CN106398742A - Method for preparing alkylation gasoline by polyether type acid ionic liquid coupling trifluoromethanesulfonic acid catalysis - Google Patents
Method for preparing alkylation gasoline by polyether type acid ionic liquid coupling trifluoromethanesulfonic acid catalysis Download PDFInfo
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- CN106398742A CN106398742A CN201611139568.7A CN201611139568A CN106398742A CN 106398742 A CN106398742 A CN 106398742A CN 201611139568 A CN201611139568 A CN 201611139568A CN 106398742 A CN106398742 A CN 106398742A
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 21
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 title abstract description 16
- 238000005804 alkylation reaction Methods 0.000 title abstract description 15
- 230000029936 alkylation Effects 0.000 title abstract description 14
- 239000002253 acid Substances 0.000 title abstract description 11
- 239000004721 Polyphenylene oxide Substances 0.000 title abstract description 6
- 230000008878 coupling Effects 0.000 title abstract description 6
- 238000010168 coupling process Methods 0.000 title abstract description 6
- 238000005859 coupling reaction Methods 0.000 title abstract description 6
- 229920000570 polyether Polymers 0.000 title abstract description 6
- 238000007171 acid catalysis Methods 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 24
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001282 iso-butane Substances 0.000 claims abstract description 12
- 235000013847 iso-butane Nutrition 0.000 claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 9
- 239000008236 heating water Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 abstract description 24
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 abstract description 24
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000005191 phase separation Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000005457 ice water Substances 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000004445 quantitative analysis Methods 0.000 description 7
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000011973 solid acid Substances 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910006069 SO3H Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 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
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- -1 iso-butane alkane Chemical class 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 238000007296 Stetter synthesis reaction Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000003442 catalytic alkylation reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000011557 critical solution Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/60—Controlling or regulating the processes
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/62—Catalyst regeneration
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a new method for preparing alkylation gasoline by catalysis. The new method is characterized in that Bronsted polyether type acid ionic liquid coupling trifluoromethanesulfonic acid is used as a catalyst, and is used for catalyzing iso-butane and isobutene to perform alkylation reaction, so as to prepare the alkylation gasoline. The method has the advantages that the temperature control property of ionic liquid is utilized, the temperature-control phase separation and catalyzing in the alkylation gasoline preparation process is firstly realized, and the purposes of simple separation and effective recycling of the catalyst are realized; the catalyzing system presents the high selectivity of C8 products and high selectivity of TMP (trimethylpentane).
Description
Technical field
The present invention relates to the new method of gasoline alkylate is prepared in a kind of catalysis, in particular to a kind of polyether-typeAcidic ion liquid coupling TFMS catalyzing iso-butane alkane and isobutene alkylated reaction prepare gasoline alkylate
New method.
Background technology
The mixing of the isomery C8 alkane that gasoline alkylate is made up of trimethylpentane (TMP) and dimethylhexane (DMH)
Thing, has the advantages that octane number is high, steam forces down, the not non-hydrocarbon component such as sulfur-bearing and nitrogen, is excellent blended gasoline.Alkylation vapour
The TMP/DMH value of oil is bigger, and octane number is higher, and oil quality is also better.At present, the yield of the gasoline alkylate in the whole world is
102000000 tons/year, account for the 13%-15% of gasoline total flow.In recent years, with economic fast development and people to environmental protection
Gradually stepping up of consciousness, increasing to the demand of the gasoline alkylate of cleaning.Therefore, the clean manufacturing skill of gasoline alkylate
Each major company of the Shu Shi world and the problem of researchers primary study.
