CN102639469B - Process for preparing an alkylate - Google Patents

Process for preparing an alkylate Download PDF

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Publication number
CN102639469B
CN102639469B CN201080034714.4A CN201080034714A CN102639469B CN 102639469 B CN102639469 B CN 102639469B CN 201080034714 A CN201080034714 A CN 201080034714A CN 102639469 B CN102639469 B CN 102639469B
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China
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effluent
ionic liquid
hydrocarbon
reactor
liquid phase
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CN201080034714.4A
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Chinese (zh)
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CN102639469A (en
Inventor
刘植昌
徐春明
张睿
孟祥海
A·C·帕罗尼
P·A·A·克鲁森尔
A·V·P·范登博世
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中国石油大学(北京)
国际壳牌研究有限公司
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Priority to CNPCT/CN2009/000891 priority
Application filed by 中国石油大学(北京), 国际壳牌研究有限公司 filed Critical 中国石油大学(北京)
Priority to CN201080034714.4A priority patent/CN102639469B/en
Priority to PCT/EP2010/061509 priority patent/WO2011015661A2/en
Publication of CN102639469A publication Critical patent/CN102639469A/en
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Abstract

The present invention provides process for preparing an alkylate comprising contacting in a reactor a hydrocarbon mixture comprising at least an isoparaffin and an olefin with an acidic ionic liquid catalyst under alkylation conditions to obtain an alkylate, which process further comprises: - withdrawing an alkylate-comprising reactor effluent from the reactor, wherein the reactor effluent comprises an ionic liquid phase and a hydrocarbon phase; - separating at least part the reactor effluent into an ionic liquid phase effluent and a multiple-phase effluent in a first separation unit; - separating at least part of the multiple-phase effluent into a hydrocarbon phase effluent and another effluent in a second separation unit; and recycling at least part of the ionic liquid phase effluent to the reactor.

Description

Prepare the method for alkylate oil

Technical field

The invention provides the method for preparing alkylate oil.

Background technology

Demand to alkylate oil fuel mix raw material is increasing.As fuel mix composition, alkylate oil combines low-steam pressure and high-octane characteristic.

Nearly all alkylate oil is all under the existence by an acidic catalyst suitable, to make isobutane and butene reaction make.The most conventional catalyzer is HF and sulfuric acid, but has also reported other catalyzer, as solid acid catalyst.Recently, use the isoparaffin of acidic ionic liquid catalysts and the alkylation of alkene to cause concern as the replacement scheme of the alkylation of HF and sulfuric acid catalysis.

For example, in US7285698, disclose the method for the manufacture of alkylate oil, it uses compound ion liquid catalyst to make isobutane and butene reaction.In the method for US7285698, Trimethylmethane and butylene are offered to reactor, and under alkylating condition, make reactant contact to form alkylate oil with compound ion liquid.Separate reactor effluent, is recycled to reactor mutually by ionic liquid, processes hydrocarbon phase to reclaim described alkylate oil simultaneously.

For example, at (Z.Liu such as Liu, R.Zhang, C.Xu, R.Xia.Ionic liquid alkylation process produces high-quality gasoline, Oil and Gas Journal, the 104th volume, the 40th phase, 2006), in, mention and can improve the catalyzer for IL to sulfuric acid alkylation unit.But, also mention in order to improve separating of reactor effluent (, ionic-liquid catalyst and hydrocarbon phase) and must transform sedimentation unit.

In US2005/0119423, the method for preparing polyalphaolefin with ionic-liquid catalyst is disclosed.In the method for US2005/0119423, reactor effluent is offered to separator to obtain the phase that comprises polyalphaolefin, this phase still comprises residual ionic-liquid catalyst.Thereby US2005/0119423 proposes to make the Xiang Yushui mixing that comprises polyalphaolefin to make catalyst deactivation, makes subsequently the Xiang Yushui that comprises polyalphaolefin separate in two extra continuous separating steps.

In this area, need ionic liquid alkylation, the method has been improved the separation of reactor effluent.

Summary of the invention

Nowadays the reactor effluent that has been found that ionic liquid alkylation reactor can be divided into effectively by fractional separation acidic ion liquid phase and hydrocarbon phase.

