CN100348320C - Ion liquid catalyst for producing alkylated oil and its preparation method - Google Patents
Ion liquid catalyst for producing alkylated oil and its preparation method Download PDFInfo
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Abstract
The present invention relates to an ionic liquid catalyst for producing alkylation oil and a preparation method thereof. The existing ionic liquid is modified by sulfur-containing or oxygen-containing organic compounds and benzene or alkyl derivatives of benzene. The modified ionic liquid as the catalyst to prepare the alkylation oil can improve the selectivity of alkylation reaction so that an alkylation product has high octane number, and the proportion of C8 in an alkylation oil solution can reach 70 to 90%. The catalyst has the outstanding advantages that the proportion of trimethylpentane in a C8 component reaches more than 90%; simultaneously, the product yield can be further improved; the yield can reach 170 to 180% of the olefin feed volume.
Description
Technical field:
The present invention relates to a kind of ionic-liquid catalyst of producing alkylate oil and preparation method thereof.
Background technology:
Along with the develop rapidly and the human pay attention to day by day to environmental protection of auto industry, countries in the world constantly increase the demand of unleaded high-knock rating gasoline, and aromatic hydrocarbons and olefin(e) centent also will be received restriction in the gasoline simultaneously.In this case, calling in alkylate oil in gasoline is a kind of effective ways of keeping gasoline high-octane rating and low-steam pressure.
As everyone knows, the catalyst that present industrial alkane and olefin alkylation adopted is mainly liquid strong acid such as the concentrated sulfuric acid or hydrofluoric acid.But problems such as these liquid strong acid have, and corrosivity is strong, production operation is difficult, product postprocessing trouble and environmental pollution are serious.Pay much attention to the protection environment for human survival in the world today; walk under the main trend of sustainable development path, researching and developing alkylation catalyst of new generation and reaction process has become important and need to be resolved hurrily research topic in petrochemical industry catalysis and the reaction engineering field.
In recent years, the research to the alkylation aspect both at home and abroad concentrates in the development of solid acid catalyst and process matched therewith thereof, in the hope of solving the pollution that concentrated sulfuric acid method and hydrofluoric acid method cause and the problem of equipment corrosion.But all there is a common defective in the various novel solid catalyst that are used for the abovementioned alkyl reaction of report at present, and promptly catalysqt deactivation is very fast.The supercritical reaction system of the academy of sciences of CNPC and the Alkylene technology of American UOP company have obtained effect preferably, but also have the too high problem of production cost.
Ionic liquid (ILs) is a kind of salt that at room temperature exists with liquid form, and is at present in the ascendant about the research of ion liquid preparation and application facet.US5994602, US5824832, W099/03163 are with the alkylating catalyst of ionic liquid as benzene and derivative and alkene.French Patent (FRP) FR2626572 utilizes imidazole type or four to replace the catalyst of amine type ionic liquid as isoparaffin and olefin alkylation, but the product of this patent is based on the C6 and the C7 of isomery, the content of C8 alkane is very low in the product, does not possess actual application value; And imidazoles is that cationic ionic liquid is because its synthetic difficulty and price problem are difficult to obtain popularization and utilization.
The researcher of Petroleum Univ. is in its patent (CN1432627A), disclose with the ionic liquid-catalyzed iso-butane that contains single metallic element and the alkylated reaction of butylene, obtained result preferably, C8 content can be brought up to about 70%, after this they have made the composite anion ILs (CN1500764A) that contains two or more metal again, with it is that the yield of the alkylate oil of Preparation of Catalyst can reach 170～180% of alkene feed volume, the shared ratio of C8 can reach 60-80% in the alkylate oil, the trimethylpentane ratio reaches more than 70% in its C8 component, RON (research octane number (RON)) can reach 93-98, but because two kinds of slaines compatibility in preparation is relatively poor, be difficult for being prepared into ionic liquid, and preparation process is comparatively loaded down with trivial details.
Summary of the invention:
The purpose of this invention is to provide a kind of ionic-liquid catalyst of producing alkylate oil and preparation method thereof, adopt the alkyl derivative of sulfur-bearing or oxygen containing organic compound, benzene or benzene that existing ionic liquid is carried out modification, ionic liquid with this modification is the Preparation of Catalyst alkylate oil, improve the selectivity of alkylated reaction, make alkylation products have higher octane number, can further improve the yield of product simultaneously.
