CN108441258B - Preparation method of alkylated gasoline - Google Patents
Preparation method of alkylated gasoline Download PDFInfo
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- CN108441258B CN108441258B CN201810248846.5A CN201810248846A CN108441258B CN 108441258 B CN108441258 B CN 108441258B CN 201810248846 A CN201810248846 A CN 201810248846A CN 108441258 B CN108441258 B CN 108441258B
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- Prior art keywords
- ionic liquid
- mnfe
- alkylated gasoline
- isobutane
- catalyst
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002608 ionic liquid Substances 0.000 claims abstract description 46
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 36
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000001282 iso-butane Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- 229910017163 MnFe2O4 Inorganic materials 0.000 claims description 26
- 239000013067 intermediate product Substances 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000002159 nanocrystal Substances 0.000 claims description 8
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- 235000017281 sodium acetate Nutrition 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 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 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process 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
- 239000006185 dispersion Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 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
- 238000011156 evaluation Methods 0.000 description 8
- 239000011973 solid acid Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000005804 alkylation reaction Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000011831 acidic ionic liquid Substances 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- 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
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J31/0281—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 the nitrogen being a ring member
- B01J31/0282—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 the nitrogen being a ring member of an aliphatic ring, e.g. morpholinium
-
- 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
- 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
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/56—Addition to acyclic hydrocarbons
- C07C2/58—Catalytic processes
- C07C2/62—Catalytic processes with acids
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of alkylated gasoline, which takes isobutane and 1-butene as raw materials, takes a supported binuclear polyacid ionic liquid as a catalyst, and is carried out at the temperature of 70 DEG CoC. The reaction pressure is 2.0MPa, and the mass space velocity is 3h‑1The fixed bed reactor (2) with a molar ratio of isobutane to 1-butene of 20: 1. The invention provides a supported binuclear polyacid ionic liquid catalyst which has high catalytic activity, good reaction stability, easy recycling and high olefin conversion rate and TMP yield, and is applied to the preparation of alkylated gasoline by taking isobutane and butylene 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 preparation method of alkylated gasoline.
Background
With the deterioration of the quality of processed crude oil and the continuous upgrading of the quality of gasoline products in China, the traditional gasoline production mode and the produced gasoline products face huge challenges. The alkylated gasoline with high octane number and low vapor pressure, which is produced by taking butylene and isobutane as raw materials and carrying out alkylation reaction, is an environment-friendly gasoline blending component with high octane number and can replace MTBE and ethanol, and does not contain aromatic hydrocarbon and olefin or sulfur. The alkylation catalyst applied in industry mainly uses concentrated sulfuric acid and hydrofluoric acid, but has the defects of large acid consumption, serious equipment corrosion and environmental pollution, difficult cyclic utilization of the catalyst and the like. The solid acid catalyst is applied to the catalyst for preparing the alkylated gasoline, the defects of the liquid acid catalyst are solved to a certain extent, but the solid acid catalyst is easy to lose, is difficult to repeat and regenerate during separation, has large mass transfer and diffusion resistance, relatively small acid center number, uneven distribution and the like, and limits the industrial application of the solid acid catalyst because the solid acid catalyst has the defects of large tendency of olefin polymerization reaction, generated polyolefin can cause coking and inactivation of the solid acid catalyst, and the solid acid heterogeneous catalyst has the defects of easy loss, difficult repetition and regeneration and use, large mass transfer and diffusion resistance, and the like.
The ionic liquid catalyzed alkylated gasoline has obvious advantages in catalytic activity, selectivity, reuse and other aspects. 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 the ionic liquid is not easy to recycle. Compared with the traditional ionic liquid, the supported binuclear multi-acidic ionic liquid has the advantages of high acid density, strong structural stability, high reaction stability, easiness in recycling and the like, and no report related to the application of the binuclear ionic liquid in the preparation of the alkylated gasoline exists at present.