Therefore, the invention provides a kind of method of preparing alkylate oil, described method is included in and under alkylation conditions, in reactor, makes the hydrocarbon mixture that at least comprises isoparaffin and alkene contact with acidic ionic liquid catalysts, thereby obtains alkylate oil, and described method also comprises:

-collect the reactor effluent that comprises alkylate oil from described reactor, wherein said reactor effluent comprises ionic liquid phase and hydrocarbon phase;

-at least a portion of described reactor effluent is separated into ionic liquid phase effluent and heterogeneous effluent in the first separating unit;

-at least a portion of described heterogeneous effluent is separated into hydrocarbon phase effluent and another effluent in the second separating unit; With

-at least a portion of described ionic liquid phase effluent is recycled to described reactor.

The invention has the advantages that without adding water or other compound to containing in the hydrocarbon phase of alkylate oil.In addition, need not specially make catalyst deactivation or otherwise be damaged, thereby reducing catalyst consumption of the present invention.

Accompanying drawing explanation

In Fig. 1, provide the schematic diagram of the inventive method.

Embodiment

In the method for the invention, by making isoparaffin and olefine reaction prepare alkylate oil.The alkylate oil obtaining is particularly suitable for the object that gasoline mixes.In the method for the invention, isoparaffin and alkene are offered to reactor.The hydrocarbon mixture that makes to comprise isoparaffin and alkene in described reactor be suitable for alkylating catalyzer and contact.Conventionally the alkene being provided by outside is provided described hydrocarbon mixture, that is, and and fresh alkene, and comprise isoparaffin.Described isoparaffin can be the isoparaffin being provided by outside, that is, and and fresh alkene, and/or by the isoparaffin of any other part recirculation of the method.Fresh isoparaffin and alkene separately can be offered to the method, but normally fresh isoparaffin and fresh alkene be offered to described reactor as the mixture that comprises isoparaffin and alkene.In the present invention, described catalyzer is acidic ionic liquid catalysts (below also referred to as catalyzer).

The ability of known ion liquid catalyst alkylated reaction in this area.It is the cationic compound ion liquid comprising derived from containing the amine of alkyl or the hydrohalogen of pyridine for catalyzer of the present invention.Preferably, described positively charged ion comprises by four nitrogen-atoms that substituting group is saturated, has a hydrogen atom and an alkyl in described substituting group at least.More preferably, described alkyl substituent is at least one group being selected from methyl, ethyl, propyl group, butyl, amyl group and hexyl.Suitable cationic example comprises triethyl ammonium (NEt 3h +) and methyl-diethyl ammonium positively charged ion (MeNEt 2h +) or

The negatively charged ion of compound ion liquid is the halogenide of the Lewis acid based on aluminium, particularly aluminium preferably, preferably aluminum chloride (III).Because the lewis acidic acidity of aluminum chloride is very high, therefore preferably the halogenide of aluminum chloride or other aluminium is combined to form coordination anion with another kind of or more metal halide, vitriol or nitrate, particularly, derived from the coordination anion of two or more metal halides, wherein at least one metal halide is the halogenide of aluminium.Metal halide, vitriol or the nitrate of suitable other can be selected from halogenide, vitriol or the nitrate of following metal, and described metal selects the group of IB family element, the IIB family element of the periodic table of elements and the transition element of the periodic table of elements composition of the free periodic table of elements.The example of suitable metal comprises copper, iron, zinc, nickel, cobalt, molybdenum or platinum.Described metal halide, vitriol or nitrate preferable alloy halogenide, more preferably metal chloride or metal bromide, for example, the muriate of the muriate of the muriate of the muriate of copper (I), copper (II), nickel (II), iron (II).Preferably, the scope of the compound of aluminium and the mol ratio of other metallic compounds is 1: 100~100: 1, more preferably 1: 1~100: 1, or and then more preferably 2: 1~30: 1.The coordination anion that comprises aluminium and another kind of metal by use, the alkylate oil product that can be improved.Method for the preparation of this catalyzer is for example described in US7285698.Particularly preferred catalyzer is to comprise derived from the positively charged ion of triethyl ammonium chloride with derived from the acidic ionic liquid catalysts of the muriatic coordination anion of aluminum chloride (III) and copper (II).

As mentioned above, the hydrocarbon mixture that comprises isoparaffin and alkene contacts with catalyzer.Described hydrocarbon mixture in reactor with described catalyst mix with form reaction mixture.Along with the carrying out of reaction, reaction mixture also will comprise product except comprising hydrocarbon reaction thing and acidic ion liquid.Hydrocarbon mixture can complete by any suitable means (comprising dynamic mixer and static mixer) for mixing two or more liquid with mixing of catalyzer.In the time contacting with catalyzer, isoparaffin and alkene react under alkylation conditions, thereby form alkylate oil.

