CN102574752A - Process for preparing an alkylate - Google Patents
Process for preparing an alkylate Download PDFInfo
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- CN102574752A CN102574752A CN2010800346955A CN201080034695A CN102574752A CN 102574752 A CN102574752 A CN 102574752A CN 2010800346955 A CN2010800346955 A CN 2010800346955A CN 201080034695 A CN201080034695 A CN 201080034695A CN 102574752 A CN102574752 A CN 102574752A
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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 a hydrocarbon phase effluent and a multiple-phase effluent in a centrifugal separation unit; and fractionating at least part of said hydrocarbon phase effluent into at least a stream comprising alkylate and a stream comprising isoparaffin.
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 process 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 centrifugal separation unit.
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 centrifugal separation unit is separated into hydrocarbon phase elute and heterogeneous elute;
-with at least a portion of said hydrocarbon phase elute at least fractionation be the stream that comprises the stream of alkylate oil and comprise isoparaffin.
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, do not make catalyst deactivation wittingly or otherwise be damaged, thereby reduce catalyst consumption of the present invention.
Description of drawings
Fig. 1 provides the synoptic diagram of method of the present invention.
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 (I).
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 centrifugal separation unit to separate this reactor effluent.Said centrifugal separation unit can be any centrifugal separation unit that is suitable for separating at least two kinds of immiscible liquid phases.Preferably, said centrifugal separation unit is a cyclonic separation type separating unit, because such cyclonic separation type 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 settling vessel 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.The centrifugal separation unit of here mentioning is to separate the separating unit of two liquid phases based on cf-.The separating unit of here mentioning is to comprise a separator (for example, cyclonic separator) or the separating unit of two above separators (for example, two cyclonic separators) of being arranged in parallel.
Should be appreciated that typical plant-scale centrifugal separation 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 hydrocarbon phase elute and the heterogeneous elute that comprises acidic ion liquid and hydrocarbon.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.
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 in spinning field.
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 isoparaffin or alkene at high proportion.From at least a portion of the hydrocarbon phase elute of separator without chemical treatment in the middle of any at least fractionation be to comprise the hydrocarbon stream of alkylate oil and the stream that comprises isoparaffin.In case of necessity, can make said hydrocarbon phase elute in other centrifugal separation unit (like cyclonic separator), perhaps in the settling vessel unit, carry out other physical separation processes, thereby further reduce the ionic liquid mark in the hydrocarbon elute.Although sedimentation unit has relatively large volume than for example cyclonic separator; Even but the settling vessel unit is as second separating unit; The present invention still can provide favourable part, because this second sedimentation unit is still much little than being used for the sedimentation unit of traditional method of separate reactor elute.Preferably, said method before also being included in fractionation hydrocarbon phase elute provides to other settling vessel unit said hydrocarbon phase elute 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 chemical treatment of indication here is the processing that a kind of or more compounds in the pure basically hydrocarbon elute is decomposed.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.Through the pure basically hydrocarbon elute of fractionation, as comprise the stream of n-paraffin, can also obtain other hydrocarbon stream.
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.
In the method for the invention, at least a portion of the heterogeneous elute that obtains from centrifugal separation unit is preferably got back in the reactor drum through recycling.Said heterogeneous elute comprises the acidic ionic liquid catalysts of the overwhelming majority (even not being whole basically words), and this is the part of reactor effluent.Yet as stated, said heterogeneous elute also comprises the hydrocarbon of suitable volume.Although can these hydrocarbon be got back in the reactor drum together with one recycling of acidic ion liquid, but preferred this heterogeneous elute that further separates is to reduce recirculation volume.
Preferably, method of the present invention also comprises said heterogeneous elute is offered second separating unit.This separating unit can be any separating unit that is suitable for separating two immiscible liquid phases.The instance of suitable separating unit comprises settling vessel separating unit and centrifugal separation unit.Preferably, said separator 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.Preferably, said cyclonic separator is a Dutch cyclone.In second separating unit, this heterogeneous elute is separated into ionic liquid phase elute and another elute that comprises hydrocarbon and acidic ion liquid.
The ionic liquid phase elute of here mentioning comprise ionic liquid mutually with based on said ionic liquid mutually total liquid weight of elute be the hydrocarbon phase of 0 volume %～20 volume %, preferred 0 volume %～10 volume %.Preferably, to comprise the total liquid weight based on 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.
At least a portion of ionic liquid phase elute preferably is recycled in the reactor drum.