Disclosure of Invention
In order to overcome the technical defects in the prior art, the invention discloses a preparation method of alkylated gasoline, and aims to provide a supported binuclear polyacid-based ionic liquid catalyst which has high catalytic activity, good reaction stability, easy recycling, high olefin conversion rate and high TMP yield, and is applied to 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 preparation method of alkylated gasoline, which takes isobutane and 1-butene as raw materials, takes a supported binuclear polyacid ionic liquid as a catalyst, and is carried out at the temperature of 70 DEG CoC. The reaction pressure is 2.0MPa, and the mass space velocity is 3h-1Reacting in a fixed bed reactor, wherein the molar ratio of isobutane to 1-butene is 20: 1;
the preparation method of the supported binuclear polyacid ionic liquid comprises the following steps:
1）MnFe2O4preparation of
FeCl is added3·6H2O and Mn (Ac)2·4H2Dissolving O in ethylene glycol solution, adding sodium acetate and P123, and performing ultrasonic treatment for 30min to fully disperse to obtain a mixture; then reacting the mixture for 24-48 h in a water bath at 180-220 ℃ to obtain a suspension, naturally cooling the suspension to room temperature, centrifuging, washing and drying to obtain MnFe2O4Magnetic nanocrystals;
2）MnFe2O4surface TiO of2Coating of
MnFe obtained in the step 1)2O4Dispersing magnetic nanocrystal in dispersed phase prepared by mixing ethylene glycol and deionized water, adding ammonia water, performing ultrasonic treatment for 20min, dropwise adding tetrabutyl titanate under vigorous stirring, stirring at room temperature for 1 hr, performing centrifugal separation, and collecting solid product at 105 deg.CTreating for 12h, and roasting at 300 ℃ for 4h to obtain MnFe2O4@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 MnFe2O4@TiO2Placing a carrier in an aqueous solution, adding ionic liquid N into the aqueous solution, performing dispersion treatment for 30 min-2 h under the ultrasonic condition of 150 w-350 w, and then placing the carrier in a vacuum drying oven at 70 ℃ for treatment for 12h to obtain a supported binuclear polyacid ionic liquid;
wherein the structural formula of the ionic liquid N 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), FeCl3·6H2O、Mn(Ac)2·4H2The ratio of the amounts of O, sodium acetate and P123 was 6:3:50:4, and the concentration of the sodium acetate species in the mixture was 0.625 mol/L.
As a preferred embodiment, 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 MnFe2O4The mass volume ratio of the magnetic nanocrystal to the glycol is 5 g/L.
As a preferred embodiment, in step 3), the ionic liquid N and MnFe2O4@TiO2The mass ratio of the carrier is 15wt% -30 wt%, and MnFe2O4@TiO2The mass-to-volume ratio of the carrier to water was 1g/30 mL.
As a preferred embodiment, the process for the production of alkylated gasoline has a molar ratio of isobutane to 1-butene of 20: 1.
In addition, the invention also discloses a preferable preparation method of the ionic liquid N, which is prepared by the following steps:
1) stirring and mixing 1, 6-dibromohexane and morpholine for 30-60 min at room temperature in a nitrogen atmosphere, then dropwise adding 1, 4-butane sultone, then transferring to a microwave reactor, treating for 40-60 min at 60-90 ℃ under 300-500W, carrying out vacuum filtration, washing for 3-5 times with anhydrous acetone, and finally carrying out vacuum drying at 70 ℃ to obtain an intermediate product Z;
2) dropwise adding concentrated sulfuric acid into the intermediate product Z at room temperature, stirring for 1h to fully mix the concentrated sulfuric acid and the intermediate product Z, and then transferring the intermediate product Z into a hydrothermal reaction kettle to treat the intermediate product Z for 6-10 h at 80-100 ℃; and (3) washing the liquid obtained after the reaction is finished for 2-4 times by using anhydrous acetone, and then carrying out vacuum drying for 2h at the temperature of 60 ℃ to obtain the ionic liquid N.
As a preferred embodiment, in step 1), the amount ratio of the substances of 1, 6-dibromohexane, morpholine and 1, 4-butane sultone is 1:2: 2; preferably, in step 2), the mass ratio of concentrated sulfuric acid to intermediate product Z is 2: 1.
Compared with the prior art, the invention has the following advantages:
(1) compared with the conventional acidic ionic liquid catalyst, the supported dual-core polyacid ionic liquid catalyst has the advantages of high acid density, strong structural stability, high reaction stability, easiness in recycling and the like, and meanwhile, the conversion rate of the obtained butylene in the alkylation reaction process is high, and C is high8The selectivity of trimethylpentane in the hydrocarbon is obviously improved;
(2) the supported binuclear polyacid ionic liquid disclosed by the invention has the advantages that the ionic liquid is low in usage amount and good in repeatability, reaction products are convenient to separate, the preparation and use conditions are simple, the basic corrosion of equipment is low, the harm to the environment is low, and the like;
(3) multiple SO on supported binuclear polyacid ionic liquid3Synergistic effect between H sites and SO4 2-With TiO2The super acid formed between the two can obviously accelerate the reaction rate and improve the product selectivity, thereby shortening the reaction time and reducing the reaction temperature and pressure.