Collected the reactor effluent (in addition also referred to as reactor effluent) that comprises alkylate oil by reactor.Described reactor effluent comprises hydrocarbon phase and ionic liquid phase.To comprise hydrocarbon and the total liquid weight based on described hydrocarbon phase be the acidic ion liquid of 0 volume %~5 volume %, the preferably dissolving of 0 volume %~3 volume %, the acidic ion liquid of the dissolving of 0 volume %~0.5 volume % more preferably to the hydrocarbon phase of indication herein.Preferably, total liquid weight that described hydrocarbon phase comprises based on described hydrocarbon phase is the hydrocarbon of 95 volume %~100 volume %, is preferably the hydrocarbon of 97 volume %~100 volume %.Ionic liquid herein refers to that comprising acidic ion liquid and the total liquid weight based on described ionic liquid phase is 0 volume %~20 volume %, the preferred ionic liquid phase of the hydrocarbon of the dissolving of 0 volume %~10 volume % mutually.Preferably, to comprise mutually the total liquid weight based on described ionic liquid phase be 80 volume %~100 volume %, the preferred acidic ion liquid of 90 volume %~100 volume % to described ionic liquid.Although should be appreciated that hydrocarbon phase and ionic liquid are immiscible mutually, however still can have a small amount of hydrocarbon be dissolved in ionic liquid mutually in, vice versa, a small amount of acidic ionic liquid catalysts is also dissolved in hydrocarbon phase.

Described reactor effluent still comprises the unreacted isoparaffin of suitable volume.Therefore, a part for reactor effluent can be recycled in described reactor to maintain the high molar ratio of isoparaffin with respect to alkene.In the method for the invention, at least a portion of reactor effluent provides to the first separating unit to separate this reactor effluent.

Should be appreciated that typical plant-scale separating unit can not be divided into described reactor effluent the two or more effluents that only comprises a phase (for example, hydrocarbon phase or ionic liquid phase).But, nowadays have been found that the heterogeneous effluent that reactor effluent can be divided into ionic liquid phase effluent and comprise hydrocarbon and acidic ion liquid.The ionic liquid phase effluent of herein mentioning refers to that comprising ionic liquid phase and the total liquid weight based on described ionic liquid phase effluent is 0 volume %~20 volume %, the preferred effluent of the hydrocarbon phase of 0 volume %~10 volume %.Preferably, to comprise the total liquid weight based on described ionic liquid phase effluent be 80 volume %~100 volume %, the preferred ionic liquid phase of 90 volume %~100 volume % to described ionic liquid phase effluent.

In the above-mentioned separation of two kinds of immiscible phases, collect substantially pure effluent by separator, it mainly comprises a phase, and acceptable is the two-phase that described heterogeneous effluent comprises suitable volume.Within such separation belongs to technician's the conventional skill of separation field.

Described ionic liquid phase effluent is recycled to described reactor at least partly.

In the method for the invention, at least a portion of the heterogeneous effluent being obtained by the first separating unit is delivered to the second separating unit subsequently without chemical treatment in the middle of any.The chemical treatment of indication is herein the processing that makes the one or more of compound decomposition in heterogeneous effluent.

Described heterogeneous effluent comprises the overwhelming majority (even if not being substantially whole words) hydrocarbon, and this is a part for reactor effluent.But as mentioned above, described heterogeneous effluent also comprises the acidic ion liquid of suitable volume.

In the second separating unit, described heterogeneous effluent is separated into hydrocarbon phase effluent and another effluent.The hydrocarbon phase effluent of indication is that to comprise hydrocarbon phase and the gross weight based on described hydrocarbon phase effluent be 0 volume %~5 volume %, preferably ionic liquid phase, the more preferably effluent of the ionic liquid phase of 0 volume %~0.5 volume % of 0 volume %~3 volume % herein.Preferably, to comprise the gross weight based on described hydrocarbon phase effluent be the hydrocarbon phase of 95 volume %~100 volume %, the preferred hydrocarbon phase of 97 volume %~100 volume % to described hydrocarbon phase effluent.

