CN108441258A - A kind of preparation method of gasoline alkylate - Google Patents
A kind of preparation method of gasoline alkylate Download PDFInfo
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- CN108441258A CN108441258A CN201810248846.5A CN201810248846A CN108441258A CN 108441258 A CN108441258 A CN 108441258A CN 201810248846 A CN201810248846 A CN 201810248846A CN 108441258 A CN108441258 A CN 108441258A
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- China
- Prior art keywords
- preparation
- mnfe
- ionic liquid
- butane
- gasoline alkylate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002608 ionic liquid Substances 0.000 claims abstract description 38
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 20
- 239000001282 iso-butane Substances 0.000 claims abstract description 18
- 235000013847 iso-butane Nutrition 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 36
- 229910017163 MnFe2O4 Inorganic materials 0.000 claims description 21
- 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 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000013067 intermediate product Substances 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical class BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 7
- 239000002159 nanocrystal Substances 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- 235000017281 sodium acetate Nutrition 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 238000005253 cladding Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000001273 butane Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 208000011580 syndromic disease Diseases 0.000 claims description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims 2
- 238000000527 sonication Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 238000011156 evaluation Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- FLTJDUOFAQWHDF-UHFFFAOYSA-N 2,2-dimethylhexane Chemical compound CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 230000029936 alkylation Effects 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
- 238000012546 transfer Methods 0.000 description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 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
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011973 solid acid 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
- 229910003163 Mn(Ac)2·4H2O Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002156 mixing Methods 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
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000003930 superacid 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
It is using iso-butane and 1 butylene as raw material, using support type double-core polyacid ionic liquid as catalyst, in temperature 70 the invention discloses a kind of preparation method of gasoline alkylateoC, reaction pressure 2.0MPa, mass space velocity 3h‑1Fixed bed reactors in react, the molar ratio of iso-butane and 1 butylene is 20:1.The present invention provides a kind of catalytic activity height, reaction stability is good, is easy recycling, the support type double-core polyacid ionic-liquid catalyst of the high income of olefin conversion and TMP, and is applied to and prepares gasoline alkylate as raw material using iso-butane and butylene.
Description
Technical field
The invention belongs to technical field of petrochemical industry, are related to a kind of catalyst, more particularly to a kind of gasoline alkylate
Preparation method.
Background technology
As China processes the deterioration of crude quality, the continuous upgrading of product gasoline quality, traditional gasoline production mode
And the gasoline products of production are facing huge challenge.Using butylene and iso-butane as raw material, produced by alkylated reaction
Without aromatic hydrocarbons, alkene, the not high-octane rating of sulfur-bearing, low-vapor pressure gasoline alkylate, be that a kind of can replace MTBE and ethyl alcohol
Environmentally friendly high-knock rating gasoline blend component.The alkylation catalyst industrially applied based on the concentrated sulfuric acid and hydrofluoric acid,
But the defects of there are acid consumptions for it greatly, equipment is corroded and environmental pollution is serious and catalyst is not easy to recycle.Solid acid is urged
Agent is applied to catalyst preparation gasoline alkylate, solves defect existing for liquid acid catalyst to a certain extent, still
Since it is there is also olefinic polyreaction trend is larger, the polyolefin of generation can lead to solid acid catalyst coking and deactivation again, Gu
It is easy to run off, repeats and regenerated using difficulty when body acid heterogeneous catalyst is in the presence of separation, mass transfer and diffusional resistance are larger, acid site number
Measure it is relatively fewer and the defects of be unevenly distributed, to limit its industrial applications.
It is ionic liquid-catalyzed prepare gasoline alkylate all shown in catalytic activity, selectivity and reuse etc. it is bright
Aobvious advantage.Acid strength has significant impact to iso-butane and butene alkylation, and is applied to production alkylation at present
The ionic liquid of gasoline belongs to monokaryon ionic liquid, but its reaction stability and thermal stability are required for further strengthening,
And it is not easily recycled utilization.The more acidic ion liquids of support type double-core have sour density height, structure compared with conventional ion liquid
Stability is strong, reaction stability is high, the advantages that being easily recycled, and there is presently no be applied to double-core ionic liquid to prepare alkane
The relevant report of base gasoline.