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 # 1:
a) mixing 1, 6-dibromohexane and morpholine according to a molar ratio of 1:2 at room temperature, stirring for 60min under a nitrogen atmosphere, continuously dropwise adding 1, 4-butane sultone, transferring the mixture into a microwave reactor, treating for 60min at 60 ℃ and 300W, performing vacuum filtration, washing for 5 times with anhydrous acetone, and finally performing vacuum drying at 70 ℃ to obtain an intermediate product Z; wherein the molar ratio of the 1, 4-butane sultone to the morpholine is 1: 1;
b) dropwise adding concentrated sulfuric acid to the intermediate product Z at room temperature, wherein the molar ratio of the concentrated sulfuric acid to the intermediate product Z is 2:1, stirring at room temperature for 1h to fully mix the concentrated sulfuric acid and the intermediate product Z, and then transferring the intermediate product Z to a hydrothermal reaction kettle to treat at 100 ℃ for 6 h; washing the liquid obtained after the reaction by using anhydrous acetone for 4 times, and then drying the liquid in vacuum at the temperature of 60 ℃ for 2 hours to obtain ionic liquid N;
c)MnFe2O4preparation of
3.0 mmol of FeCl3·6H2O and 1.5mmol Mn (Ac)2·4H2Dissolving O in 40.0mL of glycol solution, adding 25.0 mmol of sodium acetate and 2.0mmol of P123, and performing ultrasonic treatment for 30min to fully disperse the O; the mixture was then transferred to a 50 mL hydrothermal kettle at 200 ℃ and held for 48 h; after the hydrothermal kettle is naturally cooled, centrifuging, washing and drying the obtained suspension to obtain MnFe2O4Magnetic nanocrystals;
d）MnFe2O4surface TiO of2Coating of
Weighing the MnFe prepared in the step 1)2O40.1g of particles, dispersing the product in 20mL of ethylene glycol and 7.5mL of deionized water, adding 2.0mL of ammonia water, performing ultrasonic treatment for 20min, dropwise adding 0.30mL of tetrabutyl titanate under the condition of vigorous stirring, continuously stirring at room temperature for 1h, separating, treating at 105 ℃ for 12h, and roasting at 300 ℃ for 4h to obtain MnFe2O4@TiO2A carrier;
e) loading of ionic liquids
Taking 1g of MnFe2O4@TiO2The carrier was placed in 30mL of an aqueous solution, and then added thereto
Dispersing 0.3g of ionic liquid N for 30min under 350w of ultrasonic conditions, and then placing the ionic liquid N in a vacuum drying oven at 70 ℃ for 12h to obtain a dried 1# catalyst-supported binuclear polyacid ionic liquid;
2) evaluation of catalyst # 1
Weighing 1g of 1# catalyst by taking isobutane and 1-butene as raw materials, and carrying out reaction at the temperature of 70 DEG CoC. The reaction pressure is 2.0MPa, and the mass space velocity is 3h-1Reacting in a fixed bed reactor for 200 hours, wherein the molar ratio of isobutane to 1-butene is 20: 1; evaluation of the conversion of the obtained 1-butene was 99.8%, the obtained C8The content of trimethylpentane in the hydrocarbon was 83.5%.
