CN102639469A - Process for preparing an alkylate - Google Patents
Process for preparing an alkylate Download PDFInfo
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- CN102639469A CN102639469A CN2010800347144A CN201080034714A CN102639469A CN 102639469 A CN102639469 A CN 102639469A CN 2010800347144 A CN2010800347144 A CN 2010800347144A CN 201080034714 A CN201080034714 A CN 201080034714A CN 102639469 A CN102639469 A CN 102639469A
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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
Technical field
The present invention provides the method for preparing alkylate oil.
Background technology
Increasing demand to alkylate oil fuel mix raw material increases.The mixing element that acts as a fuel, alkylate oil has combined low-steam pressure and high-octane characteristic.
Nearly all alkylate oil all is through in the presence of the proper acidic catalyzer, Trimethylmethane and butene reaction being made.Catalyzer the most commonly used is HF and sulfuric acid, but has also reported other catalyzer, like solid acid catalyst.Recently, the alkylation of the isoparaffin of use acidic ionic liquid catalysts and alkene has caused concern as the replacement scheme of the alkylation of HF and sulfuric acid catalysis.
For example in US7285698, disclose the method that is used to make alkylate oil, it uses compound ion liquid catalyst to make Trimethylmethane and butene reaction.In the method for US7285698, Trimethylmethane and butylene are offered reactor drum, and reactant is contacted with compound ion liquid form alkylate oil.The separate reactor elute is recycled to reactor drum mutually with ionic liquid, handles hydrocarbon phase simultaneously to reclaim said alkylate oil.
For example at (Z.Liu, R.Zhang, C.Xu such as Liu; R.Xia.Ionic liquid alkylation process produces high-quality gasoline; Oil and Gas Journal, the 104th volume, the 40th phase; 2006) in, mention and to improve to be used for the IL catalyzer the sulfuric acid alkylation unit.But, also mention in order to improve separating of reactor effluent (that is, ionic-liquid catalyst and hydrocarbon phase) and must transform sedimentation unit.
In US2005/0119423, disclose and used ionic-liquid catalyst to prepare the method for polyalphaolefin.In the method for US2005/0119423, reactor effluent is offered separator to obtain to comprise the phase of polyalphaolefin, this phase still comprises residual ionic-liquid catalyst.Thereby US2005/0119423 proposes to make the Xiang Yushui that comprises polyalphaolefin to mix and makes catalyst deactivation, in two extra continuous separating steps, makes phase and the water sepn that comprises polyalphaolefin subsequently.
Need the ionic liquid alkylation in this area, this method improvement the separation of reactor effluent.
Summary of the invention
Nowadays the reactor effluent that has been found that the ionic liquid alkylation reactor can be divided into acidic ion liquid phase and hydrocarbon phase effectively through fractional separation.
Therefore; The present invention provides a kind of method for preparing alkylate oil; Said method is included in the hydrocarbon mixture that comprises isoparaffin and alkene is at least contacted with acidic ionic liquid catalysts, thereby obtains alkylate oil, and said method also comprises:
-collect the reactor effluent that comprises alkylate oil from said reactor drum, wherein said reactor effluent comprises ionic liquid phase and hydrocarbon phase;
-at least a portion with said reactor effluent in first separating unit is separated into ionic liquid phase elute and heterogeneous elute;
-in second separating unit, at least a portion of said heterogeneous elute is separated into hydrocarbon phase elute and another elute; With
-at least a portion of said ionic liquid phase elute is recycled to said reactor drum.
The invention has the advantages that and need not in the hydrocarbon phase that contains alkylate oil, to add entry or additional compounds.In addition, need not specially make catalyst deactivation or otherwise be damaged, thereby reduce catalyst consumption of the present invention.
Description of drawings
Provided the synoptic diagram of the inventive method among Fig. 1.
