CN1432627A - Method of utilizing ionic liquid as catalyst in preparing alkylated oil - Google Patents
Method of utilizing ionic liquid as catalyst in preparing alkylated oil Download PDFInfo
- Publication number
- CN1432627A CN1432627A CN 02100716 CN02100716A CN1432627A CN 1432627 A CN1432627 A CN 1432627A CN 02100716 CN02100716 CN 02100716 CN 02100716 A CN02100716 A CN 02100716A CN 1432627 A CN1432627 A CN 1432627A
- Authority
- CN
- China
- Prior art keywords
- reaction
- ionic liquid
- butylene
- alkylated oil
- alkylated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
In the alkylated oil preparing process, room temperature acid ionic liquid is used as catalyst and isobutane and olefin are used as material. The catalyst is prepared through reaction between alkylamine hydrohalide or pyridine hydrohalide and metal halide. The alkylation reaction is performed at -20 to +80 deg.c and 0.1-1.6 MPa, and the material isobutane/olefin ratio is 1-200. The alkylated oil yield may reach 160-180 vol% of olefin, and its C8 component may reach 60-80%. The catalyst has no descent in yield of alkylated oil and C8 selectivity after being used for 10 times and has excellent regeneration performance. The present inventino can inhibit olefin condensation, cyclization and other side reactions; and the ionic liquid has no corrosion and no volatility and is easy to separate from alkylated oil.
Description
Technical field
The present invention relates to prepare the method for alkylated oil, be specifically related to a kind of method of utilizing ionic liquid for catalyst in preparing alkylated oil.
Technical background
Along with the develop rapidly and the human pay attention to day by day to environment protection of automotive industry, countries in the world constantly increase the demand of unleaded stop bracket gasoline, and aromatic hydrocarbons and the olefin(e) centent in the gasoline also will be restricted simultaneously.In this case, calling in alkylated oil in gasoline is a kind of effective ways of keeping gasoline high-octane rating and low-vapor pressure.
As everyone knows, the catalyzer that present industrial alkane and olefin alkylation adopted is mainly liquid strong acid such as the vitriol oil or hydrofluoric acid.But these liquid strong acid have, and corrodibility is strong, production operation is difficult, product postprocessing trouble and have problem such as serious environmental pollution.Pay much attention to the protection environment for human survival in the world today; walk under the megatrend 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 complex 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 sulfuric acid process and hydrofluoric acid method cause and the problem of etching apparatus.The existing a lot of reports of various novel solid catalyzer that are used for the abovementioned alkyl reaction, but all there is a common defective, the initial activity that is catalyzer is fine, and its deactivation rate under usual conditions is very fast, and several hours even dozens of minutes conversion of olefines rate just drop to very low level from 100%.The major cause of inactivation be on the acidic site of solid acid catalyst the alkene in the raw material self and with reaction process in the alkene or the side reactions such as carbonium ion generation polymerization, cyclisation that generate, produce the macromolecule hydrocarbon compound of C9-C36, not only covered the activity of such catalysts center, and the duct of meeting blocking catalyst.For this reason, people expect utilizing the dissolving power of supercutical fluid excellence, developed the alkylation reaction system under super critical condition, but because the catalytic active center of above-mentioned catalyzer mainly concentrates in the micropore of catalyzer, and the dissolving power of supercutical fluid in micropore reduces greatly, so, though overcritical prolonged in the catalysis cycle to some extent, but present result of study shows, the overcritical coking and deactivation that can not eliminate catalyzer fully, and the temperature of supercritical reaction is higher, reduces with the selectivity of the prolongation alkylated reaction in reaction times.
Solid acid catalyst comparatively successful example aspect alkylation has the supercritical reaction system of academy of sciences of CNPC and the Alkylene technology of American UOP company.But all also there is certain defective in above-mentioned two kinds of technologies, improve greatly as the requirement of super-critical anti reply equipment, exist simultaneously above-mentionedly to prolong the problem that selectivity reduces with the reaction times; Catalyzer can cyclic regeneration in the Alkylene technology, but needs to use a large amount of solvents in the technology, and the regeneration of these solvents also can bring many problems.Above-mentioned two kinds of technologies all need to set up the brand-new production equipment of a cover simultaneously, will certainly take a large amount of funds.