Example 2
1) Preparation of catalyst # 2:
a) mixing 1, 6-dibromohexane and morpholine according to a molar ratio of 1:2 at room temperature, stirring for 30min under a nitrogen atmosphere, continuously dropwise adding a certain amount of 1, 4-butane sultone, transferring the mixture into a microwave reactor, treating for 40min at 90 ℃ and 500W, performing vacuum filtration, washing for 5 times by using anhydrous acetone, and finally performing vacuum drying at 70 ℃ to obtain an intermediate product Z; wherein the molar ratio of the 1, 4-butane sultone to the morpholine is 1: 1;
b) dropwise adding concentrated sulfuric acid to the intermediate product Z at room temperature, wherein the molar ratio of the concentrated sulfuric acid to the intermediate product Z is 2:1, stirring at room temperature for 1 hour to fully mix the concentrated sulfuric acid and the intermediate product Z, and then transferring the intermediate product Z to a hydrothermal reaction kettle to treat at 80 ℃ for 10 hours. After the reaction is finished, obtaining liquid, washing the liquid for 4 times by using anhydrous acetone, and drying the liquid in vacuum at the temperature of 60 ℃ for 2 hours to obtain ionic liquid N;
c)MnFe2O4the preparation procedure is the same as in example 1
d）MnFe2O4Surface TiO of2Coating the same as in example 1
e) Loading of ionic liquids
Taking 1g of MnFe2O4@TiO2Putting the carrier into 30mL of aqueous solution, adding 0.15g of ionic liquid N into the aqueous solution, performing dispersion treatment for 2 hours under the ultrasonic condition of 150w, and then putting the carrier into a vacuum drying oven at 70 ℃ for treatment for 12 hours to obtain a 2# catalyst-supported binuclear polyacid ionic liquid in a dry state;
2) evaluation of catalyst # 2
Weighing 1g of No. 2 catalyst by taking isobutane and 1-butene as raw materials, and carrying out reaction at the temperature of 70 DEG CoC. The reaction pressure is 2.0MPa, and the mass space velocity is 3h-1Reacting in a fixed bed reactor for 200 hours, wherein the molar ratio of isobutane to 1-butene is 20: 1; evaluation of the conversion of the obtained 1-butene was 99.1%, the obtained C8The content of trimethylpentane in the hydrocarbon was 81.9%.
Example 3
1) Preparation of catalyst # 3:
a) mixing 1, 6-dibromohexane and morpholine according to a molar ratio of 1:2 at room temperature, stirring for 45min under a nitrogen atmosphere, continuously dropwise adding 1, 4-butane sultone, transferring the mixture into a microwave reactor, treating for 50min at 80 ℃ and 400W, performing vacuum filtration, washing for 4 times by using anhydrous acetone, and finally performing vacuum drying at 70 ℃ to obtain an intermediate product Z; wherein the molar ratio of the 1, 4-butane sultone to the morpholine is 1: 1;
b) dropwise adding concentrated sulfuric acid to the intermediate product Z at room temperature, wherein the molar ratio of the concentrated sulfuric acid to the intermediate product Z is 2:1, stirring at room temperature for 1h to fully mix the concentrated sulfuric acid and the intermediate product Z, and then transferring the intermediate product Z to a hydrothermal reaction kettle to treat at 90 ℃ for 8 h; after the reaction is finished, obtaining liquid, washing the liquid for 3 times by using anhydrous acetone, and drying the liquid in vacuum at the temperature of 60 ℃ for 2 hours to obtain ionic liquid N;
c)MnFe2O4the preparation procedure is the same as in example 1
d）MnFe2O4Surface TiO of2Coating the same as in example 1
e) Loading of ionic liquids
Taking 1g of MnFe2O4@TiO2The carrier was placed in 30mL of an aqueous solution, and 0.15g of the carrier was added thereto
Dispersing the ionic liquid N for 1h under the ultrasonic condition of 150w, and then treating the ionic liquid N in a vacuum drying oven at 70 ℃ for 12h to obtain a 3# catalyst-supported binuclear polyacid ionic liquid in a dry state;
2) evaluation of catalyst # 3:
weighing 1g of 3# catalyst by taking isobutane and 1-butene as raw materials, and carrying out reaction at the temperature of 70 DEG CoC. The reaction pressure is 2.0MPa, and the mass space velocity is 3h-1Reacting in a fixed bed reactor for 200 hours, wherein the molar ratio of isobutane to 1-butene is 20: 1; evaluation of the conversion of the obtained 1-butene was 98.9%, the obtained C8The content of trimethylpentane in the hydrocarbon was 82.6%.