Embodiment
In the method for the invention, through making isoparaffin and olefine reaction prepare alkylate oil.Resulting alkylate oil is particularly suitable for gasoline blended purpose.In the method for the invention, isoparaffin and alkene are offered reactor drum.In said reactor drum, make the hydrocarbon mixture that comprises isoparaffin and alkene and be suitable for alkylating catalyzer and contact.Said hydrocarbon mixture comprises the alkene that is provided by the outside usually, that is, and and fresh alkene, and comprise isoparaffin.Said isoparaffin can be the isoparaffin that is provided by the outside, that is, and and fresh alkene, and/or by the isoparaffin of any other part recycling of this method.Can fresh isoparaffin and alkene separately be offered this method, but normally fresh isoparaffin and fresh alkene offered said reactor drum as the mixture that comprises isoparaffin and alkene.In the present invention, said catalyzer is acidic ionic liquid catalysts (below be also referred to as catalyzer).
The ability of known ion liquid catalyst alkylated reaction in this area.Be used for catalyzer of the present invention and be comprising the cationic compound ion liquid of hydrohalogen of amine or the pyridine of the self-contained alkyl of deriving.Preferably, said positively charged ion comprise by four substituting groups saturated nitrogen-atoms, have a Wasserstoffatoms and an alkyl in the said substituting group at least.More preferably, said alkyl substituent is at least one group that is selected from methyl, ethyl, propyl group, butyl, amyl group and the hexyl.Suitable cationic instance comprises triethyl ammonium (NEt
3H
+) and methyl-diethyl ammonium positively charged ion (MeNEt
2H
+) or
The negatively charged ion of compound ion liquid is preferably based on the halogenide of the Lewis acid, particularly aluminium of aluminium, preferred aluminum chloride (III).Because the lewis acidic acidity of aluminum chloride is very high; Therefore preferred halogenide with aluminum chloride or other aluminium combines to form coordination anion with another kind of or more metal halide, vitriol or nitrate salt; Particularly derived from the coordination anion of two or more metal halides, wherein at least a metal halide is the halogenide of aluminium.Metal halide, vitriol or the nitrate salt of suitable other can be selected from halogenide, vitriol or the nitrate salt of following metal, and said metal is selected from the group of being made up of the transition element of the IIB family element of the IB family element of the periodic table of elements, the periodic table of elements and the periodic table of elements.The instance of suitable metal comprises copper, iron, zinc, nickel, cobalt, molybdenum or platinum.Said metal halide, vitriol or nitrate salt preferable alloy halogenide, more preferably metal chloride or metal bromide, for example, the muriate of the muriate of the muriate of copper (I), copper (II), the muriate of 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.Comprise the coordination anion of aluminium and another kind of metal, the alkylate oil product that can be improved through use.The method that is used for preparing this catalyzer for example is described in US7285698.Preferred especially 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 stated, the hydrocarbon mixture that comprises isoparaffin and alkene contacts with catalyzer.Said hydrocarbon mixture in reactor drum with said catalyst mix to 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.Mixing of hydrocarbon mixture and catalyzer can be accomplished through any suitable means (comprising dynamic mixer and static mixer) that are used to mix two or more liquid.When contacting with catalyzer, isoparaffin and alkene react under alkylation conditions, thereby form alkylate oil.
Collect the reactor effluent (being also referred to as reactor effluent in addition) that comprises alkylate oil by reactor drum.Said reactor effluent comprises hydrocarbon phase and ionic liquid mutually.The hydrocarbon phase of indication comprises hydrocarbon and is the dissolved acidic ion liquid of 0 volume %～5 volume %, preferred 0 volume %～3 volume %, the dissolved acidic ion liquid of 0 volume %～0.5 volume % more preferably based on total liquid weight of said hydrocarbon phase here.Preferably, total liquid weight that said hydrocarbon phase comprises based on said hydrocarbon phase is the hydrocarbon of 95 volume %～100 volume %, is preferably the hydrocarbon of 97 volume %～100 volume %.The ionic liquid here is meant mutually and comprises acidic ion liquid and be the ionic liquid phase of the dissolved hydrocarbon of 0 volume %～20 volume %, preferred 0 volume %～10 volume % based on said ionic liquid total liquid weight mutually.Preferably, to comprise the total liquid weight based on said ionic liquid phase mutually be the acidic ion liquid of 80 volume %～100 volume %, preferred 90 volume %～100 volume % to said ionic liquid.Although should be appreciated that hydrocarbon phase and ionic liquid is immiscible mutually, however still can have a spot of hydrocarbon be dissolved in ionic liquid mutually in, vice versa, promptly a spot of acidic ionic liquid catalysts also is dissolved in the hydrocarbon phase.