Invention content
In order to overcome technological deficiency existing in the prior art, the invention discloses a kind of preparation sides of gasoline alkylate
Method, it is desirable to provide a kind of catalytic activity is high, reaction stability is good, be easy to recycle, the high income of olefin conversion and TMP
Support type double-core polyacid base ionic-liquid catalyst, and be applied to and alkylation vapour is prepared as raw material using iso-butane and butylene
Oil.
The present invention is achieved through the following technical solutions：
It is using iso-butane and 1- butylene as raw material, with support type pair the invention discloses a kind of preparation method of gasoline alkylate
Core polyacid ionic liquid is catalyst, in temperature 70oC, reaction pressure 2.0MPa, mass space velocity 3h-1Fixed bed reactors in
The molar ratio of reaction, iso-butane and 1- butylene is 20:1；
Wherein, steps are as follows for the preparation side of the support type double-core polyacid ionic liquid：
1）MnFe2O4Preparation
By FeCl3·6H2O and Mn (Ac)2·4H2O is dissolved in ethylene glycol solution, and sodium acetate and P123 are then added thereto,
It is ultrasonically treated 30min and is allowed to fully dispersed, obtain mixture；Then mixture is reacted under 180 ~ 220 DEG C of water bath condition
24 ~ 48h obtains suspension, and after suspension cooled to room temperature, MnFe is obtained after centrifugation, washing, drying2O4Magnetism is received
Meter Jing；
2）MnFe2O4Surface TiO2Cladding
By step 1）In obtained MnFe2O4Magnetic Nanocrystals Containing is dispersed in the dispersed phase mixed by ethylene glycol and deionized water
In, ammonium hydroxide and ultrasound 20min are then added, butyl titanate is then added dropwise under conditions of being vigorously stirred, is continued at room temperature
It is centrifuged after stirring 1h, the solid product after centrifugation handles 12h at 105 DEG C, is obtained then at 300 DEG C of calcination process 4h
To MnFe2O4@TiO2Carrier；TiO2On the one hand cladding can significantly improve the specific surface area of catalyst, on the other hand can with from
SO on sub- liquid4 2-Effect forms solid super-strong acid, and then the reactivity of fortifying catalytic agent；
3) load of ionic liquid
By MnFe2O4@TiO2Carrier is placed in aqueous solution, then thereto be added ionic liquid N 150w ~ 350w ultrasonic item
Decentralized processing 30min ~ 2h under part, then place it in 70 DEG C of vacuum drying chambers handle 12h obtain support type double-core polyacid from
Sub- liquid；
Wherein, the structural formula of ionic liquid N is as follows：
。
Wherein, " stirring " in the technical program refers to the mixing speed of 400 ~ 600r/min.
Step 1 as a preferred implementation manner,）In, FeCl3·6H2O、Mn(Ac)2·4H2O, sodium acetate and P123
The ratio between amount of substance is 6:3:50:4, sodium acetate substance withdrawl syndrome is 0.625mol/L in mixture.
Step 2 as a preferred implementation manner,）In, ethylene glycol, deionized water, ammonium hydroxide, butyl titanate volume ratio
It is 200:75:20:3, MnFe2O4The mass volume ratio of Magnetic Nanocrystals Containing and ethylene glycol is 5g/L.
Step 3 as a preferred implementation manner,）In, ionic liquid N and MnFe2O4@TiO2The mass ratio of carrier is
15wt% ~ 30wt%, MnFe2O4@TiO2The mass volume ratio of carrier and water is 1g/30mL.