Can be recycled in first separating unit or combine available from another elute of second separating unit with the reactor effluent that offers first separating unit.Through another elute of recycling, can not lose catalyzer or hydrocarbon.
Observe, in the process of alkylated reaction, formed solid.The solid of here mentioning is undissolved solid particulate.Said solid mainly is made up of the metal, metallic compound and/or the metal-salt that are included at first in the acidic liquid catalysts.Preferably; Said solid comprises based on the metal of total weight of solids at least 10 weight %; That is, with the form of metal, covalently bound form or ionic form, wherein said metal is to be incorporated into the metal in the said method as the part of acidic ionic liquid catalysts.Said solid can also comprise as the pollutent in hydrocarbon mixture or the acidic ion liquid and is incorporated into the composition in the reaction mixture.Select as another kind, said solid can relate to the product of the chemical reaction of any above-claimed cpd.
Said solid can have virtually any size, but has been found that the mean sizes that solid has is generally 0.1 μ m～10 μ m.Particularly, based on total number of solid particulate, at least 50% solid has the particle diameter less than 5 μ m, is more especially 80% solid and has the particle diameter 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, promptly; Accumulate in the elute that is rich in acidic ionic liquid catalysts to a great extent, in promptly heterogeneous elute and/or the ionic liquid phase elute.This is because solid has higher density.When heterogeneous elute and/or ionic liquid phase elute when part is recycled to reactor drum at least, buildup of solids causes solids content very high in reaction mixture in reaction mixture, and this is disadvantageous.Since due to the solid deposition, the highly filled pipeline and the obstruction of leaving the pipeline of separating unit that for example can cause path or the valve in the reactor drum and lead to separating unit in the reaction mixture.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; Heterogeneous elute and/or ionic liquid phase elute are offered the 3rd separating unit that is suitable for separate solid and liquid and remove solid the elute mutually from heterogeneous elute and/or ionic liquid, thereby from heterogeneous elute and/or ionic liquid phase elute, remove solid.In the present invention, by removing part solid at least in heterogeneous elute and/or the ionic liquid phase elute.Preferably, remove solid, reach reaction mixture and comprise based on the ionic liquid phase gross weight in the reactor drum and be the solid of 5 weight % at the most, the preferred solid degree of 2 weight % at the most by heterogeneous elute and/or ionic liquid phase elute.Through from ionic liquid phase elute but not remove solid the heterogeneous elute, the liquid volume through the 3rd separating unit reduces, thereby allows to use littler 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 process.These processes 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 from reduce realizing that the time that solid and separating of liquid are required and the angle of energy input are useful.
Can be with solid in any form by removing in the process, solid is removed with the form of slurry of solids usually.Such slurry only comprises for example some residual acidic ion liquids except comprising solid.
Although when forming solid, lost the part catalyzer according to thinking, but the alkylation performance of catalyzer does not receive obvious influence.The loss that forms the catalyzer cause owing to solid only means the sub-fraction inactivation or the loss of total catalyst levels, and remaining catalyzer is uninfluenced.
Optional is that the catalyzer in heterogeneous elute and/or the ionic liquid phase elute can be with acid, preferred hydrogen halide, more preferably hydrogenchloride contacts so that said catalyst regeneration.Preferably; Heterogeneous elute through making at least part and/or ionic liquid phase elute are recycled to reactor drum makes acidic ionic liquid catalysts regeneration, and through at least a portion of the elute that is recycled, adding at least a portion regeneration that hydrogenchloride makes the acidic ionic liquid catalysts in the elute that is recycled.
More preferably, hydrogenchloride is added at least a portion of ionic liquid phase elute.Through after the hydrocarbon of removing the overwhelming majority, catalyzer is contacted with hydrogenchloride, reduced the disadvantageous chlorination of hydrocarbon.Hydrogenchloride and acidic ionic liquid catalysts reaction.Add hydrogenchloride and no longer be consumed until hydrogenchloride, 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.
Preferably, the gaseous hydrogen chloride of interpolation and the elute of institute recycling mix to guarantee good contact the between gas and the liquid phase.