Said reactor effluent still comprises the unreacted isoparaffin of suitable volume.Therefore, the part of reactor effluent can be recycled in the said reactor drum to keep the high molar ratio of isoparaffin with respect to alkene.In the method for the invention, at least a portion of reactor effluent provide to first separating unit to separate this reactor effluent.
Should be appreciated that typical plant-scale separating unit can not be divided into the two or more elutes that only comprises a phase (for example, hydrocarbon phase or ionic liquid phase) with said reactor effluent.Yet, nowadays have been found that and can reactor effluent be divided into ionic liquid phase elute and the heterogeneous elute that comprises hydrocarbon and acidic ion liquid.The ionic liquid phase elute of here mentioning be meant comprise ionic liquid mutually with based on said ionic liquid mutually total liquid weight of elute be the elute of the hydrocarbon phase of 0 volume %～20 volume %, preferred 0 volume %～10 volume %.Preferably, to comprise the total liquid weight based on said ionic liquid phase elute be the ionic liquid phase of 80 volume %～100 volume %, preferred 90 volume %～100 volume % to said ionic liquid phase elute.
In the above-mentioned separation of two kinds of immiscible phases, collected pure basically elute by separator, it mainly comprises a phase, and acceptable is two phases that said heterogeneous elute comprises suitable volume.Such separation belongs within technician's the conventional skill of separation field.
Said ionic liquid phase elute part at least is recycled to said reactor drum.
In the method for the invention, at least a portion of the heterogeneous elute that is obtained by first separating unit is delivered to second separating unit subsequently without chemical treatment in the middle of any.The chemical treatment of indication here is the processing that a kind of or more compounds in the heterogeneous elute is decomposed.
Said heterogeneous elute comprises the overwhelming majority (even not being whole basically words) hydrocarbon, and this is the part of reactor effluent.Yet as stated, said heterogeneous elute also comprises the acidic ion liquid of suitable volume.
In second separating unit, said heterogeneous elute separates into hydrocarbon phase elute and another elute.Here the hydrocarbon phase elute of indication be comprise hydrocarbon phase and gross weight based on said hydrocarbon phase elute be 0 volume %～5 volume %, preferred 0 volume %～3 volume % ionic liquid mutually, the more preferably elute of the ionic liquid phase of 0 volume %～0.5 volume %.Preferably, to comprise based on the gross weight of said hydrocarbon phase elute be the hydrocarbon phase of 95 volume %～100 volume %, the hydrocarbon phase of preferred 97 volume %～100 volume % to said hydrocarbon phase elute.
First and/or second separating unit can be any separating unit that is suitable for separating two immiscible liquid phases.The instance of suitable separating unit comprises settlement separate unit and centrifugal separation unit.Preferably, first and/or second separating unit is a 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, separate the required time owing to comparing to shorten with traditional sedimentation unit, the common volume of centrifugal separation unit is less, needs less floor space, the more important thing is, the amount of liquid lighter hydrocarbons, particularly Trimethylmethane is wanted much less.Preferably, said cyclonic separator is Dutch cyclone (hydro-cyclone).The Dutch cyclone here be meant be designed for branch dried up-cyclonic separator of hydrocarbon mixture.Preferred first and second separating units all are cyclonic separation type separating units.
The separating unit of here mentioning is to comprise a separator (like, cyclonic separator) or the separating unit of two above separators being arranged in parallel.
In the excessive situation of the volume of reactor effluent, the two or more combination of first and second separating units of parallel connection configuration can also be provided.