The first and/or second separating unit can be any separating unit that is suitable for separating two immiscible liquid phases.The example of suitable separating unit comprises settlement separate unit and centrifugal separation unit.Preferably, the first and/or second separating unit is centrifugal separation unit, is more preferably cyclonic separation type separating unit, because such separating unit allows to separate fast and continuously two immiscible liquid phases.In addition, owing to comparing and can shorten the required time that separates with traditional sedimentation unit, the common small volume of centrifugal separation unit, needs less floor space, the more important thing is, the amount of liquid lighter hydrocarbons, particularly Trimethylmethane is wanted much less.Preferably, described cyclonic separator is Dutch cyclone (hydro-cyclone).Dutch cyclone herein refers to the cyclonic separator that is designed for Separation of Water-hydrocarbon mixture.Preferably the first and second separating units are all cyclonic separation type separating units.

The separating unit of herein mentioning is to comprise a separator (as, cyclonic separator) or the separating unit of more than two separator of being arranged in parallel.

In the excessive situation of the volume of reactor effluent, can also provide the two or more combination of the first and second separating units of configuration in parallel.

Described hydrocarbon phase effluent still comprises the unreacted isoparaffin of suitable volume.Therefore, a part for hydrocarbon phase effluent can be recycled in described reactor to maintain the high molar ratio of isoparaffin with respect to alkene.At least a portion of hydrocarbon phase effluent at least fractionation is the stream that comprises alkylate oil and the stream that comprises isoparaffin.

If needed, the ionic liquid mark in hydrocarbon effluent can be by making hydrocarbon phase effluent in other centrifugal separation unit (as cyclonic separator) or accepting other physical separation processes and further reduce in sedimentation unit.Although sedimentation unit has relatively large volume than for example cyclonic separator, even if but sedimentation unit is as the second separating unit, the present invention still can provide favourable part, because the second sedimentation unit is still much smaller than being used in the traditional method of separate reactor effluent sedimentation unit used.Preferably, described method is also included in provides to other sedimentation unit described hydrocarbon phase effluent to remove other ionic liquid to before the fractionation of hydrocarbon phase effluent.

The stream that comprises isoparaffin is reused to form a part for the isoparaffin charging that offers described method conventionally.At least a portion of this stream that can comprise isoparaffin by recirculation also makes it combine to carry out with the isoparaffin that is supplied to the method.

The hydrocarbon stream that comprises alkylate oil obtaining can be used for preparing aviation spirit or as the mixing element for gasoline.Other hydrocarbon stream also can be by fractionation pure hydrocarbon effluent substantially, as the stream that comprises n-paraffin obtains.

Described hydrocarbon phase effluent can be by carrying out fractionation by any method that is suitable for fractionation hydrocarbon stream.Preferably, described hydrocarbon phase effluent is by carrying out fractionation with one or more distillation unit.

Another effluent that derives from the second separating unit can be recycled in the first separating unit, or is combined with the reactor effluent that offers the first separating unit.

Observe, in the process of alkylated reaction, formed solid.The solid of herein mentioning is undissolved solid particulate.Described solid can have any size, but has been found that the mean sizes that solid has is 0.1 μ m~5 μ m.Particularly, the particle diameter that the solid of the total number at least 50% based on solid particulate has is less than 5 μ m, and the particle diameter that more especially 80% solid has is less than 5 μ m.

Although in the process of mixing, these solids are dispersed in whole reaction mixture, but have been found that solid in the time of separate reactor effluent, that is, accumulate in to a great extent in ionic liquid phase effluent.This is because solid has higher density.In the time that described ionic liquid phase effluent is recycled to reactor at least partly, buildup of solids, in reactor mixture, causes solids content very high in reaction mixture, and this is disadvantageous.Due to the precipitation of solid, highly filled in reaction mixture for example can cause path or the valve in reactor and lead to the pipeline of separating unit and the obstruction of the pipeline that stretched out by separating unit.In addition, when highly filled, solid can be coalescent and form large aggregation, causes the danger of stopping up to increase.

Therefore, preferably, in the method for the invention, ionic liquid phase effluent is offered and is suitable for the 3rd separating unit of separate solid and liquid and removes solid from substantially pure acidic ion liquid effluent, thereby remove solid from ionic liquid phase effluent.In the present invention, by least a portion of removing solid in ionic liquid phase effluent.Preferably, the degree that solid is removed by ionic liquid phase effluent be reaction mixture to comprise acidic ionic liquid catalysts gross weight based in reactor be the solid of 5 % by weight at the most, the preferably solid of 2 % by weight at the most.By from ionic liquid phase effluent but not reactor effluent is removed solid, thereby reduce by the liquid volume of the 3rd separating unit, thereby allow to use less separating unit.

Described the 3rd separating unit can be any separating unit that is suitable for removing solid and liquid, includes but not limited to filtration, precipitation and centrifugal method.These methods are well-known in the art.