Ionic liquid is a kind of a kind of salt that at room temperature exists with liquid form, it has many special nature, very low almost nil as its saturation vapour pressure, can dissolve many organism and inorganics, do not have corrodibility, can prepare different tart ionic liquids by the kind and the quantity of allocating its zwitterion.At present in the ascendant about the research of ion liquid preparation and application facet, ion liquid kind of preparing and related Application Areas are also more and more many.
Many about with the ionic liquid being that catalyzer or solvent carry out the patent of alkylated reaction, but mostly be the alkylation of benzene and derivative and alkene greatly, as US 5994602, US 5824832, WO 99/03163 etc.French Patent FR 2626572 utilizes imidazole type or four to replace the catalyzer of amine type ionic liquids as isoparaffin and alkene, but in the reaction product of this patent based on the C6 or the C7 of isomery, the content of C8 alkane is very low in the product, does not possess actual application value; And, imidazole type ion liquid since its synthetic difficulty and price problem well do not utilized and promoted.
US 5731101, WO 00/41809 and Chinese patent publication number CN1225617A provide a kind of preparation process of room temperature ionic liquid cheap and easy to get.With the hydrohalogen and the metal halide reaction of the amine that contains alkyl, the preparation ionic liquid, it at room temperature is liquid state.Patent has been described this ionic liquid as benzene and olefin alkylation Application of Catalyst.
Summary of the invention
The object of the present invention is to provide a kind of is catalyzer with the tart ionic liquid at room temperature that is cheap and easy to get, is the method for feedstock production alkylated oil with butylene and Trimethylmethane
The method for preparing alkylated oil that the present invention proposes, with acid ionic liquid at room temperature is catalyzer, is raw material with Trimethylmethane and alkene, and described alkylated reaction carries out in-20 ℃～+ 80 ℃ scopes, reaction pressure is 0.1～1.6MPa, and raw material alkane alkene ratio is 1: 1～200: 1; Wherein said room-temperature ion liquid body catalyst is with the hydrohalogen of the amine that contains alkyl or the hydrohalogen and the metal halide prepared in reaction of pyridine.
In the aforesaid method, the nitrogen-atoms of the hydrohalogen of the described amine that contains alkyl or the hydrohalogen of pyridine is saturated by four substituting groups, and wherein has at least one to be hydrogen atom and at least one alkyl substituent.Alkyl substituent can be methyl, ethyl.
In the aforesaid method, described metal halide is selected from the muriate of aluminium, copper, iron and zinc, is preferably aluminum chloride.
In the aforesaid method, described alkylated reaction is the reaction of Trimethylmethane and C4 alkene, and wherein C4 alkene is two or more mixture of 2-butylene, iso-butylene, 1-butylene or they.
Used ion liquid characteristics are that positively charged ion is provided by the hydrohalogen of the amine that contains alkyl or the hydrohalogen of pyridine among the present invention, in this kind ionic liquid, as with nitrogen-atoms being the words that have the basis, nitrogen-atoms is saturated by four substituting groups, and wherein has at least one to be hydrogen atom and at least one alkyl substituent.The used metal halide of preparation ionic liquid is the metal halide of covalent bonding, and particularly preferred metal is selected from elements such as aluminium, gallium, iron, copper, zinc, and wherein most preferred metal is an aluminium; Halogenide both can be that muriate also can be bromide, especially preferably muriate.
The used alkene of raw material for alkylation of the present invention is 2-butylene, 1-butylene, iso-butylene or their mixture, and used alkane is Trimethylmethane.Major ingredient in the product is the high C8 isoparaffin of octane value.The present invention has high product selectivity and yield, and ionic liquid can separate very simply and recover catalytic activity, and technological process does not produce pollutents such as discarded solvent, waste water, is a kind of technological process of environmental protection.