Said hydrocarbon phase elute still comprises the unreacted isoparaffin of suitable volume.Therefore, the part of hydrocarbon phase elute can be recycled in the said reactor drum to keep the high molar ratio of isoparaffin with respect to alkene.At least a portion of hydrocarbon phase elute fractionation at least is the stream that comprises the stream of alkylate oil and comprise isoparaffin.
If desired, then the ionic liquid mark in the hydrocarbon elute can further reduce through making the hydrocarbon phase elute in other centrifugal separation unit (like cyclonic separator) or in sedimentation unit, accept other physical separation processes.Although sedimentation unit has relatively large volume than for example cyclonic separator; Even but sedimentation unit is as second separating unit; The present invention still can provide favourable part, because second sedimentation unit is still much little than being used in the traditional method of separate reactor elute used sedimentation unit.Preferably, said method also be included in to before the fractionation of hydrocarbon phase elute with said hydrocarbon phase elute provide to other sedimentation unit to remove other ionic liquid.
The circulation that comprises isoparaffin is often utilized a part that offers the isoparaffin charging of said method with formation again.This can through recycling comprise isoparaffin stream at least a portion and it is combined with the isoparaffin that is supplied to this method carry out.
The hydrocarbon stream that comprises alkylate oil that obtains can be used for preparing aviation spirit or as the mixing element that is used for gasoline.Other hydrocarbon stream also can be through the pure basically hydrocarbon elute of fractionation, as the stream that comprises n-paraffin obtains.
Said hydrocarbon phase elute can come fractionation through using any method that is suitable for the fractionation hydrocarbon stream.Preferably, said hydrocarbon phase elute comes fractionation through using one or more distillation unit.
Another elute that derives from second separating unit can be recycled in first separating unit, perhaps combines with the reactor effluent that offers first separating unit.
Observe, in the process of alkylated reaction, formed solid.The solid of here mentioning is undissolved solid particulate.Said solid can have virtually 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 has based on the solid of total number at least 50% of solid particulate is less than 5 μ m, is more especially particle diameter that 80% solid has less than 5 μ m.
Although these solid dispersed are in the entire reaction mixture in the blended process, but when the separate reactor elute, have been found that solid, that is, accumulate in to a great extent in the ionic liquid phase elute.This is because solid has higher density.When said ionic liquid phase elute at least partly was recycled to reactor drum, buildup of solids caused solids content very high in reaction mixture in reactor mixture, and this is disadvantageous.Because due to the solid deposition, highly filled in the reaction mixture for example can cause path or the valve in the reactor drum and lead to the pipeline of separating unit and the obstruction of the pipeline that stretched out by separating unit.In addition, be in when highly filled, solid can coalescence and form big aggregation, and the danger that causes stopping up increases.
Therefore; Preferably; In the method for the invention, ionic liquid phase elute is offered the 3rd separating unit that is suitable for separate solid and liquid and from pure basically acidic ion liquid elute, removes solid, thereby from ionic liquid phase elute, remove solid.In the present invention, by removing solid at least a portion in the ionic liquid phase elute.Preferably, the degree that solid is removed by ionic liquid phase elute is that reaction mixture comprises based on the acidic ionic liquid catalysts gross weight in the reactor drum and is the solid of 5 weight % at the most, the preferred solid of 2 weight % at the most.Through from ionic liquid phase elute but not reactor effluent is removed solid, thereby reduce liquid volume, thereby allow to use littler separating unit through the 3rd separating unit.
Said the 3rd separating unit can be any separating unit that is suitable for removing solid and liquid, includes but not limited to filtration, deposition and centrifugal method.These methods are well-known in the art.
Because the special property that has of ionic liquid, preferably under acidic ionic liquid catalysts is the temperature of liquid, carry out solid and remove.Particularly, preferably at 5 ℃～80 ℃, more preferably 20 ℃～60 ℃ temperature is removed solid.Through under higher temperature, removing solid, ion liquid viscosity is lower, and this is of value to minimizing and obtains solid and separating of liquid of required time and energy input.