The invention provides a kind of ionic-liquid catalyst of producing alkylate oil, with the hydrohalide of the amine that contains alkyl or the hydrohalide of pyridine is the cationic source material, metal halide is the ionic liquid of negative ion source material preparation, it is characterized in that: add the modifier of content at 200-20000ppm in the ionic liquid preparation process, said modifier is the alkyl derivative of carbon disulfide, butanethiol, benzene, benzene or their mixture.
Above-mentioned metal halide is a kind of in the halide of aluminium, copper, nickel, zinc or their mixture, is preferably alchlor.
Nitrogen-atoms is saturated by four substituting groups in the hydrohalide of the described amine that contains alkyl or the hydrohalide of pyridine, and wherein has a hydrogen atom and an alkyl substituent at least.The hydrohalide that contains the amine of alkyl is preferably the hydrochloric acid quaternary amine, and the hydrohalide of pyridine is preferably pyridine hydrochloride.
Sulfur-bearing or oxygen containing organic compound in the described modifier have the organic compound of lone pair electrons on sulphur or the oxygen atom in the preferred molecule.Benzene and alkyl derivative thereof can also substitute with the organic compound of the typical structure with this two classes material representative.Modifier is preferably benzene, toluene, acetone, carbon disulfide, butanethiol or their mixture.
The above-mentioned ionic-liquid catalyst of the present invention adopts following method preparation, comprises following two steps:
A: under the protection of drying nitrogen; metal halide is slowly added in the hydrohalide of the hydrohalide of the amine that contains alkyl or pyridine; metal halide is 1～2: 1 with the mol ratio of the hydrohalide of hydrohalide of amine that contains alkyl or pyridine; stir at ambient temperature and be no less than 30 minutes; be warming up to 80 ℃ then; continue to stir, until the liquid that generates homogeneous.
B: under the protective condition of room temperature, drying nitrogen, in above-mentioned ionic liquid, add the modifier of the alkyl derivative contain sulfur-bearing or the oxygen containing thing that organises, benzene or benzene, and be stirred to modifier and dissolve in ionic liquid fully, make ionic-liquid catalyst.
When ionic liquid of the present invention is used to produce alkylate oil as catalyst, its reaction condition and prior art are basic identical, are raw material with iso-butane and butylene, carry out alkylated reaction at-20～80 ℃, reaction pressure is 0.1～1.5Mpa, and the alkane alkene ratio of raw material is 1～200: 1.Wherein butylene is two or more a mixture of 2-butylene, isobutene, 1-butylene or they.Choosing of reaction pressure to guarantee that reaction raw materials maintenance liquid condition is a lower limit under the reaction condition.Produce the autoclave of the selected reactor of alkylate oil for the device of band stirring, or industrial sulfuric acid or the employed continuous process units of hydrofluoric acid method alkylated reaction, or other successive reaction apparatus.
The invention effect: the yield of the alkylate oil that the present invention is prepared can reach 170～180% of alkene feed volume, the proportion of C8 can reach 70～90% in the alkylated oil, its outstanding advantage is that the proportion in the C8 component of trimethylpentane reaches more than 90 in the C8 component, the octane number of gained alkylate oil can reach RON (research octane number (RON)) 100, the ionic-liquid catalyst that makes with the method for the invention can use more than 10 times repeatedly, and catalytic activity does not subtract.Modifier used in the present invention is cheap and easy to get, and method of modifying is simple, helps reducing catalyst production cost.
The alkylate oil that uses the ionic liquid-catalyzed generation of modification of the present invention is through Mass Spectrometer Method, its composition all is an isoparaffin, there are not macromolecular alkene and aromatic hydrocarbons to generate, there is not to find to contain the organic matter that modification is used simultaneously, illustrate that not only method of the present invention can restrain side reactions such as alkene condensation and cyclisation and take place, and illustrate that the organic modifiers and the ionic liquid generation chemical action that add are fixed up modifier, can not be lost in the alkylation products and go.Ion liquid another outstanding feature of the present invention is that it does not almost have corrosivity to equipment, and is non-volatile, separate easily with alkylate oil, and be a kind of alkylation catalyst of green.