Example 4
The catalyst # 1 of example 1 was subjected to cycle evaluation, and the evaluation results thereof 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 (8)
1. A method for preparing alkylated gasoline is characterized in that: isobutane and 1-butene are used as raw materials, a supported binuclear polyacid ionic liquid is used as a catalyst, and the temperature is 70 DEGoC. The reaction pressure is 2.0MPa, and the mass space velocity is 3h-1Fixed bed reaction ofReacting in a reactor, wherein the molar ratio of isobutane to 1-butene is 20: 1;
the preparation method of the supported binuclear polyacid ionic liquid comprises the following steps:
1）MnFe2O4preparation of
FeCl is added3·6H2O and Mn (Ac)2·4H2Dissolving O in ethylene glycol solution, adding sodium acetate and P123, and performing ultrasonic treatment for 30min to obtain a mixture; then reacting the mixture for 24-48 h in a water bath at 180-220 ℃ to obtain a suspension, naturally cooling the suspension to room temperature, centrifuging, washing and drying to obtain MnFe2O4Magnetic nanocrystals;
2）MnFe2O4surface TiO of2Coating of
MnFe obtained in the step 1)2O4Dispersing magnetic nanocrystals in a dispersed phase prepared by mixing ethylene glycol and deionized water, adding ammonia water, performing ultrasound treatment for 20min, dropwise adding tetrabutyl titanate under vigorous stirring, stirring at room temperature for 1h, performing centrifugal separation, treating the centrifugally separated solid product at 105 deg.C for 12h, and roasting at 300 deg.C for 4h to obtain MnFe2O4@TiO2A carrier;
3) loading of ionic liquids
Mixing MnFe2O4@TiO2Placing a carrier in an aqueous solution, adding ionic liquid N into the aqueous solution, performing dispersion treatment for 30 min-2 h under the ultrasonic condition of 150 w-350 w, and then placing the carrier in a vacuum drying oven at 70 ℃ for treatment for 12h to obtain a supported binuclear polyacid ionic liquid;
wherein the structural formula of the ionic liquid N is shown as follows:
2. the process for producing an alkylated gasoline according to claim 1 wherein: in step 1), FeCl3·6H2O、Mn(Ac)2·4H2The ratio of the amounts of O, sodium acetate and P123 was 6:3:50:4, and the concentration of the sodium acetate species in the mixture was 0.625 mol/L.
3. The process for 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 MnFe2O4The mass volume ratio of the magnetic nanocrystal to the glycol is 5 g/L.
4. The process for 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 MnFe2O4The mass volume ratio of the magnetic nanocrystal to the glycol is 5 g/L.
5. The process for producing an alkylated gasoline according to claim 1 wherein: the molar ratio of 1-butene to isobutane is 1: 25-1: 80; the volume ratio of the catalyst to the raw material is 1: 20-1: 60.
6. A process for the production of an alkylated gasoline according to any one of claims 1 to 5 wherein: the ionic liquid N is prepared by the following steps:
1) stirring and mixing 1, 6-dibromohexane and morpholine for 30-60 min at room temperature in a nitrogen atmosphere, then dropwise adding 1, 4-butane sultone, then transferring to a microwave reactor, treating for 40-60 min at 60-90 ℃ under 300-500W, carrying out vacuum filtration, washing for 3-5 times with anhydrous acetone, and finally carrying out vacuum drying at 70 ℃ to obtain an intermediate product Z;
2) dropwise adding concentrated sulfuric acid into the intermediate product Z at room temperature, stirring for 1h, and then transferring the intermediate product Z into a hydrothermal reaction kettle to treat for 6-10 h at 80-100 ℃; and (3) washing the liquid obtained after the reaction is finished for 2-4 times by using anhydrous acetone, and then carrying out vacuum drying for 2h at the temperature of 60 ℃ to obtain the ionic liquid N.
7. The process for producing an alkylated gasoline according to claim 6 wherein: in step 1), the mass ratio of 1, 6-dibromohexane, morpholine and 1, 4-butane sultone is 1:2: 2.
8. The process for producing an alkylated gasoline according to claim 6 wherein: in step 2), the mass ratio of concentrated sulfuric acid to intermediate product Z is 2: 1.
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| CN202010196619.XA CN111250159A (en) | 2018-03-25 | 2018-03-25 | Preparation method of catalyst for gasoline production |
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| US7538256B2 (en) * | 2006-12-12 | 2009-05-26 | Chevron U.S.A., Inc. | Reduction of organic halides in alkylate gasoline |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101543786A (en) * | 2008-03-27 | 2009-09-30 | 中国石油化工股份有限公司 | Magnetic solid acid catalyst and preparation method and application thereof |
| US7919664B2 (en) * | 2008-07-31 | 2011-04-05 | Chevron U.S.A. Inc. | Process for producing a jet fuel |
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