Solid can be in any form by removing in the method, and solid is removed with the form of slurry of solids usually.Such slurry comprises for example some residual acidic ion liquids except solid.
Optional is, the catalyzer in the ionic liquid phase elute can with acid, preferably hydrogen halide is more preferably the hydrogenchloride contact so that said catalyst regeneration.Preferably; Acidic ionic liquid catalysts is to be recycled in the reactor drum and regenerated through at least a portion with ionic liquid phase elute, and at least a portion of the acidic ionic liquid catalysts in the elute of recycling is through hydrogenchloride being added into recycling is flowed out at least a portion of thing and regenerated.
Through after the hydrocarbon of removing the overwhelming majority, catalyzer is contacted with hydrogenchloride, reduced unwelcome chlorination to hydrocarbon.Hydrogenchloride and acidic ionic liquid catalysts reaction.Add hydrogenchloride until there not being hydrogenchloride to be consumed again, that is, and until reaching capacity.The consumption of hydrogenchloride can be followed the trail of through monitoring pressure.Preferably, with the interpolation of rule step completion hydrogenchloride at interval, optional being added into treated in the regenerated batch-wise ionic liquid, measures simultaneously and respectively adds the pressure between the step.Through in little step, adding hydrogenchloride, reduced the generation of unwelcome hydrogenchloride pneumatic jack when saturated.
The interpolation of hydrogenchloride can be accomplished to the unitary stream of the next one from a unit stream through hydrogenchloride being injected in one or more unit or being injected into one or more.The interpolation of hydrogenchloride for example can be accomplished through the Venturi absorber that uses Venturi absorber, preferably is arranged on the downstream that are used to remove the solid device.
As stated, some gasiform hydrogenchloride are arranged in the reactor drum, but the unreacted gaseous hydrogen chloride that is caused by the hydrogenchloride supersaturation owing to acidic ion liquid gathers in reactive system and remains unwelcome although can be received in.Can residual gaseous hydrogen chloride be removed from reactive system, for example can be through carrying out purge with rare gas elementes such as nitrogen.But, such method needs follow-up storage and the processing of extra means with the nitrogen that is used to provide nitrogen and polluted by hydrogenchloride.In addition, lost and be provided for regenerated part hydrogenchloride.Preferably; Through (for example making the acid ionic-liquid catalyst of other exhausted; The elute of the form with the stream that comprises used catalyst) sneaking into the recycling that comprises the regenerated acidic ionic liquid catalysts (promptly; The elute that comprises the recycling of the hydrogenchloride that is added) in, gathers thereby reduced this hydrogenchloride.The acid ionic-liquid catalyst of the exhausted of here mentioning is as catalyzer but still not by hydrogenchloride regenerated acidic ionic liquid catalysts in chemical reaction.Through making acid ionic liquid of this exhausted and the gaseous hydrogen chloride reaction that exists owing to initial supersaturation, can consume remaining hydrogenchloride.The exhausted ionic-liquid catalyst can be introduced by external source, and but, the part that also can make ionic liquid phase elute is without the by-pass of mixed regeneration subsequently of regenerating also.For example, can regeneration of ionic liquid phase elute, it is mixed with another elute available from second separator, other elute still comprises exhausted (that is, not regenerated) ionic-liquid catalyst.
The solid of from method, removing can be dropped, but preferably utilizes the composition in the solid again, for example is used to prepare fresh acidic ionic liquid catalysts.
In the method for the invention, contact with catalyzer, thereby isoparaffin and olefine reaction are to form alkylate oil through under alkylation conditions, making the reaction mixture that comprises isoparaffin and alkene.
Preferably, said hydrocarbon mixture comprises Trimethylmethane, iso-pentane or its mixture at least as isoparaffin.Said hydrocarbon mixture preferably comprise at least have 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 instance 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 be preferably more than 1, be generally 1: 1～40: 1, more preferably 1: 1～20: 1 mol ratio is fed in the method.In the situation of successive reaction, excessive isoparaffin can be recycled to be used for hydrocarbon mixture once more.