Gasoline alkylate mainly passes through C4 alkene (including 1- butylene, 2- butylene and isobutene) and the different chain of C4 under acid catalysis
The alkylated reaction preparation of alkane (iso-butane).Alkyl from the thirties in last century, with the concentrated sulfuric acid or hydrofluoric acid as catalyst
Change gasoline producing process just to have industrialized and used till today.It is obvious that these strong acid catalysts belong to the unfriendly catalyst of environment,
As spent acid discharge capacity is big, serious to equipment corrosion.In addition, these acid catalyst consumptions are big, and can not weigh for disposable consumption
Multiple use, causes manufacturing cost to increase.These shortcomings existing for traditional liquid acid catalyst, in recent years, substantial amounts of solid
Acid is studied and is used for catalyzing and synthesizing gasoline alkylate (CN200510053489.X；CN200810102238.X；
CN201010121921.5；CN201510599098.1).Combined by ABB Lummus company and Akzo Nobel catalyst plant and push away
The AlkyClean technology going out is first solid acid catalyst technology being used for commercial mass production, the pass of AlkyClean technology
Key is using special solid acid catalyst (alumina zeolites of platiniferous) with using new fixed bed reactors.Produce per year at present
1.55 hundred million liters of alkylate oil projects start in Shandong Zibo in August, 2015.Although AlkyClean solid acid catalysis technology has
There is very big industrialization potential, but still need to overcome solid acid catalyst defect inherently, such as mass transfer and diffusional resistance are big, easily
The shortcomings of inactivation.
Ionic liquid forces down because it has the advantages that steam, heat endurance high, structure can design, reusable, as
The eco-friendly solvent of one class or catalyst are used for many chemical reaction processes.Research shows, Lewis acid chlorine aluminic acid class from
Sub- liquid is applied to catalysis to be prepared gasoline alkylate and shows obvious advantage (Catal in terms of catalysis activity and selectivity
Lett,2011,141:1405-1419；Catalysis journal, 2004,25 (1):60-64；Chemical Reaction Engineering and technique, 2004,20
(3):229-234).However, such ionic liquid is more sensitive to liquid to steam ratio, easily cause the irreversible inactivation of catalyst.
Acidic ion liquid is relatively stable, but because its acidity is weaker, catalytic alkylation reaction effect is undesirable.Patent
CN201510923900.8 reports containing multipleThe ionic liquid-catalyzed alkylated reaction of acid centre, obtains
Higher alkylate oil yield.In recent years, utilizeWith Lewis double presence of acidic ionic liquid catalyst preparation alkylation vapour
Oil, its good result show preferable development prospect (Catal Commun, 2012,26:68-71,
CN201410141365.6).
Some special groups are assembled in the structure of ionic liquid by chemical reaction, prepare functionalization ionic liquid
Body, is one of focus of current ionic liquid research.Polyether chain is incorporated in the cation of ionic liquid, generally can give from
The performance of sub- liquid " temperature control ".A kind of quaternary ammonium salt temperature controlled ionic liquid containing polyether chain of patent 200610046354.5 invention
1, the system that such ionic liquid is formed with organic solvent has the function of " high temperature is miscible, phase splitting at room temperature ", therefore can pass through
" temperature control " realization " homogeneous reaction, two-phase laminated flow ", makes homogeneous complex reaction catalyst be able to simple and effective separate and recover and follow
Ring uses.This temperature controlled system has been used for hydroformylation reaction (CN200610046355.X) and the hydrogenation of higher olefins
In (CN200610046354.5 and 200810229763.8), catalyst shows good recycling.In these reactions
In, temperature controlled ionic liquid acts mainly as the carrier of catalyst, to realize the easy recovery of catalyst.
[(C2H5)3N(CH2CH2O)nCH3]+[CH3SO3]-
1
Document Green Chemistry, 2010,12,1196-1200 and Tetrahedron, 2010,66 (47), 9145-
9150 report a kind of thiazoles temperature controlled ionic liquid 2 and a kind of triazole type temperature controlled ionic liquid 3 respectively, respectively with this two class from
Sub- liquid is the precursor of N- heterocyclic carbone catalyst, and with ionic-liquid catalyst from as a phase, is prepared with certain proportion
Toluene and normal heptane are a phase, can realize " homogeneous reaction, the two-phase laminated flow " of Stetter reaction, ionic liquid by " temperature control "
Body catalyst can simply reclaim and reuse.
It is new that present invention design synthesizes a classAcid temperature controlled ionic liquid, for TFMS
(CF3SO3H) coupling and catalyzing prepares the process of gasoline alkylate, achieves Thermoregulated phase separation catalysis first and prepares gasoline alkylate,
Not only catalyst can efficiently recycle, and reaction has high C8 selectivity of product and high TMP is selective.