Due to the special property that ionic liquid has, at the temperature that is preferably liquid in acidic ionic liquid catalysts, carry out the removal of solid.Particularly, preferably at 5 ℃~80 ℃, the temperature of more preferably 20 ℃~60 ℃ is removed solid.By remove solid at higher temperature, the viscosity of ionic liquid is lower, and this is of value to minimizing and obtains solid time and the energy input required with separating of liquid.

Solid can be in any form by removing in method, and solid is removed with the form of slurry of solids conventionally.Such slurry comprises for example some residual acidic ion liquids except solid.

Optionally, the catalyzer in ionic liquid phase effluent can with acid, preferably hydrogen halide, is more preferably hydrogenchloride and contacts so that described catalyst regeneration.Preferably, acidic ionic liquid catalysts is by least a portion of ionic liquid phase effluent is recycled in reactor and is regenerated, and at least a portion of the acidic ionic liquid catalysts in the effluent of recirculation is to regenerate at least a portion by hydrogenchloride being added into recirculation outflow thing.

By making catalyzer contact with hydrogenchloride, reduced the unwelcome chlorination to hydrocarbon after removing most hydrocarbon.Hydrogenchloride reacts with acidic ionic liquid catalysts.Add hydrogenchloride until do not have hydrogenchloride to be consumed again, that is, until reach capacity.The consumption of hydrogenchloride can be followed the trail of by monitoring pressure.Preferably, complete the interpolation of hydrogenchloride with the step at regular interval, optional being added in ionic liquid in batches to be regenerated measured the pressure between each interpolation step simultaneously.By add hydrogenchloride in little step, reduce the generation of unwelcome hydrogenchloride pneumatic jack when saturated.

The interpolation of hydrogenchloride can complete to the stream of next unit from a unit stream by hydrogenchloride being injected in one or more unit or being injected into one or more.The interpolation of hydrogenchloride for example can by with Venturi absorber, the Venturi absorber that is preferably arranged on the downstream of the device for removing solid completes.

As mentioned above, although can be received in the hydrogenchloride that has some gaseous states in reactor, but in reactive system, gather and remain unwelcome because acidic ion liquid is chlorinated unreacted gaseous hydrogen chloride that hydrogen supersaturation causes.Residual gaseous hydrogen chloride can be removed from reactive system, for example can be by carrying out purge with rare gas elementes such as nitrogen.But, such method needs extra means for nitrogen being provided and being chlorinated follow-up storage and the processing of the nitrogen of hydrogen contamination.In addition, lost a part of hydrogenchloride that is provided for regeneration.Preferably, for example, by (making other spent acid ionic-liquid catalyst, with the form of the stream that comprises used catalyst) sneak into the acidic ionic liquid catalysts that comprises regeneration recirculation effluent (, the effluent of the recirculation that comprises added hydrogenchloride) in, gather thereby reduced this hydrogenchloride.The spent acid ionic-liquid catalyst of herein mentioning is the acidic ionic liquid catalysts that has been used as catalyzer but still is not chlorinated hydrogen regeneration in chemical reaction.By this spent acid ionic liquid is reacted with the gaseous hydrogen chloride existing due to initial supersaturation, can consume remaining hydrogenchloride.Can be introduced by external source with the ionic-liquid catalyst of crossing, but, also can make a part for ionic liquid phase effluent without the by-pass of mixed regeneration subsequently of regenerating also.For example, can regeneration of ionic liquid phase effluent, make subsequently it mix with another effluent available from the second separator, other effluent still comprises (, not regeneration) ionic-liquid catalyst of using.

The solid of removing from method can be dropped, but preferably recycles the composition in solid, for example, for the preparation of fresh acidic ionic liquid catalysts.

In the method for the invention, by making the reaction mixture that comprises isoparaffin and alkene contact with catalyzer under alkylation conditions, thereby isoparaffin and olefine reaction are to form alkylate oil.

Preferably, described hydrocarbon mixture at least comprises Trimethylmethane, iso-pentane or its mixture as isoparaffin.Described hydrocarbon mixture preferably at least comprise there are 2 to 8 carbon atoms, more preferably 3 to 6 carbon atoms and then the more preferably alkene of 4 or 5 carbon atoms.The example of suitable alkene comprises propylene, 1-butylene, 2-butylene, iso-butylene, 1-amylene, 2-amylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2 butylene.

