CN101234945B - Method for on-line producing alkymer from regenerative ionic liquid catalyst - Google Patents

Method for on-line producing alkymer from regenerative ionic liquid catalyst Download PDF

Info

Publication number
CN101234945B
CN101234945B CN2007100634596A CN200710063459A CN101234945B CN 101234945 B CN101234945 B CN 101234945B CN 2007100634596 A CN2007100634596 A CN 2007100634596A CN 200710063459 A CN200710063459 A CN 200710063459A CN 101234945 B CN101234945 B CN 101234945B
Authority
CN
China
Prior art keywords
ionic liquid
liquid
reactor
butylene
reaction
Prior art date
Application number
CN2007100634596A
Other languages
Chinese (zh)
Other versions
CN101234945A (en
Inventor
陈标华
张傑
黄崇品
乔聪震
Original Assignee
北京化工大学
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 北京化工大学 filed Critical 北京化工大学
Priority to CN2007100634596A priority Critical patent/CN101234945B/en
Publication of CN101234945A publication Critical patent/CN101234945A/en
Application granted granted Critical
Publication of CN101234945B publication Critical patent/CN101234945B/en

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

Abstract

The invention relates to a method for producing alkylate finish, in particular to a method by which alkylate finish can be produced with an online continuously regenerated ionic liquid catalyst. Metal aluminum or aluminum trichloride is used as the aluminum resource for replenishing AlCl3 lost due to oil-phase entrainment or decomposition of ironic liquid when meeting water, thereby realizing continuous aluminum replenishment to prolong the service life of the catalyst, so the method is applicable to raw materials with relatively high water content. At the same time, the method can reduce theamount of HCl in the catalytic reaction system, maintaining the selectivity of the target production, isooctane, at a high level in the product and reducing corrosion of existent HCl.

Description

A kind of method of online producing alkymer from regenerative ionic liquid catalyst

Technical field:

The present invention relates to a kind of production alkylate oil agent method, but the method for particularly a kind of on-line continuous producing alkymer from regenerative ionic liquid catalyst agent.

Background technology:

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 olefin(e) centent also will be restricted in the gasoline simultaneously.In this case, calling in alkylated oil in gasoline is a kind of effective ways of keeping gasoline high-octane rating and low-steam 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 problems such as these liquid strong acid have, and corrodibility is strong, production operation is difficult, product postprocessing trouble and environmental pollution are serious.Chinese patent CN1432627A, CN1500764A, CN1836780A is a Primary Catalysts with chlorine aluminic acid ionic liquid, add auxiliary agent, catalyzing iso-butane alkane and olefin alkylation reaction, the yield of product alkylate oil can reach the 170-180% of alkene feed volume, and the shared ratio of C8 can reach 60-80% in the alkylate oil, its outstanding advantage is that the trimethylpentane ratio reaches more than 70% in the C8 component, and RON (research octane number (RON)) can reach 93-98.

But chlorine aluminic acid ionic liquid catalyzing iso-butane alkane and butene alkylated in an inactivation that major issue is exactly a catalyzer facing.Owing to inevitably contain a spot of water in the reaction raw materials, can cause the hydrolysis of aluminum chloride, promptly it removes the generation hydrogenchloride after meeting water, also forms some oxygenated species, and most probable oxygenated species is Al 3Cl 9OH -And Al 2Cl 6OH -, making loss of active component, reactive behavior descends gradually, also can change the proportioning of modified additive in catalyzer simultaneously, influences the selectivity of target product.Another may cause AlCl 3The reason that runs off is AlCl 3With the material that has electron donation in the system (as benzene or alkene) complexing, be brought into oil phase, though aromatic hydrocarbons addition in ionic liquid is very little, this factor also be can not ignore in scale operation.No matter be the sort of reason, the major cause of ionic liquid inactivation all is AlCl 3Loss, therefore in reaction process, it is extremely important that chlorine aluminic acid ionic liquid is mended aluminium regeneration.

The mode of mending aluminium can be divided into off-line and online two kinds.It is intermittent process that off-line is mended aluminium, and complicated operation will inevitably ingress of air in the process, causes the further degraded of active ingredient.Online original position is mended the continuity that aluminium can guarantee process, in the system of sealing, can reduce the loss of active ingredient to greatest extent, can access the reaction result more efficient and more stable than periodical operation.At present, in producing alkylate oil, adopt ionic-liquid catalyst to carry out on-line continuous regenerated method and yet there are no report.