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 the reactor drum is preferably-20 ℃～100 ℃, more preferably 0 ℃～50 ℃.Said temperature under any circumstance all must be higher than ion liquid fusing point.
For steam in the inhibited reaction device forms, said method is carried out under pressure, and the pressure in the preferred reactor is 0.1MPa～1.6MPa.
Hydrocarbon mixture can contact with catalyzer in any suitable alkylation reactor.Said hydrocarbon mixture can contact with catalyzer in semicontinuous or continuation method.
Provided the synoptic diagram of the inventive method among Fig. 1.
Among Fig. 1, the hydrocarbon mixture that will comprise alkene and isoparaffin (for example, butylene and Trimethylmethane) offers reactor drum 100 through pipeline 105.Acidic ionic liquid catalysts also offers reactor drum 100 through pipeline 110.In reactor drum 100, hydrocarbon mixture and catalyzer mix under alkylation conditions.Through pipeline 115, collect by reactor drum and to comprise that solid comprises the reactor effluent of alkylate oil.The part of this elute can directly be recycled in the said reactor drum, perhaps combines with pipeline 105 via recirculation line 117.At least a portion of elute is supplied to first separating unit 120, for example, cyclonic separator.In first separating unit 120, reactor effluent separates into ionic liquid phase elute and heterogeneous elute under the influence of cf-or gravity.Said ionic liquid phase elute can be recycled in the reactor drum via pipeline 130.
Make said heterogeneous elute be supplied to second separating unit 140, the for example cyclonic separator from first separating unit 120 via pipeline 135.In second separating unit 140, said heterogeneous elute separates into hydrocarbon phase elute and another elute.Said another elute is collected by second separating unit 140 via pipeline 147, combines with pipeline 115, and is recycled in first separating unit.The part of hydrocarbon phase elute can directly be recycled in the reactor drum, perhaps combines with pipeline 105 via recirculation line 117 and 119.At least a portion of hydrocarbon phase elute offers fractionator 125 through pipeline 145.The product that comprises alkylate oil is reclaimed by the bottom of fractionator 125 through pipeline 127.The alkylate oil product for example can be used for the purpose of fuel mix.In addition, the stream that comprises isoparaffin is reclaimed by fractionator 125, then via pipeline 129 recycling, thereby becomes the part of the hydrocarbon mixture in the pipeline 105.Other the stream (not shown) that comprises hydrocarbon also can be reclaimed by fractionator 125.
A part of or whole ionic liquid phase elutes can be transferred to the 3rd separating unit 155 through pipeline 150 by pipeline 130, for example, and separating centrifuge.In separating centrifuge 155, under the influence of cf-,, reclaim solid via pipeline 160 then by removing solid in the ionic liquid phase elute.Remaining ionic liquid phase elute is discharged by separating centrifuge 155 through pipeline 165.Optional is that hydrogen chloride gas offers ionic liquid phase elute by gas container 175 through pipeline 170.Optional is to use mixing device (not shown) such as Venturi absorber that hydrogen chloride gas is sneaked in the pipeline 165.Part through making catalyzer is carried out hydrogenchloride regeneration through pipeline 130 bypasses, and any remaining gaseous hydrogen chloride can react with the ionic-liquid catalyst in the pipeline 130 when then pipeline 165 and 130 linked together.The bypass (not shown) can also be set near the point of crossing of pipeline 165 and 170.Like this, can also be by removing solid in the ionic-liquid catalyst that is not reproduced.
Said ionic liquid phase elute directly returns reaction zone 100 subsequently.In case of necessity, extra fresh acidic ionic liquid catalysts or the acid ionic-liquid catalyst of the outside exhausted of supplying can offer reaction zone 100 via pipeline 180.
Embodiment
Through following non-limiting example the present invention is described.
Embodiment 1
In order to show that wherein hydrocarbon phase is through the effect of the method for the present invention of at least two separating steps acquisitions; Use cyclonic separator sample separation reactor effluent, said elute comprises the mixture of hydrocarbon reaction thing (mainly being Trimethylmethane) and alkylate oil product and ionic-liquid catalyst.