The molar ratio of iso-butane and 1- butylene is in the preparation method of the gasoline alkylate as a preferred implementation manner,
20:1。
It is to be made by the steps in addition, the invention also discloses a kind of preferred preparation method of ionic liquid N
's：
1）At ambient temperature, after 1,6- dibromo-hexanes and morpholine being stirred 30 ~ 60min in a nitrogen atmosphere, thereto
Isosorbide-5-Nitrae-butane sultone is added dropwise, be then transferred in microwave reactor under 60 ~ 90 DEG C, the power of 300 ~ 500W processing 40 ~
It after 60min, is filtered by vacuum, is used in combination anhydrous propanone to wash 3 ~ 5 times, is finally dried in vacuo at 70 DEG C, obtains centre
Product Z；
2）At ambient temperature, after the concentrated sulfuric acid being added dropwise into intermediate product Z, stirring 1h makes it be sufficiently mixed, and is then shifted
To in hydrothermal reaction kettle at 80 ~ 100 DEG C handle 6 ~ 10h；It will obtain after reaction after liquid washs 2 ~ 4 times with anhydrous propanone,
It is dried in vacuo 2h at 60 DEG C, obtains ionic liquid N.
Step 1 as a preferred implementation manner,）In, the object of 1,6- dibromo-hexane, morpholine and Isosorbide-5-Nitrae-butane sultones
The ratio between amount of matter is 1:2:2；Preferably, step 2）In, the ratio between amount of substance of the concentrated sulfuric acid and intermediate product Z is 2:1.
Compared with prior art, the present invention has the following advantages：
（1）The support type double-core polyacid ionic-liquid catalyst of the present invention has acid compared with conventional acid ionic-liquid catalyst
The advantages that density is high, structural stability is strong, reaction stability is high, catalyst is easily recycled, while in alkylated reaction mistake
Butene conversion height, the C obtained in journey8Trimethylpentane is selectively obviously improved in hydrocarbon；
（2）It is few and repeated good that the support type double-core polyacid ionic liquid of the present invention can substantially reduce ionic liquid usage amount
The good, convenient separation of reaction product, preparation and use condition is fairly simple, equipment is corroded small and endangered substantially environment small substantially
The advantages that；
（3）Multiple SO on support type double-core polyacid ionic liquid3Synergistic effect between H and SO4 2-With TiO2Between formed
Super acids can significantly accelerate reaction rate and improve selectivity of product, and then shorten the reaction time, reduce reaction
Temperature and pressure.
Specific implementation mode
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained without creative efforts, all
Belong to the scope of protection of the invention.
Embodiment 1
1）The preparation of 1# catalyst：
a）At ambient temperature, according to molar ratio 1:2 ratio is mixed 1,6- dibromo-hexanes and morpholine, in nitrogen atmosphere
Lower stir process 60min continues thereafter with dropwise addition Isosorbide-5-Nitrae-butane sultone thereto, and transfers them in microwave reactor in 60
DEG C, 60min is handled under the power of 300W, is then filtered by vacuum, and is used in combination anhydrous propanone to wash 5 times, finally at 70 DEG C
Under be dried in vacuo, obtain intermediate product Z；Wherein the molar ratio of 1,4- butane sultones and morpholine is 1:1；
b）The concentrated sulfuric acid is added drop-wise to intermediate product Z at room temperature, the wherein molar ratio of the concentrated sulfuric acid and intermediate product Z is 2:1, in room
The lower stir process 1h of temperature makes it be sufficiently mixed, and is then transferred in hydrothermal reaction kettle the processing 6h at 100 DEG C；After reaction
After obtained liquid washs 4 times with anhydrous propanone, it is dried in vacuo 2h at 60 DEG C, obtains ionic liquid N；