The specific embodiment:
The preparation of ionic-liquid catalyst
Embodiment 1:
The alchlor of 0.56 mole (74.98 gram) is slowly added in the triethylamine hydrochloride of 0.282 mole (39.76 gram), under the drying nitrogen protection, stirred at ambient temperature 30 minutes, heat temperature raising to 80 ℃ continues to stir 2 hours then, obtains ionic liquid.Under protection of nitrogen gas, in synthetic ionic liquid well, add the butanethiol modifier of 1000ppm, at room temperature be stirred to butanethiol and dissolved in ionic liquid fully 1 hour.
Embodiment 2:
Substitute butanethiol modifier with benzene, the benzene addition is 20000ppm, and other condition is with embodiment 1.
Embodiment 3:
The alchlor of 0.56 mole (74.98 gram) is slowly added in the trimethylamine hydrochloride of 0.37 mole (35.47 gram); make solvent with normal heptane, the drying nitrogen protection was stirred 30 minutes at ambient temperature; heat temperature raising to 80 ℃ then continues to stir and obtained ionic liquid in 2 hours.Under protection of nitrogen gas, in synthetic good ionic liquid, add 100ppm butanethiol and 100ppm benzene modifier, at room temperature be stirred to modifier and dissolve in ionic liquid fully.
Embodiment 4:
With acetone is modifier, substitutes triethylamine hydrochloride with pyridine hydrochloride, and other condition is with embodiment 1.
Embodiment 5:
With carbon disulfide is modifier, and the carbon disulfide addition is 200ppm, and other condition is with embodiment 1.
Embodiment 6:
With toluene is modifier, and the toluene addition is that other condition of 2000ppm is with embodiment 1.
Embodiment 7:
With the alchlor of 0.56 mole (74.98 gram), the NiCl of the CuCl of 0.056 mole (5.54 gram) and 0.106 mole (7.26 gram)
2, slowly join in the hydrochloric acid tripropyl amine (TPA) of 0.51 mole (91.38 gram), under the drying nitrogen protection, stirred at ambient temperature 30 minutes, heat temperature raising to 80 ℃ continues to stir 2 hours then.Obtain ionic liquid after the cooling.Under protection of nitrogen gas, in synthetic good ionic liquid, add the 1000ppm butanethiol, at room temperature be stirred to modifier and dissolve in ionic liquid fully.
Embodiment 8:
With benzene is modifier, and the addition of benzene is 200ppm, and other condition is with embodiment 7.
Embodiment 9:
With acetone is modifier, and the addition of acetone is that other condition of 2000ppm is with embodiment 7.
Embodiment 10:
With carbon disulfide is modifier, and the addition of carbon disulfide is 600ppm, and other condition is with embodiment 7.
Embodiment 11:
With toluene is modifier, and the addition of toluene is that other condition of 5000ppm is with embodiment 7.
Ionic liquid-catalyzed iso-butane and butene alkylated
Embodiment 12:
The ionic liquid 200ml of preparation in the foregoing description 1 is added the autoclave that band stirs, be pressurized to 0.5Mpa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the compound 1200ml of iso-butane and butylene, butylene is the 2-butylene, the mixture of 1-butylene or isobutene or these three kinds of butylene, alkane alkene ratio is 10: 1 in the raw material, reacts 10 minutes down at 30 ℃.Reaction bleeds off unreacted iso-butane after finishing, and leaves standstill in separatory funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylate oil.Obtain alkylate oil after the separation.
Embodiment 13:
The ionic liquid 200ml of preparation in the foregoing description 2 is added the autoclave that band stirs, be pressurized to 0.5Mpa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the compound 1200ml of iso-butane and butylene, butylene is the 2-butylene, the mixture of 1-butylene or isobutene or these three kinds of butylene, alkane alkene ratio is 10: 1 in the raw material, reacts 10 minutes down at 30 ℃.Reaction bleeds off unreacted iso-butane after finishing, and leaves standstill in separatory funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylate oil.Obtain alkylate oil after the separation.