Isoparaffin and alkene being preferably more than 1, be generally 1: 1~40: 1, the mol ratio of more preferably 1: 1~20: 1 is fed in method.In the situation of successive reaction, excessive isoparaffin can be recycled with again for hydrocarbon mixture.

Alkylation conditions (or processing condition) is those conditions of HF as known in the art and sulfuric acid alkylation.The processing condition of actually operating also depend on but are not limited to the accurate composition of hydrocarbon mixture and catalyzer.

Temperature in reactor is preferably-20 ℃~100 ℃, more preferably 0 ℃~50 ℃.Described temperature under any circumstance all must be higher than the fusing point of ionic liquid.

For steam in inhibited reaction device forms, described method is carried out under pressure, and the pressure in preferred reactor is 0.1MPa~1.6MPa.

Hydrocarbon mixture can contact with catalyzer in any suitable alkylation reactor.Described hydrocarbon mixture can contact with catalyzer in semicontinuous or continuation method.

In Fig. 1, provide the schematic diagram of the inventive method.

In Fig. 1, the hydrocarbon mixture that will comprise alkene and isoparaffin (for example, butylene and Trimethylmethane) offers reactor 100 by pipeline 105.Acidic ionic liquid catalysts also offers reactor 100 by pipeline 110.In reactor 100, hydrocarbon mixture and catalyzer mix under alkylation conditions.By pipeline 115, collected the reactor effluent that comprises alkylate oil that comprises solid by reactor.A part for this effluent can directly be recycled in described reactor, or via recirculation line 117 and pipeline 105 combinations.At least a portion of effluent is supplied to the first separating unit 120, for example, cyclonic separator.In the first separating unit 120, under the impact of centrifugal force or gravity, reactor effluent is separated into ionic liquid phase effluent and heterogeneous effluent.Described ionic liquid phase effluent can be recycled in reactor via pipeline 130.

Make described heterogeneous effluent be supplied to the second separating unit 140, for example cyclonic separator via pipeline 135 from the first separating unit 120.In the second separating unit 140, described heterogeneous effluent is separated into hydrocarbon phase effluent and another effluent.Described another effluent is collected by the second separating unit 140 via pipeline 147, with pipeline 115 combinations, and is recycled in the first separating unit.A part for hydrocarbon phase effluent can directly be recycled in reactor, or via recirculation line 117 and 119 and pipeline 105 combinations.At least a portion of hydrocarbon phase effluent offers fractionator 125 by pipeline 145.The product that comprises alkylate oil is reclaimed by the bottom of fractionator 125 by pipeline 127.Alkylate oil product for example can be used for the object of fuel mix.In addition, the stream that comprises isoparaffin is reclaimed by fractionator 125, then via pipeline 129 recirculation, thereby becomes the part of the hydrocarbon mixture in pipeline 105.Other the stream (not shown) that comprises hydrocarbon also can be reclaimed by fractionator 125.

The ionic liquid phase effluent of part or all can be transferred to the 3rd separating unit 155 by pipeline 150 by pipeline 130, for example, and separating centrifuge.In separating centrifuge 155, under the impact of centrifugal force, by removing solid in ionic liquid phase effluent, then reclaim solid via pipeline 160.Remaining ionic liquid phase effluent is discharged by separating centrifuge 155 through pipeline 165.Optionally, hydrogen chloride gas offers ionic liquid phase effluent by gas container 175 through pipeline 170.Optionally, use mixing device (not shown) hydrogen chloride gas to be sneaked in pipeline 165 as Venturi absorber.Carry out hydrogenchloride regeneration by a part that makes catalyzer through pipeline 130 bypasses, when pipeline 165 and 130 links together, any remaining gaseous hydrogen chloride can react with the ionic-liquid catalyst in pipeline 130.Can also near the point of crossing of pipeline 165 and 170, bypass (not shown) be set.Like this, can also be by removing solid in the ionic-liquid catalyst not being reproduced.

Described ionic liquid phase effluent directly returns to reaction zone 100 subsequently.If desired, the spent acid ionic-liquid catalyst of extra fresh acidic ionic liquid catalysts or outside supply can offer reaction zone 100 via pipeline 180.

Embodiment

By following non-limiting example, the present invention is described.

Embodiment 1

In order to show the effect of the method for the present invention that wherein hydrocarbon phase obtains by least two separating steps, use cyclonic separator sample separation reactor effluent, the mixture that described effluent comprises hydrocarbon reaction thing (being mainly Trimethylmethane) and alkylate oil product and ionic-liquid catalyst.