The preparation of low-temperature ionic liquids:
With the hydrohalogen of the amine that contains alkyl or the hydrohalogen and the metal halide prepared in reaction ionic liquid at room temperature of pyridine.In this kind ionic liquid, as being to have the basis with nitrogen-atoms, nitrogen-atoms is saturated by four substituting groups, and wherein has at least one to be hydrogen atom and at least one alkyl substituent.The used metal halide of preparation ionic liquid is the metal halide of covalent bonding, and particularly preferred metal is selected from elements such as aluminium, gallium, iron, copper, zinc, and wherein most preferred metal is an aluminium; Halogenide both can be that muriate also can be bromide, especially preferably muriate.It also can be that solvent mixes two kinds of reactants with alkane that the preparation method can directly mix two kinds of reactants.The ratio that contains the amount of substance of the hydrohalogen of the hydrohalogen of amine of alkyl or pyridine and metal halide is 1: 1 to 1: 2, preferably 1: 2.
Alkylated reaction:
The used alkene of raw material for alkylation is 2-butylene, 1-butylene, iso-butylene or their mixture, and used alkane is Trimethylmethane.With above-mentioned ionic liquid is catalyzer, reacts in-20 ℃～+ 80 ℃ scopes.Reaction pressure is 0.1～1.6Mpa, reaction pressure to choose to guarantee under the reaction conditions that reaction raw materials keeps liquid state be lower limit.Reactor can be selected the autoclave of band whipping appts for use, also can applicable industry on sulfuric acid or the employed continuous production device of hydrofluoric acid method alkylated reaction.
The yield of the prepared alkylated oil of the present invention can reach 160～180% of alkene feed volume, the C8 proportion can reach 60～80% in the alkylated oil, the level that reaches industrial hydrofluoric acid and sulfuric acid process alkylation process substantially from the productive rate and the selectivity aspect of alkylated oil.Used ionic-liquid catalyst carries out reusing 10 times after plain sedimentation separates after reacting completely among the present invention, and the productive rate of last alkylated oil and the selectivity of C8 isoparaffin do not descend, and the regenerability excellence of ionic-liquid catalyst is described; The composition of the obtained alkylated oil of the present invention is an isoparaffin all, does not have macromolecular alkene and aromatic hydrocarbons to produce, and illustrates that method of the present invention can suppress side reactions such as alkene condensation and cyclisation when taking place; The outstanding advantage of another of the method for the invention is that ionic liquid does not almost have corrodibility to equipment, and is non-volatile, with the alkylated oil separate easily, is a kind of alkylation process of green.
Embodiment
The present invention will be described with specific embodiment below, but application of the present invention not only is confined to the listed scope of embodiment.
Ion liquid preparation
Embodiment 1:
AlCl with 0.56 mole (74.98 gram)
3Slowly add in the hydrochloric acid triethyl ammonium of 0.282 mole (39.76 gram), make solvent with normal heptane, nitrogen protection was stirred 30 minutes at ambient temperature, and heat temperature raising to 80 ℃ continues to stir 2 hours, so that react completely then.Cooling afterreaction thing is divided into two-phase, and the upper strata is a heptane, and lower floor is for forming [NEt
3H
+] [Al
2Cl
7 -] ionic liquid.
Embodiment 2
Condition as embodiment 1 prepares ionic liquid, and used ammonium salt is the hydrochloric acid diethyl ammonium, does not need normal heptane to make solvent in the reaction process, reacts in dry air, and the reaction process heat release also forms light brown liquid, continues to stir 2 hours until reacting completely.
Embodiment 3
Condition as embodiment 1 prepares ionic liquid, and used ammonium salt is a pyridine hydrochloride.
Embodiment 4
Condition as embodiment 1 prepares ionic liquid, and used ammonium salt is the hydrochloric acid trimethyl ammonium.