Content of the invention
The invention provides the new method of gasoline alkylate is prepared in a kind of catalysis.The method is that have temperature control based on one kind
CanAcid polyether-type ionic liquid is it is achieved that Thermoregulated phase separation catalysis prepare gasoline alkylate.The present invention is first
By structure of controlling temperature unit polyether chain andAcidic-group sulfonic group (- SO3H), it is collectively incorporated into the cation of ionic liquid
In, prepare and there is temperature-control performanceAcidic ion liquid, and with strong acid TFMS (CF3SO3H) coupling is urged
Gasoline alkylate is prepared in change.This inventive method mainly has the characteristic of following three aspects：(1) pass through to change weakly acidic ionic liquid
With highly acid CF3SO3The proportioning of H and the length changing polyether chain in ionic liquid, can adjust the acidity of catalyst system and catalyzing,
Seek to be suitable for the acid range that gasoline alkylate is prepared in catalysis, improve the selectivity of alkylate oil C8 product and the choosing of TMP
Selecting property.(2) utilize the distinctive temperature-control performance of ionic liquid, when setting reaction temperature is higher than critical solution temperature, catalyst phase (from
Sub- fluid load CF3SO3H) coexisted a phase with reactant, after reaction terminates, is down to room temperature, automatic point again of catalyst phase and product
Place's two-phase, that is, reach the purpose of so-called " high temperature homogeneous reaction, low temperature two-phase laminated flow ", both can achieve efficiently urging of homogeneous reaction
Change, can achieve that the catalyst of heterogeneous catalysis is easily separated again, reclaim and recycling.(3) due to strong acid CF3SO3H be supported on from
In sub- liquid, therefore can recycle with ionic liquid, overcome the disposable problem consuming of strong acid catalyst.The present invention is to urge
Change is prepared gasoline alkylate and is provided new approaches.
The technical scheme is that and be achieved in that：
CF by certain volume ratio3SO3H and ionic liquid are added in the autoclave being furnished with mechanical agitator, envelope
Kettle, with air in high pure nitrogen displacement kettle for several times.It is then pumped into the iso-butane of certain volume and the mixing liquid of isobutene, water-bath
Heat and open mechanical agitation, react certain time under certain stir speed (S.S.), uniform temperature.Cool down autoclave with ice-water bath,
Drive kettle, upper phase is alkylate oil, can pour out, first with gas chromatography mass spectrometry chromatographic qualitative analytical reactions product, Ran Houli
Use chromatogram ration analysis selectivity of product；Lower floor's thick liquid is catalyst phase (ionic liquid loaded CF3SO3H), may be used
Direct reuse.
The structural formula of the ionic liquid described in the inventive method is as follows：
CF described in the inventive method3SO3The volume ratio of H and ionic liquid generally 0.18～0.25, reaction temperature is general
For 50～70 DEG C, the reaction time is generally 10～30min, and stir speed (S.S.) is generally 800～1000r/min.
The present invention, compared with traditional method, is characterized in：(1) ionic liquid stability is high；(2) reaction have high
Selectively, oil quality is good for TMP；(3) reaction is homogeneously carried out, and reaction rate is fast, and the required reaction time is short；(4) catalyst separates
Simply, room temperature is automatically and product split-phase；(5) strong acid is supported in ionic liquid, can be recycled, and it is good to recycle effect.
Specific implementation method
With reference to embodiment, the method for the present invention is described further, but is not limitation of the invention.
(1) synthesis step of ionic liquid
Embodiment 1：0.01mol bis- n-hexylamine and 10mL absolute ethyl alcohol are added in autoclave, are placed in refrigerator
Freezing 2h.The oxirane weighing certain volume is added in autoclave, seals kettle, with the N of 5MPa2Air 3 in displacement kettle
～5 times.Under room temperature, stirring reaction 2h is after 60 DEG C of insulation reaction 4h, cooling, release, drives kettle.Reactant mixture is moved into three mouthfuls
In flask, vacuum distillation removing absolute ethyl alcohol, to constant weight, obtains intermediate compound I, can calculate intermediate compound I according to product weightening finish method
Average degree of polymerization (n).Add 0.01mol PS in there-necked flask, add 10mL ethyl acetate to make it molten
Solution, the then intermediate compound I of the amount of material such as dropping.Completion of dropping, stirring reaction 5h at 50 DEG C.After reaction terminates, by gained
Mixture moves in single-necked flask, and vacuum distillation desolvation ethyl acetate obtains intermediate II.In 50mL single-necked flask,
Weigh 0.01mol intermediate II, add 10mL water so that it is dissolved, then dropping 10mL is dissolved with 0.01mol TFMS
(CF3SO3H the aqueous solution).Completion of dropping, gained mixture is stirred at room temperature reaction 12h.After reaction terminates, remove under reduced pressure molten
Agent water, is dried, that is, obtains object ion liquid III.