Summary of the invention:

Main purpose of the present invention is to provide a kind of alkylation of adopting on-line continuous regeneration chloro-aluminate type ionic-liquid catalyst catalyzing iso-butane alkane and alkene, the method for producing the high-octane rating alkylate oil that is used for the gasoline mediation.

The invention is characterized on continuous reaction apparatus, acidic ionic liquid catalysts is carried out online regeneration, and be used for catalyzing iso-butane alkane/butene alkylation, produce the high-octane rating alkylate oil.

The method of a kind of online producing alkymer from regenerative ionic liquid catalyst of the present invention, with Trimethylmethane and butylene is raw material, static mixing reactor is a reactor, with the ionic liquid is catalyzer, adopt the continuous processing of biliquid phase catalytic reaction, recycle stock and ionic liquid add reactor respectively and carry out alkylated reaction, reacted feed liquid is separated in phase separator, isolated ionic liquid and material are annotated back reactor recirculation, it is characterized in that: the control reactant is 1: 1~50: 1 with the ratio that ionic liquid enters the volumetric flow rate of reactor; In circulation line, the exit of reactor branch road that the ionic liquid revivifier is housed in parallel, said ionic liquid revivifier is a filling pipe of placing the aluminium source, when catalyzer need be regenerated, close main road, open bypass, the charging of stopped reaction thing only stays ionic-liquid catalyst to carry out flow circuit regeneration in the system, after regeneration is finished, close branch road, open main road, recover normal reaction.

Aforesaid method also can adopt in the entire reaction course, and reactant and ion liquid mixed liquor carry out the flow circuit reaction at branch road all the time, promptly pass through the ionic liquid revivifier all the time, to prolong catalyst life.

It is 20~60 ℃ that above-mentioned two kinds of methods all need the temperature of control catalyst ionic liquid revivifier.

In the aforesaid method, the temperature of alkylated reaction is-20~80 ℃, and pressure is 0.3~1.5Mpa, and the alkane alkene mol ratio of raw material is 10: 1~200: 1, and control reactant and ionic liquid enter the ratio of volumetric flow rate of reactor at 1: 1~50: 1.

In the aforesaid method, said ionic liquid is for being positively charged ion with the hydrohalogen of the amine that contains alkyl or the hydrohalogen of pyridine or imidazoles, the halogenide of aluminium is anionic acidic ion liquid, and adding mass content in the ionic liquid is the modified additive of 1000~5000ppm, to improve catalyzing iso-butane alkane and butene alkylated catalytic activity and the yield of C8 selectivity and product.Said modified additive is selected from the alkyl derivative of benzene or benzene.A kind of ionic-liquid catalyst of producing alkylate oil and preparation method thereof is open in the other patent that the applicant declares, and publication number is CN1836780A.

Butylene described in the abovementioned alkyl method is two or more a mixture of 2-butylene, iso-butylene, 1-butylene or they.

In the aforesaid method, the aluminium source of placing in the ionic liquid revivifier is the muriate of metallic aluminium or aluminium, is preferably metal aluminum filament, metal aluminium flake or block aluminum chloride crystal.

In the aforesaid method, the ionic liquid revivifier, outlet is provided with wire netting, prevents that solid from entering follow-up pipeline.

The invention effect: method of the present invention has realized under the operate continuously condition, ionic-liquid catalyst separates with the online original position of reaction feed liquid and the online benefit aluminium of ionic-liquid catalyst is regenerated, with metallic aluminium or aluminum chloride is the aluminium source, and additional carrying secretly with ionic liquid because of oil phase met the AlCl that water decomposition is lost 3Thereby, realize that mending aluminium continuously prolongs catalyst life, goes for the high relatively raw material of water content; Can reduce simultaneously the amount of HCl in the catalystic converter system, make the selectivity of target product octane-iso in product maintain higher level, and reduce the corrodibility that exists because of HCl.

Description of drawings:

Fig. 1 is the schematic flow sheet of online producing alkymer from regenerative ionic liquid catalyst method

1 is raw material Trimethylmethane/butylene inlet among the figure, and 2 is feedstock pump, and 3 is static mixing reactor, and 4 is the ionic liquid revivifier, and 5 is liquid liquid separator, and 6 is gas-liquid separator, and 7 is compressor, and 8 and 9 is the ionic liquid holding tank, and 10 is the ionic liquid pump.