The preparation of alkylated oil
Embodiment 5
The ionic liquid 200ml of preparation in the foregoing description 1 is added in the autoclave of band stirring, be pressurized to 0.5MPa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the mixing raw material 1200ml of Trimethylmethane and 2-butylene, 1-butylene and iso-butylene, alkane alkene ratio is 10: 1 in the raw material, reacts 20 minutes down at 10 ℃.Reaction bleeds off unreacted Trimethylmethane after finishing, and leaves standstill in separating funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylated oil.Can obtain alkylated oil after the separation.
Embodiment 6
The ionic liquid 200ml of preparation in the foregoing description 1 is added in the autoclave of band stirring, be pressurized to 0.5MPa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the mixing raw material 1200ml of Trimethylmethane and butylene (comprising 2-butylene, 1-butylene and iso-butylene), alkane alkene ratio is 20: 1 in the raw material, reacts 20 minutes down at 0 ℃.Reaction bleeds off unreacted Trimethylmethane after finishing, and leaves standstill in separating funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylated oil.Can obtain alkylated oil after the separation.
Embodiment 7
The ionic liquid 200ml of preparation in the foregoing description 2 is added in the autoclave of band stirring, be pressurized to 0.8MPa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the mixing raw material 400ml of Trimethylmethane and butylene (comprising 2-butylene, 1-butylene and iso-butylene), alkane alkene ratio is 20: 1 in the raw material, reacts 20 minutes down at 25 ℃.Reaction bleeds off unreacted Trimethylmethane after finishing, and leaves standstill in separating funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylated oil.Can obtain alkylated oil after the separation.
Embodiment 8
The ionic liquid 200ml of preparation in the foregoing description 3 is added in the autoclave of band stirring, be pressurized to 1.5MPa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the mixing raw material 200ml of Trimethylmethane and butylene (comprising 2-butylene, 1-butylene and iso-butylene), alkane alkene ratio is 20: 1 in the raw material, reacts 15 minutes down at 65 ℃.Reaction bleeds off unreacted Trimethylmethane after finishing, and leaves standstill in separating funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylated oil.Can obtain alkylated oil after the separation.
Embodiment 9
The ionic liquid 200ml of preparation in the foregoing description 4 is added in the autoclave of band stirring, be pressurized to 1.0MPa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the mixing raw material 100ml of Trimethylmethane and butylene (comprising 2-butylene, 1-butylene and iso-butylene), alkane alkene ratio is 30: 1 in the raw material, reacts 15 minutes down at 50 ℃.Reaction bleeds off unreacted Trimethylmethane after finishing, and leaves standstill in separating funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylated oil.Can obtain alkylated oil after the separation.
Embodiment 10
The ionic liquid 200ml of preparation in the foregoing description 1 is added in the autoclave of band stirring, be pressurized to 0.1MPa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the mixing raw material 1200ml of Trimethylmethane and butylene, 2-butylene, 1-butylene and iso-butylene, alkane alkene ratio is 10: 1 in the raw material, reacts 30 minutes down at-10 ℃.Reaction bleeds off unreacted Trimethylmethane after finishing, and leaves standstill in separating funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylated oil.Can obtain alkylated oil after the separation.
Embodiment 11
The ionic liquid 200ml of preparation in the foregoing description 1 is added in the autoclave of band stirring, be pressurized to 1.6MPa with nitrogen, vigorous stirring utilizes high-pressure pump to squeeze into the mixing raw material 1200ml of Trimethylmethane and 2-butylene and iso-butylene, alkane alkene ratio is 200: 1 in the raw material, reacts 20 minutes down at 80 ℃.Reaction bleeds off unreacted Trimethylmethane after finishing, and leaves standstill in separating funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylated oil.Can obtain alkylated oil after the separation.
Embodiment 12
The ionic liquid 200ml of preparation in the foregoing description 1 is added in the autoclave of band stirring, be pressurized to 1.0MPa with nitrogen, vigorous stirring utilizes high-pressure pump to squeeze into the mixing raw material 1200ml of Trimethylmethane and 1-butylene, alkane alkene ratio is 100: 1 in the raw material, reacts 20 minutes down at 10 ℃.Reaction bleeds off unreacted Trimethylmethane after finishing, and leaves standstill in separating funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylated oil.Can obtain alkylated oil after the separation.