It is 1: 1.05 hydrocarbon and ionic-liquid catalyst that said sample product reactor elute comprises volume ratio.Said ionic liquid is the ionic-liquid catalyst (preceding 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 elute of cyclonic separator is 2m
3/ hour.
Embodiment 1a (non-the present invention)
In this experiment, use single separating step that the sample product reactor elute is separated into hydrocarbon phase elute and ionic liquid elute mutually.The separating resulting that obtains is following.
Too high in order to prevent the mark of ionic liquid in the hydrocarbon phase elute, the sample product reactor elute that only reclaims 40 volume % is as the hydrocarbon phase elute.Under the situation of a separator, do not increase the ion liquid mark that wherein comprises, the mark as the reactor effluent of hydrocarbon phase elute that is reclaimed by separator can not increase.This possibly cause the pollution of alkylate oil product and the increase of ionic liquid loss.
The sample product reactor elute of remaining 60 volume % is to reclaim as ionic liquid phase elute.
Said hydrocarbon phase elute comprises with the volumeter of hydrocarbon phase elute:
The hydrocarbon of-95.5 volume %; With
The ionic liquid of-4.5 volume %.
Ionic liquid phase elute comprises with the volumeter of ionic liquid phase elute:
The hydrocarbon of-17.7 volume %; With
The ionic liquid of-82.3 volume %.
When using a separator, the hydrocarbon of the about 79 volume % that provided by the sample product reactor elute at first is recycled in the hydrocarbon elute.
Embodiment 1b
In this experiment, use two separating steps that the sample product reactor elute is separated into hydrocarbon phase elute and ionic liquid elute mutually.The separating resulting that obtains is following.
The 50 volume % that offer in the charging (that is, the sample product reactor elute) of centrifuge separator reclaim as the lower heterogeneous elute of density, and remaining 50 volume % then obtain as the higher ionic liquid phase elute of density.
Said heterogeneous elute comprises with the volumeter of heterogeneous elute:
-be the hydrocarbon of 93.8 volume %; With
The ionic liquid of-6.2 volume %.
Said ionic liquid phase elute comprises with the volumeter of ionic liquid phase elute:
-be the hydrocarbon of 90.0 volume %; With
The ionic liquid of-10.0 volume %.
The heterogeneous elute that obtains reclaims as intermediate product, and carries out the separating step of second cyclonic separator.In the separating step of second cyclonic separator; The heterogeneous elute that has been reclaimed 85 volume % by cyclonic separator is as the lighter hydrocarbon phase elute of density, and the heterogeneous elute of remaining 15 volume % reclaims as higher density phase elute (being also referred to as another elute).
Said hydrocarbon phase elute comprises with the volumeter of hydrocarbon phase elute:
-be the hydrocarbon of 98.5 volume %; With
The ionic liquid of-1.5 volume %.
Said another elute comprises with the volumeter of another elute:
-be the hydrocarbon of 68.7 volume %; With
The ionic liquid of-31.3 volume %.
When using two separators, about 86 volume % are recycled in the hydrocarbon elute in the hydrocarbon that is provided by the sample product reactor elute at first.Through using two separators (in this situation for placed in-line cyclonic separator) to separate the hydrocarbon phase elute from the sample product reactor elute, the hydrocarbon that the mark in can the recovery sample reactor effluent increases, and it is delivered in the fractionator.This be because big fractional reactor effluent as this fact that obtains from the heterogeneous elute of first separator.Cause the ionic liquid mark in this heterogeneous elute to increase although will be sent to lighter heterogeneous elute, make that owing to having second separating step final ionic liquid mark in the resulting hydrocarbon phase elute is much lower than big fractional sample product reactor elute.Therefore, the big fractional hydrocarbon in the reactor effluent can separate with ionic liquid.In embodiment 1a, only used a separator, said hydrocarbon phase elute only comprises 79 volume % of the hydrocarbon that is present at first in the reactor effluent.Yet in embodiment 1b, the hydrocarbon of 86 volume % in the reactor effluent is recovered in the hydrocarbon elute, and it comprises less ionic liquid.