As shown in Figure 1, reactor outlet is divided into two-way, and having a road of the filling pipe of placing the aluminium source is branch road, and another road is a main road, and material can switch between the two-way.When reactive behavior descends, when ionic liquid need be mended aluminium regeneration, material is switched to branch road carry out the online benefit aluminium of original position.Also can adopt in the entire reaction course, reactant and ion liquid mixed liquor carry out the flow circuit reaction at branch road all the time, promptly pass through the ionic liquid revivifier all the time, to prolong catalyst life.Simultaneously, the control reactant is 1: 1~50: 1 with the ratio that ionic liquid enters the volumetric flow rate of reactor.Ionic liquid is with after reaction product is separated in liquid liquid separator, and lower floor's ionic liquid enters the ionic liquid holding tank, adds circulation again.Product exports extraction from liquid liquid separator, isolates alkylate oil in gas-liquid separator, adds circulation after the compressed machine of unreacted Trimethylmethane compresses and liquefies again.

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.

Embodiment 1:

The preparation of ionic-liquid catalyst

By 2: 1 mol ratios aluminum chloride is slowly added in the Triethylammonium chloride, make solvent with normal heptane, drying nitrogen protection was stirred 30 minutes at ambient temperature, and heat temperature raising to 80 ℃ continues to stir 2 hours then.Cooling afterreaction thing is divided into two-phase, and the upper strata is a heptane, and lower floor is [Et for forming 3H +] [Al 2Cl 7 -] ionic liquid.Add the fresh ionic liquid of preparation in the ionic liquid jar, and add modified additive toluene, the mass concentration that makes toluene is 2000ppm.

Alkylated reaction on the continuous apparatus

Carry out the alkylated reaction of Trimethylmethane/2-butylene on continuous apparatus, Trimethylmethane in the raw material/2-butylene mol ratio is 20: 1, and material leaves reactor after the A road enters liquid liquid separator.Control reaction system pressure is 0.5MPa, 20 ℃ of temperature of reaction, and the ratio of reactant and ionic liquid circular flow was at 4: 1.Gather the reactor outlet product, analyze its composition, the results are shown in Table 1.When whenever lifting away from sub-accumulation of fluid and handle the fresh feed amount and reach 300 liters, the active of ionic-liquid catalyst obviously descends.

The fresh ionic liquid-catalyzed Trimethylmethane of table 1./2-butylene alkylated reaction

Ion liquid benefit aluminium regeneration

Keep above-mentioned reaction conditions, reactor outlet material is flowed to switch to the B road, carry out online benefit aluminium regeneration.Stopped reaction thing charging this moment only has ionic-liquid catalyst to flow in the system.20 ℃ of revivifier service temperatures are to mend aluminium aluminium source with the aluminium flake.Cyclic regeneration one hour.

The regeneration of ionic liquid reactivity worth is estimated

After regeneration finishes, in reactive system, inject reaction raw materials, and keep above-mentioned reaction conditions.Gather the reactor outlet product, analyze its composition, the results are shown in Table 2.As seen, the ionic liquid of inactivation recovers reactive behavior, and target product selectivity remains unchanged.

Table 2. aluminium flake regeneration of ionic liquid catalyzing iso-butane alkane/2-butylene alkylated reaction

Embodiment 2:

Under the condition of embodiment 1, when whenever lifting away from sub-accumulation of fluid and handle the fresh feed amount and reach 300 liters, ionic liquid catalyst activity obviously descends.At this moment serve as to mend aluminium aluminium source, 30 ℃ of revivifier service temperatures with the aluminum chloride crystal.Cyclic regeneration one hour.Inject reaction raw materials then in reactive system, operational condition is with embodiment 1.Gather the reactor outlet product, analyze its composition, the results are shown in Table 3.As seen, the ionic liquid of inactivation recovers reactive behavior, and target product selectivity remains unchanged.

Table 3. aluminum chloride regeneration of ionic liquid catalyzing iso-butane alkane/2-butylene alkylated reaction

Embodiment 3: ion liquid cyclic regeneration reaction

In the ionic liquid jar, add the fresh ionic liquid for preparing among the embodiment 1, on continuous apparatus, carry out the alkylated reaction of Trimethylmethane/butylene.Material leaves reactor after the B road enters liquid liquid separator.Control reaction system pressure is 1.0MPa, and Trimethylmethane in the raw material/2-butylene mol ratio is 50: 1,25 ℃ of temperature of reaction, and the ratio of reactant and ionic liquid circular flow was at 10: 1.The filling aluminium flake is for mending aluminium aluminium source, 40 ℃ of revivifier service temperatures in the revivifier.Gather the reactor outlet product, analyze its composition, the results are shown in Table 4.When whenever lifting away from sub-accumulation of fluid and handle the fresh feed amount and reach 600 liters, ionic liquid is inactivation not yet.