Embodiment 14:
The ionic liquid 200ml of preparation in the foregoing description 3 is added the autoclave that band stirs, be pressurized to 1Mpa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the compound 1200ml of iso-butane and butylene, butylene is the 2-butylene, the mixture of 1-butylene or isobutene or these three kinds of butylene, alkane alkene ratio is 10: 1 in the raw material, reacts 10 minutes down at 20 ℃.Reaction bleeds off unreacted iso-butane after finishing, and leaves standstill in separatory funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylate oil.Obtain alkylate oil after the separation.
Embodiment 15:
The ionic liquid 200ml of preparation in the foregoing description 4 is added the autoclave that band stirs, be pressurized to 1.5Mpa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the compound 1200ml of iso-butane and butylene, butylene is the 2-butylene, the mixture of 1-butylene or isobutene or these three kinds of butylene, alkane alkene ratio is 10: 1 in the raw material, reacts 10 minutes down at 30 ℃.Reaction bleeds off unreacted iso-butane after finishing, and leaves standstill in separatory funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylate oil.Obtain alkylate oil after the separation.
Embodiment 16:
The ionic liquid 200ml of preparation in the foregoing description 5 is added the autoclave that band stirs, be pressurized to 1.5Mpa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the compound 1200ml of iso-butane and butylene, butylene is the 2-butylene, the mixture of 1-butylene or isobutene or these three kinds of butylene, alkane alkene ratio is 10: 1 in the raw material, reacts 10 minutes down at 30 ℃.Reaction bleeds off unreacted iso-butane after finishing, and leaves standstill in separatory funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylate oil.Obtain alkylate oil after the separation.
Embodiment 17:
The ionic liquid 200ml of preparation in the foregoing description 6 is added the autoclave that band stirs, be pressurized to 1Mpa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the compound 1200ml of iso-butane and butylene, butylene is the 2-butylene, the mixture of 1-butylene or isobutene or these three kinds of butylene, alkane alkene ratio is 10: 1 in the raw material, reacts 10 minutes down at 20 ℃.Reaction bleeds off unreacted iso-butane after finishing, and leaves standstill in separatory funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylate oil.Obtain alkylate oil after the separation.
Embodiment 18:
The ionic liquid 200ml of preparation in the foregoing description 7 is added the autoclave that band stirs, be pressurized to 1Mpa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the compound 1200ml of iso-butane and butylene, butylene is the 2-butylene, the mixture of 1-butylene or isobutene or these three kinds of butylene, alkane alkene ratio is 20: 1 in the raw material, reacts 20 minutes down at 20 ℃.Reaction bleeds off unreacted iso-butane after finishing, and leaves standstill in separatory funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylate oil.Obtain alkylate oil after the separation.
Embodiment 19:
The ionic liquid 200ml of preparation in the foregoing description 8 is added the autoclave that band stirs, be pressurized to 1Mpa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the compound 1200ml of iso-butane and butylene, butylene is the 2-butylene, the mixture of 1-butylene or isobutene or these three kinds of butylene, alkane alkene ratio is 20: 1 in the raw material, reacts 20 minutes down at 30 ℃.Reaction bleeds off unreacted iso-butane after finishing, and leaves standstill in separatory funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylate oil.Obtain alkylate oil after the separation.
Embodiment 20:
The ionic liquid 200ml of preparation in the foregoing description 9 is added the autoclave that band stirs, be pressurized to 1Mpa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the compound 1200ml of iso-butane and butylene, butylene is the 2-butylene, the mixture of 1-butylene or isobutene or these three kinds of butylene, alkane alkene ratio is 20: 1 in the raw material, reacts 20 minutes down at 30 ℃.Reaction bleeds off unreacted iso-butane after finishing, and leaves standstill in separatory funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylate oil.Obtain alkylate oil after the separation.
