a vacuum drying oven at 70 ℃ for treatment for 12h to obtain a catalyst C in a dry state;
2) evaluation of catalyst Activity
After the reaction evaluation for 300 hours, the conversion rate of 1-butene of the catalyst is 99.8 percent, and C is8The trimethylpentane TMP content of the hydrocarbons was 83.7%.
Example 4
The catalyst of example 1 was subjected to a cycle evaluation, and the results obtained after the reaction evaluation are shown in the following table 1:
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 (5)
1. A process for the catalytic production of alkylated gasoline characterized by: isobutane and 1-butene are used as raw materials, a supported binuclear polyacid ionic liquid is used as a catalyst, and the temperature is 60 DEGoC. Reaction pressure 1.5MPa, mass airspeed2.5h-1Reacting in a fixed bed reactor, wherein the molar ratio of isobutane to 1-butene is 20: 1;
the supported binuclear polyacid ionic liquid is prepared by the following steps:
1) magnetic core Fe3O4Preparation of
FeCl is added3·6H2Dissolving O in ethylene glycol solution, adding sodium acetate and CTAB, and performing ultrasonic treatment for 20min to obtain a mixture; then reacting the mixture for 24 hours in a water bath condition at 200 ℃ to obtain suspension, naturally cooling the suspension to room temperature, centrifuging, washing and drying to obtain Fe3O4Magnetic nanocrystals;
2）Fe3O4surface TiO of2Coating of
Fe obtained in the step 1)3O4Dispersing magnetic nanocrystals in a dispersed phase formed by mixing ethylene glycol and deionized water, adding ammonia water, performing ultrasound for 20min, dropwise adding tetrabutyl titanate under the condition of vigorous stirring, continuously stirring at room temperature for 1h, performing centrifugal separation, treating the centrifugally separated solid product at 105 ℃ for 12h, and roasting at 350 ℃ for 4h to obtain Fe3O4@TiO2A carrier;
3) loading of ionic liquids
Mixing Fe3O4@TiO2Placing a carrier in an aqueous solution, adding an ionic liquid X into the aqueous solution, performing dispersion treatment for 20 min-1 h under the ultrasonic condition of 200 w-300 w, and then placing the carrier in a vacuum drying oven at 70 ℃ for treatment for 12h to obtain a dry-state supported binuclear polyacid ionic liquid;
wherein the structural formula of the ionic liquid X is shown as follows:
2. the process for catalytically producing an alkylated gasoline according to claim 1 wherein: in step 1), FeCl3·6H2O, acetic acidThe ratio of the amounts of sodium and CTAB species is 2: 10: 1, the concentration of the sodium acetate substance in the mixture is 0.5 mol/L.
3. The process for catalytically producing an alkylated gasoline according to claim 1 wherein: in the step 2), the volume ratio of the ethylene glycol, the deionized water, the ammonia water and the tetrabutyl titanate is 200:75:20:3, and Fe3O4The mass volume ratio of the magnetic nanocrystal to the glycol is 5 g/L.
4. The process for catalytically producing an alkylated gasoline according to claim 1 wherein: in step 3), the ionic liquid X and Fe3O4@TiO2The mass ratio of the carrier is 20-30 wt%, and the mass volume ratio of the carrier to water is 1g/20 mL.
5. The process for the catalytic production of an alkylated gasoline according to any one of claims 1 to 4 wherein: the ionic liquid X is prepared by the following steps:
1) dissolving imidazole and potassium hydroxide in N-formylmorpholine, stirring at room temperature for 30min, then dropwise adding 1, 6-dibromohexane, transferring the mixture into a microwave reactor after dropwise adding, treating for 40-60 min at 30-60 ℃ under 200-400W, then carrying out vacuum filtration, and washing for 3-5 times by using absolute ethyl alcohol to obtain a white solid Y; wherein the molar ratio of imidazole to potassium hydroxide is 1: 1; the volume molar ratio of the N-formyl morpholine to the imidazole is 50mL/200mmol, and the molar ratio of the imidazole to the 1, 6-dibromohexane is 2: 3;
2) stirring and mixing 1, 4-butane sultone and white solid Y in a mass ratio of 5:2 at 60 ℃ for 5-10 min, stirring at room temperature for 40min to obtain a mixture, transferring the mixture into a microwave reactor, treating at 40-80 ℃ for 60-100 min under the power of 200-300W, performing vacuum filtration, and washing with anhydrous acetone for 3-5 times to obtain a product W;
3) dropwise adding trifluoroacetic acid into a product W, wherein the mass ratio of the trifluoroacetic acid to the intermediate product W is 5:11, stirring at room temperature for 1h, transferring to a hydrothermal reaction kettle, treating at 80-100 ℃ for 6-8 h, washing the obtained product with anhydrous acetone for 4 times, and vacuum-drying at 60 ℃ for 2h to obtain the final ionic liquid X.
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| US8821805B2 (en) * | 2010-05-14 | 2014-09-02 | Chevron U.S.A. Inc. | Process unit with improved reactant feeding for the production of alkylate gasoline |
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| CN101851526A (en) * | 2010-06-17 | 2010-10-06 | 中国科学院过程工程研究所 | Method for producing alkylation gasoline by taking ionic liquid as accelerator of fluorosulphonic acid |
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