Table 4. aluminium flake is mended aluminium and is prolonged the ionic-liquid catalyst life-span

Embodiment 4:

In the ionic liquid jar, add the fresh ionic liquid for preparing among the embodiment 1, on continuous apparatus, carry out the alkylated reaction of Trimethylmethane/butylene.Material leaves reactor after the B road enters liquid liquid separator.Control reaction system pressure is 1.5MPa, and Trimethylmethane in the raw material/2-butylene mol ratio is 200: 1,5 ℃ of temperature of reaction, and the ratio of reactant and ionic liquid circular flow was at 20: 1.Filling aluminum chloride crystal is for mending aluminium aluminium source, 40 ℃ of revivifier service temperatures in the revivifier.Gather the reactor outlet product, analyze its composition, the results are shown in Table 5.When whenever lifting away from sub-accumulation of fluid and handle the fresh feed amount and reach 600 liters, ionic liquid is inactivation not yet.

Table 5. aluminum chloride is mended aluminium and is prolonged the ionic-liquid catalyst life-span

Annotate: table 1 to butene conversion and the alkylate oil composition (isooctane content) in the table 5 all adopts gas chromatography determination, chromatographic instrument: Varian CP3800,50mPONA capillary column, FID (flame ionization ditector)

Post case temperature programming process: 40 ℃ kept 2 minutes down, were warming up to 60 ℃ with 2 ℃/min speed, be warmed up to 130 ℃ with 1 ℃/min speed again after, be warmed up to 180 ℃ with 2 ℃/min speed, under this temperature, keep 13min.

250 ℃ of sampler temperature, 250 ℃ of detector temperatures.

Claims (2)

1. the method for an online producing alkymer from regenerative ionic liquid catalyst, with Trimethylmethane and butylene is raw material, static mixing reactor is a reactor, with the ionic liquid is catalyzer, adopt the continuous processing of biliquid phase catalytic reaction, material and ionic liquid add reactor respectively and carry out alkylated reaction, reacted feed liquid is separated in phase separator, isolated ionic liquid and material are annotated back reactor recirculation, it is characterized in that: in circulation line, the exit of reactor branch road that the ionic liquid revivifier is housed in parallel, said ionic liquid revivifier is a filling pipe of placing the aluminium source, reactant and ion liquid mixed liquor carry out the flow circuit reaction at branch road all the time in the entire reaction course, and the temperature of control catalyst ionic liquid revivifier is 20~60 ℃; The aluminium source of being placed is block aluminum chloride crystal, and the outlet setting of ionic liquid revivifier prevents that solid from entering the wire netting of follow-up pipeline; Said ionic liquid is for being positively charged ion with the hydrohalogen of the amine that contains alkyl or the hydrohalogen of pyridine or imidazoles, the halogenide of aluminium is anionic acidic ion liquid, and adding mass content in the ionic liquid is the modified additive of 1000~5000ppm, and said modified additive is the alkyl derivative of benzene or benzene; The temperature of control alkylated reaction be-20~80 ℃, and pressure is 0.3~1.5Mpa, and the alkane alkene mol ratio of raw material is 10: 1~200: 1, controls reactant and ionic liquid and enters the ratio of volumetric flow rate of reactor at 1: 1~50: 1.
2. according to the method for claim 1, it is characterized in that: described butylene is two or more a mixture of 2-butylene, iso-butylene, 1-butylene or they.
CN2007100634596A 2007-02-01 2007-02-01 Method for on-line producing alkymer from regenerative ionic liquid catalyst CN101234945B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2007100634596A CN101234945B (en) 2007-02-01 2007-02-01 Method for on-line producing alkymer from regenerative ionic liquid catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2007100634596A CN101234945B (en) 2007-02-01 2007-02-01 Method for on-line producing alkymer from regenerative ionic liquid catalyst

Publications (2)

Publication Number Publication Date
CN101234945A CN101234945A (en) 2008-08-06
CN101234945B true CN101234945B (en) 2011-04-20

Family

ID=39918888

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2007100634596A CN101234945B (en) 2007-02-01 2007-02-01 Method for on-line producing alkymer from regenerative ionic liquid catalyst

Country Status (1)