c)MnFe2O4Preparation
By 3.0 mmol FeCl3·6H2O and 1.5mmol Mn (Ac)2·4H2O is dissolved in the ethylene glycol solution of 40.0mL, so
The sodium acetate and 2.0mmol P123 of 25.0 mmol is added thereto afterwards, is ultrasonically treated 30min and is allowed to fully dispersed；Then will
The mixture is transferred in 50 mL water heating kettles in 200 DEG C and keeps 48h；After water heating kettle natural cooling, gained suspension is passed through
MnFe is obtained after centrifugation, washing, drying2O4Magnetic Nanocrystals Containing；
d）MnFe2O4Surface TiO2Cladding
Weigh step 1）The MnFe of middle preparation2O4Then product is dispersed in 20mL ethylene glycol and 7.5mL deionizations by particle 0.1g
In water, 2.0mL ammonium hydroxide is then added, then 0.30mL butyl titanates are added dropwise in ultrasonic 20min under conditions of being vigorously stirred,
Continue to detach after 1h is stirred at room temperature, 12h is then handled in 105 DEG C and obtains MnFe in 300 DEG C of calcination process 4h2O4@TiO2
Carrier；
E) load of ionic liquid
Take the MnFe of 1g2O4@TiO2Carrier is placed in 30mL aqueous solutions, is then added thereto
Then the ionic liquid N of 0.3g decentralized processing 30min under the ultrasound condition of 350w places it in 70 DEG C of vacuum drying chambers
Middle processing 12h obtains 1# catalyst-support type double-core polyacid ionic liquid of drying regime；
2) evaluation of 1# catalyst
Using iso-butane and 1- butylene as raw material, 1g1# catalyst is weighed, in temperature 70oC, reaction pressure 2.0MPa, mass space velocity
3h-1Fixed bed reactors in react 200h, the molar ratio of iso-butane and 1- butylene is 20:1；The conversion of evaluation gained 1- butylene
Rate is 99.8%, gained C8The content of trimethylpentane is 83.5% in hydrocarbon.
Embodiment 2
1）The preparation of 2# catalyst：
a）At ambient temperature, according to molar ratio 1:2 ratio is mixed 1,6- dibromo-hexanes and morpholine, in nitrogen atmosphere
Lower stir process 30min is continued thereafter with and a certain amount of Isosorbide-5-Nitrae-butane sultone is added dropwise thereto, and transfers them to microwave reaction
40min is handled under 90 DEG C, the power of 500W in device, is then filtered by vacuum, anhydrous propanone washing 5 times is used in combination, most
It is dried in vacuo at 70 DEG C afterwards, obtains intermediate product Z；Wherein the molar ratio of 1,4- butane sultones and morpholine is 1:1；
b）The concentrated sulfuric acid is added drop-wise to intermediate product Z at room temperature, the wherein molar ratio of the concentrated sulfuric acid and intermediate product Z is 2:1, in room
The lower stir process 1h of temperature makes it be sufficiently mixed, and is then transferred in hydrothermal reaction kettle the processing 10h at 80 DEG C.Reaction terminates
After obtain liquid, and after it is washed 4 times with anhydrous propanone, and 2h is dried in vacuo at 60 DEG C, obtains ionic liquid N；
c)MnFe2O4Preparation process with embodiment 1
d）MnFe2O4Surface TiO2Cladding is the same as embodiment 1
E) load of ionic liquid
Take the MnFe of 1g2O4@TiO2Carrier is placed in 30mL aqueous solutions, and the ionic liquid N that 0.15g is then added thereto exists
Then decentralized processing 2h under the ultrasound condition of 150w places it in processing 12h in 70 DEG C of vacuum drying chambers and obtains drying regime
2# catalyst-support type double-core polyacid ionic liquid；
2) evaluation of 2# catalyst
Using iso-butane and 1- butylene as raw material, 2 # catalyst of 1g is weighed, in temperature 70oC, reaction pressure 2.0MPa, quality are empty
Fast 3h-1Fixed bed reactors in react 200h, the molar ratio of iso-butane and 1- butylene is 20:1；Evaluation gained 1- butylene turns
Rate is 99.1%, gained C8The content of trimethylpentane is 81.9% in hydrocarbon.