It is hydrocarbon and the ionic-liquid catalyst of 1: 1.05 that described sample product reactor effluent comprises volume ratio.Described ionic liquid is the ionic-liquid catalyst (front China University Of Petroleum Beijing, Beijing) that comprises the muriatic coordination anion that is derived from aluminum chloride (III) and copper (I).

Service temperature maintains 30 ℃~50 ℃, and working pressure maintains 0.1MPa~0.5MPa.The maximum feed rate that offers the sample product reactor effluent of cyclonic separator is 2m 3/ hour.

Embodiment 1a (non-the present invention)

In this experiment, use single separating step that sample product reactor effluent is separated into hydrocarbon phase effluent and ionic liquid phase effluent.The separating resulting obtaining is as follows.

Too high in order to prevent the mark of ionic liquid in hydrocarbon phase effluent, only reclaim the sample product reactor effluent of 40 volume % as hydrocarbon phase effluent.The in the situation that of a separator, there is no to increase the mark of the ionic liquid wherein comprising, the mark of the reactor effluent as hydrocarbon phase effluent being reclaimed by separator can not increase.This may cause the pollution of alkylate oil product and the increase of ionic liquid loss.

The sample product reactor effluent of remaining 60 volume % is to reclaim as ionic liquid phase effluent.

Described hydrocarbon phase effluent comprises with the volumeter of hydrocarbon phase effluent:

The hydrocarbon of-95.5 volume %; With

The ionic liquid of-4.5 volume %.

Ionic liquid phase effluent comprises with the volumeter of ionic liquid phase effluent:

The hydrocarbon of-17.7 volume %; With

The ionic liquid of-82.3 volume %.

While using a separator, the hydrocarbon of the approximately 79 volume % that provided by sample product reactor effluent is at first recycled in hydrocarbon effluent.

Embodiment 1b

In this experiment, use two separating steps that sample product reactor effluent is separated into hydrocarbon phase effluent and ionic liquid phase effluent.The separating resulting obtaining is as follows.

The 50 volume % that offer in the charging (, sample product reactor effluent) of centrifuge separator reclaim compared with low heterogeneous effluent as density, and remaining 50 volume % obtain as the higher ionic liquid phase effluent of density.

Described heterogeneous effluent comprises with the volumeter of heterogeneous effluent:

-be the hydrocarbon of 93.8 volume %; With

The ionic liquid of-6.2 volume %.

Described ionic liquid phase effluent comprises with the volumeter of ionic liquid phase effluent:

-be the hydrocarbon of 90.0 volume %; With

The ionic liquid of-10.0 volume %.

The heterogeneous effluent obtaining reclaims as intermediate product, and carries out the separating step of the second cyclonic separator.In the separating step of the second cyclonic separator, reclaimed the heterogeneous effluent of 85 volume % by cyclonic separator as the lighter hydrocarbon phase effluent of density, the heterogeneous effluent of remaining 15 volume % reclaims as higher density phase effluent (also referred to as another effluent).

Described hydrocarbon phase effluent comprises with the volumeter of hydrocarbon phase effluent:

-be the hydrocarbon of 98.5 volume %; With

The ionic liquid of-1.5 volume %.

Described another effluent comprises with the volumeter of another effluent:

-be the hydrocarbon of 68.7 volume %; With

The ionic liquid of-31.3 volume %.

While using two separators, in the hydrocarbon being provided by sample product reactor effluent at first, approximately 86 volume % are recycled in hydrocarbon effluent.By using two separators (in this case for series connection cyclonic separator) to separate hydrocarbon phase effluent from sample product reactor effluent, the hydrocarbon that the mark in can recovery sample reactor effluent increases, and delivered in fractionator.This is because this fact obtaining as the heterogeneous effluent from the first separator compared with the reactor effluent of large mark.Cause the ionic liquid mark in this heterogeneous effluent to increase although the sample product reactor effluent of larger mark is sent to lighter heterogeneous effluent, make the final ionic liquid mark in obtained hydrocarbon phase effluent much lower owing to thering is the second separating step.Therefore, the hydrocarbon of the larger mark in reactor effluent can separate with ionic liquid.In embodiment 1a, only use a separator, described hydrocarbon phase effluent only comprises 79 volume % of the hydrocarbon being present at first in reactor effluent.But in embodiment 1b, the hydrocarbon of 86 volume % in reactor effluent is recovered in hydrocarbon effluent, it comprises less ionic liquid.

In addition, than embodiment 1a, described ionic liquid phase effluent comprises less hydrocarbon, even with in situation that another effluent is combined, be also like this.