In addition, than embodiment 1a, said ionic liquid phase elute comprises less hydrocarbon, in addition with another elute bonded situation in also be like this.
In the situation that the hydrocarbon phase elute is further handled in other sedimentation unit, the size of the volume of sedimentation unit is merely 42.5% of the sedimentation unit that is used to separate the total reactor elute.
Embodiment 2
This embodiment has shown the benefit of using at least one centrifugal separation unit (in this situation, being cyclonic separator) 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 elute in cyclonic separator is 1.5 minutes.Use traditional sedimentation unit in order to obtain same separating resulting, the residence time that needs usually is at least 15 minutes.Therefore, in order to keep 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 stated, this causes the total inventory (inventory) of liquid light hydrocarbon very big, and this is disadvantageous.
Claims (11)
1. method for preparing alkylate oil, said method is included in the hydrocarbon mixture that comprises isoparaffin and alkene is at least contacted with acidic ionic liquid catalysts, thereby obtains alkylate oil, and said method also comprises:
-collect the reactor effluent that comprises alkylate oil from said reactor drum, wherein said reactor effluent comprises ionic liquid phase and hydrocarbon phase;
-at least a portion with said reactor effluent in first separating unit is separated into ionic liquid phase elute and heterogeneous elute;
-in second separating unit, at least a portion of said heterogeneous elute is separated into hydrocarbon phase elute and another elute; With
-at least a portion of said ionic liquid phase elute is recycled to said reactor drum.
2. the method for claim 1, wherein said first separating unit and/or second separating unit are settling vessel separating unit or centrifugal separation unit, preferred centrifugal separation unit.
3. like each described method in the aforementioned claim, wherein, said centrifugal separation unit is the cyclonic separator separating unit.
4. each described method as in the aforementioned claim, wherein, said ionic liquid phase elute comprise ionic liquid mutually with based on said ionic liquid 0 to the 20 volume %, the hydrocarbon phase of preferred 0 to 10 volume % of total liquid weight of elute mutually.
5. each described method as in the aforementioned claim, wherein, said hydrocarbon phase elute comprise hydrocarbon phase with based on the ionic liquid of 0 to 3 volume % of total liquid weight of said hydrocarbon phase elute mutually, the ionic liquid phase of preferred 0 to 0.5 volume %.
6. like each described method in the aforementioned claim, wherein, said method also comprises:
-with said hydrocarbon phase elute at least fractionation be the stream that comprises the stream of alkylate oil and comprise isoparaffin.
7. like each described method in the aforementioned claim, wherein, said ionic liquid phase elute comprises solid, and said method also comprises:
-said ionic liquid phase elute is provided to the 3rd separating unit that is fit to separate solid and liquid; With
-said solid at least a portion of removal from said ionic liquid phase elute.
8. like each described method in the aforementioned claim, wherein, said isoparaffin is Trimethylmethane and/or iso-pentane.
9. like each described method in the aforementioned claim, wherein, said hydrocarbon mixture comprises the alkene with 3 to 6 carbon atoms, preferred 4 or 5 carbon atoms.
10. like each described method in the aforementioned claim; Wherein, Said acidic ionic liquid catalysts is the compound ion liquid of being made up of positively charged ion, negatively charged ion; Said positively charged ion the derive amine of self-contained alkyl or the hydrohalogen of pyridine; Said negatively charged ion is the heterogeneous coordination anion derived from two kinds or more kinds of metal halides, and wherein at least a metal halide is the halogenide of aluminium, and any other metal halide is the halogenide that is selected from the metal of the group of being made up of the transition element of the IIB family element of the IB family element of the periodic table of elements, the periodic table of elements and the periodic table of elements.
11. method as claimed in claim 10, wherein said catalyst pack contain the muriate of aluminum chloride and copper (I) or the muriate of copper (II).
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