Embodiment 3
1）The preparation of 3# catalyst：
a）At ambient temperature, according to molar ratio 1:2 ratio is mixed 1,6- dibromo-hexanes and morpholine, in nitrogen atmosphere
Lower stir process 45min continues thereafter with dropwise addition Isosorbide-5-Nitrae-butane sultone thereto, and transfers them in microwave reactor in 80
DEG C, 50min is handled under the power of 400W, is then filtered by vacuum, and is used in combination anhydrous propanone to wash 4 times, finally at 70 DEG C
Under be dried in vacuo, obtain intermediate product Z；Wherein the molar ratio of 1,4- butane sultones and morpholine is 1:1；
b）The concentrated sulfuric acid is added drop-wise to intermediate product Z at room temperature, the wherein molar ratio of the concentrated sulfuric acid and intermediate product Z is 2:1, in room
The lower stir process 1h of temperature makes it be sufficiently mixed, and is then transferred in hydrothermal reaction kettle the processing 8h at 90 DEG C；After reaction
Liquid is obtained, and after it is washed 3 times with anhydrous propanone, and 2h is dried in vacuo at 60 DEG C, obtains ionic liquid N；
c)MnFe2O4Preparation process with embodiment 1
d）MnFe2O4Surface TiO2Cladding is the same as embodiment 1
E) load of ionic liquid
Take the MnFe of 1g2O4@TiO2Carrier is placed in 30mL aqueous solutions, is then added 0.15g's thereto
Then ionic liquid N 1 h of decentralized processing under the ultrasound condition of 150w is placed it in 70 DEG C of vacuum drying chambers and is handled
12h obtains 3# catalyst-support type double-core polyacid ionic liquid of drying regime；
2) evaluation of 3# catalyst：
Using iso-butane and 1- butylene as raw material, 3 # catalyst of 1g is weighed, in temperature 70oC, reaction pressure 2.0MPa, quality are empty
Fast 3h-1Fixed bed reactors in react 200h, the molar ratio of iso-butane and 1- butylene is 20:1；Evaluation gained 1- butylene turns
Rate is 98.9%, gained C8The content of trimethylpentane is 82.6% in hydrocarbon.
Embodiment 4
1# catalyst in embodiment 1 is subjected to cycle evaluation, gained evaluation result is as shown in table 1 below
。
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of gasoline alkylate, it is characterised in that：Using iso-butane and 1- butylene as raw material, with support type double-core
Polyacid ionic liquid is catalyst, in temperature 70oC, reaction pressure 2.0MPa, mass space velocity 3h-1Fixed bed reactors in it is anti-
It answers, the molar ratio of iso-butane and 1- butylene is 20:1；
Wherein, steps are as follows for the preparation side of the support type double-core polyacid ionic liquid：
1）MnFe2O4Preparation
By FeCl3·6H2O and Mn (Ac)2·4H2O is dissolved in ethylene glycol solution, and sodium acetate and P123 are then added thereto, is surpassed
Sonication 30min obtains mixture；Then mixture is reacted under 180 ~ 220 DEG C of water bath condition 24 ~ 48h obtain it is suspended
Liquid obtains MnFe after suspension cooled to room temperature after centrifugation, washing, drying2O4Magnetic Nanocrystals Containing；
2）MnFe2O4Surface TiO2Cladding
By step 1）In obtained MnFe2O4Magnetic Nanocrystals Containing is dispersed in the dispersed phase mixed by ethylene glycol and deionized water
In, ammonium hydroxide and ultrasound 20min are then added, butyl titanate is then added dropwise under conditions of being vigorously stirred, is continued at room temperature
It is centrifuged after stirring 1h, the solid product after centrifugation handles 12h at 105 DEG C, is obtained then at 300 DEG C of calcination process 4h
To MnFe2O4@TiO2Carrier；
3）The load of ionic liquid
By MnFe2O4@TiO2Carrier is placed in aqueous solution, then thereto be added ionic liquid N 150w ~ 350w ultrasonic item
Decentralized processing 30min ~ 2h under part, then place it in 70 DEG C of vacuum drying chambers handle 12h obtain support type double-core polyacid from
Sub- liquid；
Wherein, the structural formula of ionic liquid N is as follows：
。
2. the preparation method of gasoline alkylate as described in claim 1, it is characterised in that：Step 1）In, FeCl3·6H2O、Mn
(Ac)2·4H2O, the ratio between amount of substance of sodium acetate and P123 is 6:3:50:4, sodium acetate substance withdrawl syndrome is in mixture
0.625mol/L。
3. the preparation method of gasoline alkylate as described in claim 1, it is characterised in that：Step 2）In, ethylene glycol, deionization
Water, ammonium hydroxide, butyl titanate volume ratio be 200:75:20:3, MnFe2O4The mass volume ratio of Magnetic Nanocrystals Containing and ethylene glycol
For 5g/L.