Embodiment 13
The ionic liquid 200ml of preparation in the foregoing description 1 is added in the autoclave of band stirring, be pressurized to 0.5MPa with nitrogen, vigorous stirring, utilize high-pressure pump to squeeze into the mixing raw material 1200ml of Trimethylmethane and butylene, 2-butylene, 1-butylene and iso-butylene, alkane alkene ratio is 150: 1 in the raw material, reacts 20 minutes down at 0 ℃.Reaction bleeds off unreacted Trimethylmethane after finishing, and leaves standstill in separating funnel, and product is divided into two-layer, and lower floor is an ionic liquid, and the upper strata is an alkylated oil.Can obtain alkylated oil after the separation.
Ion liquidly recycle experiment
Embodiment 14
As embodiment 1 described condition, the back ionic liquid that reacts completely carries out plain sedimentation and separates back repeated use 10 times.Collect each product, carry out the mensuration of the productive rate and the C8 alkane of alkylated oil.Measurement result sees Table 2.Present embodiment mainly is the selectivity and the regenerability of test ion liquid.
Alkylated oil yield and C8 ratio measuring
Collect the product of the foregoing description 5-13, carry out alkylated oil yield and C8 ratio measuring, measurement result sees Table 1.
Measuring method is:
Chromatographic instrument: HP3420,50m PONA 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 chromatograph-mas spectrometer finally to determine the kind and the productive rate of various products.
Table 1
| Embodiment | Yield (alkene charging %) | C8 ratio (%) |
| ????5 | ????176 | ????80 |
| ????6 | ????163 | ????61 |
| ????7 | ????159 | ????70 |
| ????8 | ????166 | ????68 |
| ????9 | ????170 | ????71 |
| ????10 | ????162 | ????74 |
| ????11 | ????173 | ????65 |
| ????12 | ????168 | ????69 |
| ????13 | ????162 | ????76 |
As can be seen from Table 1, the yield that the embodiment of the invention prepares alkylated oil can reach 160～180% of alkene feed volume, the C8 proportion can reach 60～80% in the alkylated oil, the level that reaches industrial hydrofluoric acid and sulfuric acid process alkylation process substantially from the productive rate and the selectivity aspect of alkylated oil.
Table 2
| Number of times | ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??7 | ??8 | ??9 | ??10 |
| Yield (%) | ??176 | ??173 | ??174 | ??172 | ??174 | ??169 | ??172 | ??174 | ??172 | ??172 |
| ??C8(％) | ??80 | ??79 | ??78 | ??79 | ??79 | ??77 | ??79 | ??78 | ??76 | ??78 |
Table 2 shows that used ionic-liquid catalyst is reused 10 times among the present invention, and the selectivity of the productive rate of alkylated oil and C8 isoparaffin does not descend, and the regenerability excellence of ionic-liquid catalyst is described.
Claims (10)
1, a kind of method for preparing alkylated oil, it is characterized in that, with acid ionic liquid at room temperature is catalyzer, is raw material with Trimethylmethane and alkene, and wherein said room-temperature ion liquid body catalyst is with the hydrohalogen of the amine that contains alkyl or the hydrohalogen and the metal halide prepared in reaction of pyridine; Described alkylated reaction carries out in-20 ℃～+ 80 ℃ scopes, and reaction pressure is 0.1～1.6MPa, and raw material alkane alkene ratio is 1: 1～200: 1.
2, the method for claim 1 is characterized in that, the nitrogen-atoms of the hydrohalogen of the described amine that contains alkyl or the hydrohalogen of pyridine is saturated by four substituting groups, and wherein has at least one to be hydrogen atom and at least one alkyl substituent.
3, method as claimed in claim 2 is characterized in that, wherein alkyl substituent can be methyl, ethyl.
4, the method for claim 1 is characterized in that, described metal halide is selected from the muriate of aluminium, copper, iron and zinc.