In situation about further processing in other sedimentation unit at hydrocarbon phase effluent, the size of the volume of sedimentation unit is only for separating of 42.5% of the sedimentation unit of total reactor effluent.

Embodiment 2

This embodiment has shown the benefit that uses at least one centrifugal separation unit (being cyclonic separator in this case) to replace traditional sedimentation unit.

Based on the 2m that delivers to cyclonic separator 3/ hour feeding rate, the residence time of sample product reactor effluent in cyclonic separator is 1.5 minutes.Use traditional sedimentation unit in order to obtain same separating resulting, the residence time conventionally needing is at least 15 minutes.Therefore,, in order to maintain identical feeding rate, traditional settling vessel must have 0.5m 3volume, this volume than the cyclonic separator of embodiment 1 has increased 10 times.As mentioned above, this causes the total inventory (inventory) of liquid light hydrocarbon very large, and this is disadvantageous.

Claims (10)

1. prepare a method for alkylate oil, described method is included in and under alkylation conditions, in reactor, makes the hydrocarbon mixture that at least comprises isoparaffin and alkene contact with acidic ionic liquid catalysts, thereby obtains alkylate oil, and described method also comprises:
-collect the reactor effluent that comprises alkylate oil from described reactor, wherein said reactor effluent comprises ionic liquid phase and hydrocarbon phase;
-at least a portion of described reactor effluent is separated into ionic liquid phase effluent and heterogeneous effluent in the first separating unit;
-at least a portion of described heterogeneous effluent is separated into hydrocarbon phase effluent and another effluent in the second separating unit; With
-at least a portion of described ionic liquid phase effluent is recycled to described reactor,
Wherein, described the first separating unit and the second separating unit are cyclonic separator separating units, the hydrocarbon phase of 0 to the 20 volume % that described ionic liquid phase effluent comprises ionic liquid phase and the total liquid weight based on described ionic liquid phase effluent, and the ionic liquid phase of described hydrocarbon phase effluent 0 to the 3 volume % that comprises hydrocarbon phase and the total liquid weight based on described hydrocarbon phase effluent.
2. the hydrocarbon phase of 0 to the 10 volume % that the method for claim 1, wherein described ionic liquid phase effluent comprises ionic liquid phase and the total liquid weight based on described ionic liquid phase effluent.
3. the ionic liquid phase of 0 to the 0.5 volume % that the method for claim 1, wherein described hydrocarbon phase effluent comprises hydrocarbon phase and the total liquid weight based on described hydrocarbon phase effluent.
4. the method for claim 1, wherein described method also comprises:
-by described hydrocarbon phase effluent at least fractionation be the stream that comprises alkylate oil and the stream that comprises isoparaffin.
5. the method for claim 1, wherein described ionic liquid phase effluent comprises solid, and described method also comprises:
-described ionic liquid phase effluent is provided to the 3rd separating unit that is applicable to separate solid and liquid; With
-from described ionic liquid phase effluent, remove at least a portion of described solid.
6. the method for claim 1, wherein described isoparaffin is Trimethylmethane and/or iso-pentane.
7. the method for claim 1, wherein described hydrocarbon mixture comprises the alkene with 3 to 6 carbon atoms.
8. the method for claim 1, wherein described hydrocarbon mixture comprises the alkene with 4 or 5 carbon atoms.
9. the method for claim 1, wherein, described acidic ionic liquid catalysts is the compound ion liquid being made up of positively charged ion, negatively charged ion, described positively charged ion is derived from containing the amine of alkyl or the hydrohalogen of pyridine, described negatively charged ion is the heterogeneous coordination anion derived from two or more metal halides, the halogenide that wherein at least one metal halide is aluminium, and any other metal halide is the halogenide of the metal of the group of the IB family element that selects the free periodic table of elements, the IIB family element of the periodic table of elements and the transition element of periodic table of elements composition.
10. method as claimed in claim 9, the muriate that wherein said catalyzer comprises aluminum chloride and copper (I) or the muriate of copper (II).
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CN101210192A (en) * 2006-12-26 2008-07-02 中国科学院兰州化学物理研究所 Process for preparing alkylated oil
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CN101679142A (en) * 2006-12-14 2010-03-24 雪佛龙美国公司 Isomerization of butene in the ionic liquid-catalyzed alkylation of light isoparaffins and olefins
CN101210192A (en) * 2006-12-26 2008-07-02 中国科学院兰州化学物理研究所 Process for preparing alkylated oil

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