(2) preparation of gasoline alkylate
Embodiment 2：To in the autoclave being furnished with mechanical agitator, add 2mL CF3SO3H and 10mL ionic liquid (n
=50), seal kettle, replace air 4 times in kettle with 5MPa high pure nitrogen.Being then pumped into 30mL mol ratio is 10：1 iso-butane and
The mixing liquid of isobutene, heating water bath simultaneously opens mechanical agitation, is 1000r/min, reacts at 60 DEG C in stir speed (S.S.)
30min.Cool down autoclave with ice-water bath, drive kettle, collect upper strata alkylation oil phase.Carry out quantitative analysis with gas-chromatography.Alkyl
The selectivity of carburetion C8 product is 65%, and wherein trimethylpentane (TMP) accounts for 99.1%.
Embodiment 3：To in the autoclave being furnished with mechanical agitator, add 1.8mL CF3SO3H and 10mL ionic liquid
(n=75), seal kettle, replace air 4 times in kettle with 5MPa high pure nitrogen.Being then pumped into 30mL mol ratio is 10：1 iso-butane
With the mixing liquid of isobutene, heating water bath simultaneously opens mechanical agitation, is 1000r/min, reacts at 60 DEG C in stir speed (S.S.)
30min.Cool down autoclave with ice-water bath, drive kettle, collect upper strata alkylation oil phase.Carry out quantitative analysis with gas-chromatography.Alkyl
The selectivity of carburetion C8 product is 68%, and wherein trimethylpentane (TMP) accounts for 99.0%.
Embodiment 4：To in the autoclave being furnished with mechanical agitator, add 2.5mL CF3SO3H and 10mL ionic liquid
(n=75), seal kettle, replace air 4 times in kettle with 5MPa high pure nitrogen.Being then pumped into 30mL mol ratio is 10：1 iso-butane
With the mixing liquid of isobutene, heating water bath simultaneously opens mechanical agitation, is 1000r/min, reacts at 60 DEG C in stir speed (S.S.)
30min.Cool down autoclave with ice-water bath, drive kettle, collect upper strata alkylation oil phase.Carry out quantitative analysis with gas-chromatography.Alkyl
The selectivity of carburetion C8 product is 79%, and wherein trimethylpentane (TMP) accounts for 98.2%.
Embodiment 5：To in the autoclave being furnished with mechanical agitator, add 2mL CF3SO3H and 10mL ionic liquid (n
=75), seal kettle, replace air 4 times in kettle with 5MPa high pure nitrogen.Being then pumped into 30mL mol ratio is 10：1 iso-butane and
The mixing liquid of isobutene, heating water bath simultaneously opens mechanical agitation, is 800r/min, reacts 30min at 60 DEG C in stir speed (S.S.).
Cool down autoclave with ice-water bath, drive kettle, collect upper strata alkylation oil phase.Carry out quantitative analysis with gas-chromatography.Alkylate oil C8
The selectivity of product is 81%, and wherein trimethylpentane (TMP) accounts for 99.8%.
Embodiment 6：To in the autoclave being furnished with mechanical agitator, add 2mL CF3SO3H and 10mL ionic liquid (n
=75), seal kettle, replace air 4 times in kettle with 5MPa high pure nitrogen.Being then pumped into 30mL mol ratio is 10：1 iso-butane and
The mixing liquid of isobutene, heating water bath simultaneously opens mechanical agitation, is 800r/min, reacts 30min at 50 DEG C in stir speed (S.S.).
Cool down autoclave with ice-water bath, drive kettle, collect upper strata alkylation oil phase.Carry out quantitative analysis with gas-chromatography.Alkylate oil C8
The selectivity of product is 78%, and wherein trimethylpentane (TMP) accounts for 99.3%.