5, method as claimed in claim 4 is characterized in that, described metal halide is an aluminum chloride.
6, the method for claim 1 is characterized in that, wherein said alkylated reaction is the reaction of Trimethylmethane and C4 alkene.
7, method as claimed in claim 6 is characterized in that, wherein C4 alkene is two or more mixture of 2-butylene, iso-butylene, 1-butylene or they.
8, the method for claim 1 is characterized in that, the alkylated reaction temperature is-20 ℃～+ 80 ℃.
9, the method for claim 1 is characterized in that, alkylated reaction pressure is 0.1～1.6Mpa.
10, the method for claim 1 is characterized in that, the alkane alkene ratio of reactant feed is 1: 1～200: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021007160A CN1184284C (en) | 2002-01-18 | 2002-01-18 | Method of utilizing ionic liquid as catalyst in preparing alkylated oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021007160A CN1184284C (en) | 2002-01-18 | 2002-01-18 | Method of utilizing ionic liquid as catalyst in preparing alkylated oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1432627A true CN1432627A (en) | 2003-07-30 |
| CN1184284C CN1184284C (en) | 2005-01-12 |
Family
ID=27627216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021007160A Expired - Lifetime CN1184284C (en) | 2002-01-18 | 2002-01-18 | Method of utilizing ionic liquid as catalyst in preparing alkylated oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1184284C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348320C (en) * | 2005-03-24 | 2007-11-14 | 北京化工大学 | Ion liquid catalyst for producing alkylated oil and its preparation method |
| CN101190861B (en) * | 2006-11-29 | 2011-07-13 | 中国石油大学(北京) | Method for catalyzing butene oligomerization by using ionic liquid as catalyst |
| CN101244972B (en) * | 2008-01-31 | 2012-05-02 | 北京华福工程有限公司 | Alkylation reaction method with ion liquid as catalyst and reactor |
| CN101405243B (en) * | 2006-03-24 | 2013-03-20 | 雪佛龙美国公司 | Alkylation process using an alkyl halide promoted ionic liquid catalyst |
| CN105142773A (en) * | 2013-04-19 | 2015-12-09 | 瑞来斯实业公司 | Ionic liquid compound |
| US9260668B2 (en) | 2009-07-17 | 2016-02-16 | Shell Oil Company | Method for revamping an HF or sulphuric acid alkylation unit and method for the production of alkylate |
| CN106947524A (en) * | 2017-03-17 | 2017-07-14 | 常州大学 | A kind of method that chlorine Ion-selective electrod catalysis prepares alkylate oil |
| CN109158126A (en) * | 2018-07-12 | 2019-01-08 | 天津大学 | A kind of metal halo acid ion liquid and its application method for catalyzing acetylene hydrochlorination |
| CN112245843A (en) * | 2020-10-20 | 2021-01-22 | 蒋小芳 | Intelligent early warning equipment for fire-fighting water of high-rise building |
| CN113680387A (en) * | 2021-08-24 | 2021-11-23 | 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7923593B2 (en) * | 2008-07-31 | 2011-04-12 | Chevron U.S.A. Inc. | Process for producing a middle distillate |
-
2002
- 2002-01-18 CN CNB021007160A patent/CN1184284C/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348320C (en) * | 2005-03-24 | 2007-11-14 | 北京化工大学 | Ion liquid catalyst for producing alkylated oil and its preparation method |
| CN101405243B (en) * | 2006-03-24 | 2013-03-20 | 雪佛龙美国公司 | Alkylation process using an alkyl halide promoted ionic liquid catalyst |
| CN101190861B (en) * | 2006-11-29 | 2011-07-13 | 中国石油大学(北京) | Method for catalyzing butene oligomerization by using ionic liquid as catalyst |
| CN101244972B (en) * | 2008-01-31 | 2012-05-02 | 北京华福工程有限公司 | Alkylation reaction method with ion liquid as catalyst and reactor |
| US9260668B2 (en) | 2009-07-17 | 2016-02-16 | Shell Oil Company | Method for revamping an HF or sulphuric acid alkylation unit and method for the production of alkylate |