Embodiment 21:
The ionic liquid 200ml of preparation in the foregoing description 10 is added the autoclave that band stirs, be pressurized to 1Mpa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the compound 1200ml of iso-butane and butylene, butylene is the 2-butylene, the mixture of 1-butylene or isobutene or these three kinds of butylene, alkane alkene ratio is 20: 1 in the raw material, reacts 20 minutes down at 30 ℃.Reaction bleeds off unreacted iso-butane after finishing, and leaves standstill in separatory funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylate oil.Obtain alkylate oil after the separation.
Embodiment 22:
The ionic liquid 200ml of preparation in the foregoing description 11 is added the autoclave that band stirs, be pressurized to 1Mpa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the compound 1200ml of iso-butane and butylene, butylene is the 2-butylene, the mixture of 1-butylene or isobutene or these three kinds of butylene, alkane alkene ratio is 20: 1 in the raw material, reacts 20 minutes down at 30 ℃.Reaction bleeds off unreacted iso-butane after finishing, and leaves standstill in separatory funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylate oil.Obtain alkylate oil after the separation.
Embodiment 23:
The ionic liquid 200ml of preparation in the foregoing description 11 is added the autoclave that band stirs, be pressurized to 1Mpa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the compound 1200ml of iso-butane and butylene, butylene is the 2-butylene, the mixture of 1-butylene or isobutene or these three kinds of butylene, alkane alkene ratio is 200: 1 in the raw material, reacts 20 minutes down at 30 ℃.Reaction bleeds off unreacted iso-butane after finishing, and leaves standstill in separatory funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylate oil.Obtain alkylate oil after the separation.
Embodiment 24:
The ionic liquid 200ml of preparation in the foregoing description 11 is added the autoclave that band stirs, be pressurized to 1Mpa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the compound 1200ml of iso-butane and butylene, butylene is the 2-butylene, the mixture of 1-butylene or isobutene or these three kinds of butylene, alkane alkene ratio is 200: 1 in the raw material, reacts 20 minutes down at 60 ℃.Reaction bleeds off unreacted iso-butane after finishing, and leaves standstill in separatory funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylate oil.Obtain alkylate oil after the separation.
Collect above-mentioned 12～24 product, carry out the yield and the C8 ratio of alkylate oil, the TMP assay, measurement result sees Table 1.
The mensuration of the yield of alkylated oil and C8 ratio
Assay method is:
Chromatograph: Varian CP3800, the 50mPONA capillary column, the temperature programming process: 40 ℃ kept 2 minutes down, be warming up to 60 ℃ with 2 ℃/min speed, after being warmed up to 130 ℃ with 1 ℃/min speed again, be warmed up to 180 ℃, under this temperature, keep 13min with 2 ℃/min speed.
Determine the retention time of every kind of product by n-compound, utilize mass spectrum to determine the kind of every kind of product.
Table 1
| Embodiment | Yield (alkene charging %) | C8 *Ratio (%) | TMP *Account for the ratio (%) of C8 |
| Unmodified ionic liquid ** | 155 | 56 | 62 |
| Embodiment 12 | 176 | 79 | 85 |
| Embodiment 13 | 166 | 72 | 86 |
| Embodiment 14 | 163 | 79 | 85 |
| Embodiment 15 | 165 | 68 | 86 |
| Embodiment 16 | 172 | 72 | 87 |
| Embodiment 17 | 179 | 74 | 85 |
| Embodiment 18 | 182 | 89 | 95 |
| Embodiment 19 | 176 | 88 | 94 |
| Embodiment 20 | 174 | 84 | 90 |
| Embodiment 21 | 176 | 86 | 94 |
| Embodiment 22 | 178 | 88 | 95 |
| Embodiment 23 | 179 | 90 | 96 |
| Embodiment 24 | 178 | 85 | 91 |
*: C8 is an isooctane, have ten surplus isomer, the octane number difference of various isomers; TMP is a trimethylpentane, be in the C8 isomers octane number at the isooctane more than 100.The height of C8 and TMP content directly influences the height of alkylate oil octane number in the alkylate oil.*: be correction data, not adding organic modifier ionic-liquid catalyst among the embodiment 1, carry out the result that alkylated reaction is made according to the reaction condition of embodiment 12.