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 among this paper the above, although can be received in 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.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, the extra means of such process need are with the follow-up storage and the processing of the nitrogen that is used to provide nitrogen and polluted by hydrogenchloride.In addition, lost a part that is provided for regenerated hydrogenchloride.Preferably; (for example make the acid ionic-liquid catalyst of other exhausted; Form with the stream that comprises used catalyst) sneaks in the elute of the recycling that comprises the regenerated acidic ionic liquid catalysts (promptly; Comprise in the elute of institute's recycling of the hydrogenchloride that is added), gather 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 elute that also can make a part of ionic liquid phase elute, heterogeneous elute or other the recycling that comprises catalyzer is without the by-pass of mixed regeneration subsequently of regenerating also.For example, the ionic-liquid catalyst in can regeneration of ionic liquid phase elute makes this elute mix with another elute available from second separator then, and this another elute still comprises exhausted (that is, not regenerated) ionic-liquid catalyst.
The solid of removing in the process 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, the hydrocarbon mixture that comprises isoparaffin and alkene is contacted with catalyzer, thereby make isoparaffin and olefine reaction to form alkylate oil.
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 process.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 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 all must be higher than ion liquid fusing point in any situation.
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 successive processes.
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 the reactor effluent that solid comprises alkylate oil.The part of this elute can directly be recycled in the said reactor drum via recirculation line 117, perhaps combines with pipeline 105.At least a portion of elute is supplied to first centrifugal separation unit 120, for example, cyclonic separator.In first centrifugal separation unit 120, reactor effluent separates into hydrocarbon phase elute and heterogeneous elute under the influence of cf-.The part of hydrocarbon phase elute can be directly recycled to reactor drum via recirculation line 117 and 119, perhaps combines with pipeline 105.At least a portion of hydrocarbon phase elute offers fractionator 125 through pipeline 130.The product that comprises alkylate oil is reclaimed by the bottom of fractionator 125 through pipeline 135.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 140 recycling, thereby becomes the part of the Trimethylmethane feed in the pipeline 105.Other the stream (not shown) that comprises hydrocarbon also can be reclaimed by fractionator 125.
Heterogeneous elute offers second separating unit 144 via pipeline 145, for example, and cyclonic separator.In second separating unit 144, heterogeneous elute separates into ionic liquid phase elute and another elute.This another elute can be collected by second separating unit 140 via pipeline 149, combines with pipeline 115, and then is circulated to first separating unit.Ionic liquid phase elute can be recycled to reactor drum via pipeline 147.Can part or all of ionic liquid phase elute be transferred to the 3rd separating unit 155 through pipeline 150 from pipeline 147, for example, 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 is offered ionic liquid phase elute by gas container 175 through pipeline 170.Optional is, the mixing device (not shown), and for example Venturi absorber is used for making hydrogen chloride gas to sneak into pipeline 165.Part through making catalyzer is avoided the regeneration carried out with hydrogenchloride through pipeline 147, when pipeline 165 and 147 arrives together any remaining gaseous hydrogen chloride can with the ionic-liquid catalyst reaction in the pipeline 147.The bypass (not shown) can also be set near the point of crossing of pipeline 165 and 170.Like this, can also be by without removing solid in the regenerated ionic-liquid catalyst.
Said ionic liquid phase elute directly returns reaction zone 100 subsequently.In case of necessity, can the acid ionic-liquid catalyst of the exhausted of other fresh acidic ionic liquid catalysts or outside supply be offered reaction zone 100 via pipeline 180.
Embodiment
Through following non-limiting example the present invention is described.
Embodiment 1
Non-traditional settling vessel comes the effect of separate reactor elute in order to show the use cyclonic separator; Use cyclonic separator sample separation reactor effluent, said sample product reactor elute comprises hydrocarbon reaction thing and mixture of products and ionic-liquid catalyst.
It is 1: 1.05 hydrocarbon and ionic-liquid catalyst that said sample product reactor elute comprises volume ratio.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.
40 volume % of sample product reactor elute are recovered as the hydrocarbon phase elute.The sample product reactor elute of remaining 60 volume % is recovered 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 %.
Said 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, be provided at first that about 79 volume % of hydrocarbon are recycled in the hydrocarbon elute in the sample product reactor elute.
In the situation that the hydrocarbon phase elute is further handled in other sedimentation unit, the size of the volume of this sedimentation unit is merely 40% of the sedimentation unit that is used to separate the total reactor elute.
Claims (12)
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 centrifugal separation unit is separated into hydrocarbon phase elute and heterogeneous elute;
-with at least a portion of said hydrocarbon phase elute at least fractionation be the stream that comprises the stream of alkylate oil and comprise isoparaffin.
2. the method for claim 1, said method also comprises
-said heterogeneous elute is offered second separating unit;
-said heterogeneous elute is separated into ionic liquid phase elute and another elute,
Wherein, at least a portion with said ionic liquid phase elute is recycled to said reactor drum.