| CN105142773B (en) * | 2013-04-19 | 2018-05-18 | 瑞来斯实业公司 | Ion liquid compound |
| CN105142773A (en) * | 2013-04-19 | 2015-12-09 | 瑞来斯实业公司 | Ionic liquid compound |
| CN106947524A (en) * | 2017-03-17 | 2017-07-14 | 常州大学 | A kind of method that chlorine Ion-selective electrod catalysis prepares alkylate oil |
| CN109158126A (en) * | 2018-07-12 | 2019-01-08 | 天津大学 | A kind of metal halo acid ion liquid and its application method for catalyzing acetylene hydrochlorination |
| CN109158126B (en) * | 2018-07-12 | 2021-10-29 | 天津大学 | Metal halide acid radical ionic liquid for catalyzing hydrochlorination of acetylene and application method thereof |
| CN112245843A (en) * | 2020-10-20 | 2021-01-22 | 蒋小芳 | Intelligent early warning equipment for fire-fighting water of high-rise building |
| CN113680387A (en) * | 2021-08-24 | 2021-11-23 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1184284C (en) | 2005-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1203032C (en) | Preparing method for alkylate agent using compound ion as catalyst | |
| CN1184284C (en) | Method of utilizing ionic liquid as catalyst in preparing alkylated oil | |
| US8017821B2 (en) | Process for isomerization of tetrahydrodicyclopentadiene using supported acidic ionic liquid as a catalyst | |
| CN103168088A (en) | Production of a high octane alkylate from ethylene and isobutane | |
| CN101177371A (en) | Method for alkylation of isoparaffin and olefin catalyzed by ion liquid | |
| CN101210192A (en) | Process for preparing alkylated oil | |
| CN102558230A (en) | Quaternary phosphor salt acidic ionic liquid and application thereof in synthesizing benzyltoluene | |
| CN105492470A (en) | Apparatus and method for removing halogens generated during preparation of polybutene | |
| CN104755165A (en) | Process for reducing chloride in hydrocarbon products using an ionic liquid catalyst | |
| CN1038835C (en) | Isoparaffin-olefin alkylation | |
| CN102134507B (en) | Method for preparing alkylate by modifying concentrated sulfuric acid by using trifluoroethanol or ionic liquid as assistant | |
| CN1836780A (en) | Ion liquid catalyst for producing alkylated oil and its preparation method | |
| CN1927785A (en) | Method of preparing propylene and ethylene by catalytic cracking olefin | |
| US10307742B2 (en) | Beta zeolite catalyst for preparation of mixture of BTEX (benzene, toluene, ethylbenzene, xylene) from poly aromatic hydrocarbons and preparation method thereof | |
| CN100363314C (en) | Process for polymerization preparation of diesel oil from C4 components containing butylene | |
| CN106916237B (en) | A kind of acidity polymeric ionic liquid and its preparation method and application | |
| CN1966476A (en) | Iron-catalysed allylic alkylation | |
| CN102351970A (en) | Method for preparing poly-1,3-pentadiene | |
| CN1834074A (en) | Solid acid alkylating process of isomerized alkane and olefin | |
| CN106398742B (en) | Method for preparing alkylated gasoline by coupling polyether type acidic ionic liquid with trifluoromethanesulfonic acid as catalyst | |
| CN106635141B (en) | A kind of method of adamantyl ionic liquid co-catalysis production gasoline alkylate | |
| CN1665591A (en) | Method for selective hydrogenation of polyunsaturated compounds into monounsaturated compounds using a homogeneous catalyst | |
| CN1990436A (en) | Process for preparing ethylene, propylene and aromatic hydrocarbons by C4 alkene catalytic conversion | |
| CN1463262A (en) | Method for producing adamantane | |
| CN112871121B (en) | Self-suction type continuous isomerization reaction device for alkane and use method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20050112 |
|
| CX01 | Expiry of patent term |