Ion liquid reaction experiment repeatedly
Embodiment 25
As embodiment 22 described conditions, the back ionic liquid that reacts completely carries out plain sedimentation and separates back repeated use 10 times. and collect each product, carry out the productive rate and the C8 alkane Determination on content of alkylate oil.Measurement result sees Table 2.Present embodiment mainly is to measure ion liquid selectivity and repeat performance.
Table 2
| Number of times | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Yield (alkene charging %) | 176 | 178 | 176 | 177 | 175 | 176 | 177 | 177 | 175 | 176 |
| C8 ratio (%) | 88 | 89 | 88 | 87 | 86 | 88 | 87 | 88 | 86 | 88 |
Claims (5)
1. ionic-liquid catalyst of producing alkylate oil, with the hydrohalide of the amine that contains alkyl or the hydrohalide of pyridine is the cationic source material, nitrogen-atoms is saturated by four substituting groups in the hydrohalide of the said amine that contains alkyl or the hydrohalide of pyridine, and wherein has a hydrogen atom and an alkyl substituent at least; Metal halide is the ionic liquid of negative ion source material, it is characterized in that: add the modifier of 200-20000ppm in the ionic liquid preparation process, said modifier is the alkyl derivative of carbon disulfide, butanethiol, benzene, benzene or their mixture.
2. according to the ionic-liquid catalyst of claim 1, it is characterized in that: metal halide is a kind of in the halide of aluminium, copper, nickel, zinc or their mixture.
3. according to the ionic-liquid catalyst of claim 2, it is characterized in that: metal halide is an alchlor.
4. according to the ionic-liquid catalyst of claim 1, it is characterized in that: the hydrohalide that contains the amine of alkyl is the hydrochloric acid quaternary amine; The hydrohalide of pyridine is a pyridine hydrochloride.
5. the preparation method of any ionic-liquid catalyst of claim 1-4 comprises following two steps:
A: will contain the hydrohalide of amine of alkyl or the hydrohalide of pyridine earlier and be dissolved in the normal heptane, then under the protection of room temperature, drying nitrogen, slowly add metal halide, metal halide is 1～2: 1 with the mol ratio of the hydrohalide of hydrohalide of amine that contains alkyl or pyridine, stirring is no less than 30 minutes, be warming up to 80 ℃ again, continue to stir, until the liquid that generates homogeneous;
B: under the protective condition of room temperature, drying nitrogen, in above-mentioned ionic liquid, add modifier, and be stirred to modifier and dissolve in ionic liquid fully, make ionic-liquid catalyst.
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| US7553999B2 (en) * | 2006-12-14 | 2009-06-30 | Chevron U.S.A. Inc. | Isomerization of butene in the ionic liquid-catalyzed alkylation of light isoparaffins and olefins |
| CN101234945B (en) * | 2007-02-01 | 2011-04-20 | 北京化工大学 | Method for on-line producing alkymer from regenerative ionic liquid catalyst |
| CN102574752A (en) * | 2009-08-06 | 2012-07-11 | 中国石油大学(北京) | Process for preparing an alkylate |
| CN108160111A (en) * | 2018-01-23 | 2018-06-15 | 中国科学院过程工程研究所 | A kind of alkylation catalyst and its application |
| CN113680387B (en) * | 2021-08-24 | 2023-09-05 | 濮阳市盛源石油化工（集团）有限公司 | Catalyst for synthesizing isooctane alkylate, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000041809A1 (en) * | 1999-01-15 | 2000-07-20 | Bp Chemicals Limited | Ionic liquid catalyst for alkylation |
| CN1432627A (en) * | 2002-01-18 | 2003-07-30 | 石油大学(北京) | Method of utilizing ionic liquid as catalyst in preparing alkylated oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000041809A1 (en) * | 1999-01-15 | 2000-07-20 | Bp Chemicals Limited | Ionic liquid catalyst for alkylation |
| CN1432627A (en) * | 2002-01-18 | 2003-07-30 | 石油大学(北京) | Method of utilizing ionic liquid as catalyst in preparing alkylated oil |
Non-Patent Citations (1)
| Title |
|---|
| 离子液体的酸性测定及其催化的异丁烷/丁烯烷基化反应 杨雅立，王晓化，寇元.催化学报，第25卷第1期 2004 * |
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