3. method as claimed in claim 2, wherein, said second separating unit is settling vessel separating unit or centrifugal separation unit, preferably centrifugal separation unit.
4. like each described method in the aforementioned claim, wherein, said centrifugal separation unit is the cyclonic separator separating unit.
5. each described method as in the aforementioned claim, wherein, said hydrocarbon phase elute comprise hydrocarbon phase and total liquid weight based on said hydrocarbon phase elute be 0 to 3 volume % ionic liquid mutually, the ionic liquid phase of preferred 0 to 0.5 volume %.
6. like each described method in the claim 2～5, wherein, said ionic liquid phase elute comprise ionic liquid mutually with based on said ionic liquid mutually total liquid weight of elute be the hydrocarbon phase of 0 to 20 volume %, preferred 0 to 10 volume %.
7. like each described method in the aforementioned claim, wherein, said heterogeneous elute and/or ionic liquid phase elute comprise solid, and said method also comprises:
-said heterogeneous elute and/or ionic liquid phase elute are offered the 3rd separating unit that is suitable for separate solid and liquid; With
-by removing said solid at least a portion in said heterogeneous elute and/or the ionic liquid phase elute.
8. like each described method in the aforementioned claim, wherein, said method also comprises:
Thereby-before the said hydrocarbon phase elute of fractionation, said hydrocarbon phase elute is offered another settling vessel unit to remove extra ionic liquid.
9. like each described method in the aforementioned claim, wherein, said isoparaffin is Trimethylmethane and/or iso-pentane.
10. 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.
11. as 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 polymorphic 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.
12. method as claimed in claim 10, wherein, said catalyst pack contains the muriate of aluminum chloride and copper (I) or the muriate of copper (II).
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|---|---|---|---|
| CN2010800346955A CN102574752A (en) | 2009-08-06 | 2010-08-06 | Process for preparing an alkylate |
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| CN2009000887 | 2009-08-06 | ||
| CNPCT/CN2009/000887 | 2009-08-06 | ||
| CN2010800346955A CN102574752A (en) | 2009-08-06 | 2010-08-06 | Process for preparing an alkylate |
| PCT/EP2010/061488 WO2011015654A2 (en) | 2009-08-06 | 2010-08-06 | Process for preparing an alkylate |
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| CN2010800346955A Pending CN102574752A (en) | 2009-08-06 | 2010-08-06 | Process for preparing an alkylate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554808A (en) * | 2015-09-30 | 2017-04-05 | 中国石油大学(北京) | A kind of method and system for separating alkylation reaction product intermediate ion liquid |
| CN108211404A (en) * | 2016-12-21 | 2018-06-29 | 中国石油化工股份有限公司 | Alkylated reaction device and alkylated reaction separation method |
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| US20040133056A1 (en) * | 2002-11-12 | 2004-07-08 | Zhichang Liu | Method for manufacturing alkylate oil with composite ionic liquid used as catalyst |
| 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 |
| CN1997610A (en) * | 2004-02-09 | 2007-07-11 | 阿尔伯麦尔荷兰公司 | Alkylation process using a catalyst comprising a solid acid and a hydrogenation |
| 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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| CN1080214A (en) * | 1992-05-01 | 1994-01-05 | 菲利浦石油公司 | The alkylation of isoparaffin and alkene |
| US20040133056A1 (en) * | 2002-11-12 | 2004-07-08 | Zhichang Liu | Method for manufacturing alkylate oil with composite ionic liquid used as catalyst |
| CN1997610A (en) * | 2004-02-09 | 2007-07-11 | 阿尔伯麦尔荷兰公司 | Alkylation process using a catalyst comprising a solid acid and a hydrogenation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106554808A (en) * | 2015-09-30 | 2017-04-05 | 中国石油大学(北京) | A kind of method and system for separating alkylation reaction product intermediate ion liquid |
| CN106554808B (en) * | 2015-09-30 | 2019-01-15 | 中国石油大学(北京) | A kind of method and system separating alkylation reaction product intermediate ion liquid |
| CN108211404A (en) * | 2016-12-21 | 2018-06-29 | 中国石油化工股份有限公司 | Alkylated reaction device and alkylated reaction separation method |
| CN108211404B (en) * | 2016-12-21 | 2023-09-05 | 中国石油化工股份有限公司 | Alkylation reaction device and alkylation reaction separation method |
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Application publication date: 20120711 |