4. the preparation method of gasoline alkylate as described in claim 1, it is characterised in that：Step 2）In, ethylene glycol, deionization
Water, ammonium hydroxide, butyl titanate volume ratio be 200:75:20:3, MnFe2O4The mass volume ratio of Magnetic Nanocrystals Containing and ethylene glycol
For 5g/L.
5. the preparation method of gasoline alkylate as described in claim 1, it is characterised in that：The molar ratio of 1- butylene and iso-butane is
1:25~1:80；The volume ratio of catalyst and raw material is 1:20~1:60.
6. the preparation method of gasoline alkylate as described in any in claim 1-5, it is characterised in that：It is described；Ionic liquid N is
Made of being made by the steps：
1）At ambient temperature, after 1,6- dibromo-hexanes and morpholine being stirred 30 ~ 60min in a nitrogen atmosphere, thereto
Isosorbide-5-Nitrae-butane sultone is added dropwise, be then transferred in microwave reactor under 60 ~ 90 DEG C, the power of 300 ~ 500W processing 40 ~
It after 60min, is filtered by vacuum, is used in combination anhydrous propanone to wash 3 ~ 5 times, is finally dried in vacuo at 70 DEG C, obtains centre
Product Z；
2）At ambient temperature, after the concentrated sulfuric acid being added dropwise into intermediate product Z, 1h is stirred, hydrothermal reaction kettle is then transferred to
In at 80 ~ 100 DEG C handle 6 ~ 10h；It will obtain after reaction after liquid washs 2 ~ 4 times with anhydrous propanone, the vacuum at 60 DEG C
Dry 2h, obtains ionic liquid N.
7. the preparation method of gasoline alkylate as claimed in claim 6, it is characterised in that：Step 1）In, 1,6- dibromo-hexane,
The ratio between amount of substance of quinoline and 1,4- butane sultones is 1:2:2.
8. the preparation method of gasoline alkylate as claimed in claim 6, it is characterised in that：Step 2）In, the concentrated sulfuric acid and intermediate production
The ratio between amount of substance of object 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 |
| CN202010196635.9A CN111250160A (en) | 2018-03-25 | 2018-03-25 | Catalyst for gasoline production |
| CN201810248846.5A CN108441258B (en) | 2018-03-25 | 2018-03-25 | Preparation method of alkylated gasoline |
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- 2018-03-25 CN CN202010196635.9A patent/CN111250160A/en not_active Withdrawn
- 2018-03-25 CN CN201810248846.5A patent/CN108441258B/en not_active Expired - Fee Related
- 2018-03-25 CN CN202010196619.XA patent/CN111250159A/en not_active Withdrawn
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| US20090264694A1 (en) * | 2006-12-12 | 2009-10-22 | Chevron U.S.A., Inc. | Reduction of organic halides in alkylate gasoline |
| 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 |
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| CN105195177A (en) * | 2015-09-18 | 2015-12-30 | 宁波海越新材料有限公司 | Alkylated gasoline catalyst and preparing method thereof |
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| CN111250160A (en) | 2020-06-09 |
| CN111250159A (en) | 2020-06-09 |
| CN108441258B (en) | 2020-06-09 |
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