Country Link
CN (1) CN101234945B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8524623B2 (en) * 2008-11-26 2013-09-03 Chevron U.S.A. Inc. Electrochemical removal of conjunct polymers from chloroaluminate ionic liquids
CN101619010B (en) * 2009-07-17 2013-04-03 中国石油大学(北京) Method for regenerating and maintaining activity of ionic liquid catalyst and method for producing alkylate
CN102666444B (en) * 2009-08-06 2015-05-13 中国石油大学(北京) Process for preparing an alkylate
CN102108306B (en) 2009-12-28 2013-12-18 中国石油大学(北京) Alkylation reaction method using ionic liquid as catalyst
WO2014091016A1 (en) * 2012-12-14 2014-06-19 Shell Internationale Research Maatschappij B.V. Solids content control in ionic liquid alkylation process
CN103521264A (en) * 2013-10-17 2014-01-22 开滦能源化工股份有限公司 Regeneration method of chloroaluminate ionic liquid
US20170007993A1 (en) * 2015-07-08 2017-01-12 Chevron U.S.A. Inc. Sulfur-contaminated ionic liquid catalyzed alklyation
CN105400544B (en) * 2015-12-03 2017-03-08 天津如有科技有限公司 A kind of method that use multiple stage circulation flow reactor prepares alkylate oil

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1785940A (en) * 2004-12-08 2006-06-14 北京化工大学 Technology of ion liquid catalyzing benzene and long chain olefin alkylation reaction and its device
CN1836780A (en) * 2005-03-24 2006-09-27 北京化工大学 Ion liquid catalyst for producing alkylated oil and its preparation method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1785940A (en) * 2004-12-08 2006-06-14 北京化工大学 Technology of ion liquid catalyzing benzene and long chain olefin alkylation reaction and its device
CN1836780A (en) * 2005-03-24 2006-09-27 北京化工大学 Ion liquid catalyst for producing alkylated oil and its preparation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
实施例6,实施例12.
说明书第5页最后一段.

Also Published As

Publication number Publication date
CN101234945A (en) 2008-08-06

Similar Documents

Publication Publication Date Title
Zhai et al. Highly tunable selectivity for syngas‐derived alkenes over zinc and sodium‐modulated Fe5C2 catalyst
CN101905177B (en) The regeneration of acidic catalyst
US8936768B2 (en) Alkylation process unit for producing high quality gasoline blending components in two modes
DE60301288T2 (en) A process for paraffin isomerization and catalytic composition therefor containing an ionic liquid and a metal salt additive
Wasserscheid et al. Ionic liquids—new “solutions” for transition metal catalysis
TWI374932B (en) Integrated alkylation process using ionic liquid catalysts
US8183425B2 (en) Ionic liquid catalyst alkylation using split reactant streams
US8552243B2 (en) Process for preparing an alkylate
KR101472147B1 (en) Isomerization of Butene In The Ionic Liquid-Catalyzed Alkylation of Light Isoparaffins and Olefins
NL1018336C2 (en) Separation of olefins from paraffins.
US7538256B2 (en) Reduction of organic halides in alkylate gasoline
Corma et al. Current views on the mechanism of catalytic cracking
AU2008343578B2 (en) Ionic liquid catalyzed alkylation process employing nozzles and system implementing such process
Liu et al. Reaction performance of isobutane alkylation catalyzed by a composite ionic liquid at a short contact time
JP4273256B2 (en) Catalyst and solvent composition, and catalyst method using the composition
US8524623B2 (en) Electrochemical removal of conjunct polymers from chloroaluminate ionic liquids
Eisenberger et al. Borocation catalysis
US9096487B2 (en) Alkylation method using ionic liquid as catalyst
EP0748653B1 (en) New catalytic composition containing transition metals complexes and insatured compounds hydrogenation process
US7754636B2 (en) Removal of excess metal halides from regenerated ionic liquid catalysts
US7956230B2 (en) Reduction of organic halide contamination in hydrocarbon products
US9254450B2 (en) Alkylation process unit comprising a fractionation unit for separating hydrogen gas and hydrogen chloride
CN102933528B (en) Load ionic liquid phase liquid catalyst technique
US8088338B2 (en) System and apparatus for ionic liquid catalyst regeneration
US20090247804A1 (en) Methods for conversion of methane to useful hydrocarbons and catalysts for use therein

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
C14 Grant of patent or utility model
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20110420

Termination date: 20120201

C17 Cessation of patent right