Embodiment 7：To in the autoclave being furnished with mechanical agitator, add 2mL CF3SO3H and 10mL ionic liquid (n
=75), seal kettle, replace air 4 times in kettle with 5MPa high pure nitrogen.Being then pumped into 30mL mol ratio is 10：1 iso-butane and
The mixing liquid of isobutene, heating water bath simultaneously opens mechanical agitation, is 800r/min, reacts 30min at 70 DEG C in stir speed (S.S.).
Cool down autoclave with ice-water bath, drive kettle, collect upper strata alkylation oil phase.Carry out quantitative analysis with gas-chromatography.Alkylate oil C8
The selectivity of product is 77%, and wherein trimethylpentane (TMP) accounts for 99.2%.
Embodiment 8：To in the autoclave being furnished with mechanical agitator, add 2mL CF3SO3H and 10mL ionic liquid (n
=75), seal kettle, replace air 4 times in kettle with 5MPa high pure nitrogen.Being then pumped into 30mL mol ratio is 10：1 iso-butane and
The mixing liquid of isobutene, heating water bath simultaneously opens mechanical agitation, is 800r/min, reacts 10min at 60 DEG C in stir speed (S.S.).
Cool down autoclave with ice-water bath, drive kettle, collect upper strata alkylation oil phase.Carry out quantitative analysis with gas-chromatography.Alkylate oil C8
The selectivity of product is 72%, and wherein trimethylpentane (TMP) accounts for 98.8%.
(3) the recycling performance of catalyst
Embodiment 9-13：Experiment condition and step with embodiment 5, simply by ionic liquid and CF3SO3H is changed to embodiment 5
Sticky ionic liquid body phase (load C F of Zhong Funei lower floor3SO3H), after carrying out five times repeating back to use experiment, alkylate oil C8 product
Selectivity be 78%, wherein trimethylpentane (TMP) accounts for 99.3%.
Claims (2)
1. a kind of polyether-typeAcidic ion liquid couples the method that gasoline alkylate is prepared in TFMS catalysis, its
Feature is to add TFMS and the ionic liquid of certain volume ratio in autoclave, and being then pumped into mol ratio is 10：1
Iso-butane and the mixing liquid of isobutene, heating water bath simultaneously opens mechanical agitation, reacts certain time at a certain temperature, reaction
After end, standing, upper phase is alkylate oil, can pour out, lower catalyst agent phase (ionic liquid loaded TFMS)
Can direct reuse, the structural formula of wherein said ionic liquid is as follows：
2. in accordance with the method for claim 1, the volume ratio of TFMS and ionic liquid is 0.18～0.25, reaction temperature
Generally 50～70 DEG C of degree, the reaction time is generally 10～30min, and stir speed (S.S.) is generally 800～1000r/min.
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| CN108212212A (en) * | 2018-01-29 | 2018-06-29 | 中国科学院青岛生物能源与过程研究所 | A kind of temperature sensitive acidic ionic liquid and preparation method thereof and the purposes in catalysis microcrystalline cellulose hydrolysis |
| CN110079359A (en) * | 2019-05-17 | 2019-08-02 | 青岛科技大学 | A kind of preparation method of gasoline alkylate |
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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 |
| CN103333114A (en) * | 2013-07-18 | 2013-10-02 | 青岛科技大学 | Imidazole ionic liquid with dual functions of oxidation and temperature control and synthetic method of ionic liquid |
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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 |
| CN103333114A (en) * | 2013-07-18 | 2013-10-02 | 青岛科技大学 | Imidazole ionic liquid with dual functions of oxidation and temperature control and synthetic method of ionic liquid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108212212A (en) * | 2018-01-29 | 2018-06-29 | 中国科学院青岛生物能源与过程研究所 | A kind of temperature sensitive acidic ionic liquid and preparation method thereof and the purposes in catalysis microcrystalline cellulose hydrolysis |
| CN110079359A (en) * | 2019-05-17 | 2019-08-02 | 青岛科技大学 | A kind of preparation method of gasoline alkylate |
| CN110079359B (en) * | 2019-05-17 | 2021-05-25 | 青岛科技大学 | Preparation method of alkylated gasoline |
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