CN102666444B - Process for preparing an alkylate - Google Patents

Process for preparing an alkylate Download PDF

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Publication number
CN102666444B
CN102666444B CN201080034740.7A CN201080034740A CN102666444B CN 102666444 B CN102666444 B CN 102666444B CN 201080034740 A CN201080034740 A CN 201080034740A CN 102666444 B CN102666444 B CN 102666444B
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solid
effluent
reaction zone
ionic liquid
hydrocarbon
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CN201080034740.7A
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Chinese (zh)
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CN102666444A (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/CN2009/000884 priority
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Priority to PCT/EP2010/061447 priority patent/WO2011015639A2/en
Priority to CN201080034740.7A priority patent/CN102666444B/en
Publication of CN102666444A publication Critical patent/CN102666444A/en
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Abstract

The present invention provides process for preparing an alkylate comprising contacting in a reaction zone a hydrocarbon mixture comprising at least an isoparaffin and an olefin with an acidic ionic liquid catalyst under alkylation conditions to obtain an alkylate-comprising effluent, in which process: - solids are formed in the reaction zone; - a solids-comprising effluent comprising hydrocarbons and acidic ionic liquid is withdrawn from the reaction zone; and - at least part of the solids-comprising effluent is treated to remove at least part of the solids to obtain a solids-depleted effluent. The invention further provides a process for treating an acidic ionic liquid comprising at least 0.1wt% of solids based on the total weight of the acidic ionic liquid, wherein at least part of the solids are removed.

Description

Prepare the method for alkylate oil

Technical field

The invention provides the method preparing alkylate oil, and for the treatment of the method for acidic ion liquid.

Background technology

Increasing to the demand of alkylate oil fuel mix raw material.As fuel mix composition, alkylate oil combines low-steam pressure, without sulphur, without alkene or aromatic hydrocarbon and high-octane characteristic.

Nearly all alkylate oil is all by making isobutane and butene react obtained under the existence of suitable an acidic catalyst.Catalyzer the most conventional is HF and sulfuric acid, but also reports other catalyzer, as solid acid catalyst.Recently, the isoparaffin of acidic ionic liquid catalysts and the alkylation of alkene is used to cause concern as the replacement scheme of the alkylation of HF and sulfuric acid catalysis.

Such as in US7285698, disclose the method for the manufacture of alkylate oil, it uses compound ion liquid catalyst that isobutane and butene is reacted.In the method for US7285698, Trimethylmethane and butylene are supplied to reactor, and under alkylating condition, make reactant contact with compound ion liquid form alkylate oil.Separate reactor effluent, is recycled to reactor mutually by ionic liquid, processes hydrocarbon phase to reclaim described alkylate oil simultaneously.Use ionic-liquid catalyst can prepare good alkylate oil fuel mix composition although the method for US7285698 demonstrates, in this area, still need the method for the ionic liquid allcylation improved.

Summary of the invention

Have been found that ionic liquid allcylation method carry out may form solid in process.Along with the carrying out of reaction, these solids, in reaction zone inner accumulated, likely cause the blocking of path and/or valve.Method of the present invention is used to address this problem.

Therefore, the invention provides a kind of method preparing alkylate oil, described method comprises the hydrocarbon mixture making at least to comprise isoparaffin and alkene under alkylating conditions in the reaction region and contacts with acidic ionic liquid catalysts thus obtain the effluent comprising alkylate oil, in the process:

-in described reaction zone, form solid;

-collect the effluent comprising solid containing hydrocarbon and acidic ion liquid by described reaction zone; With

-to described comprise the effluent of solid process at least partially remove described solid at least partially, thus obtain solid reduce effluent.

The solid formed in alkylation process by removing at least partially, can prevent gathering of the solid in reaction zone.

In another aspect, the invention provides a kind of method for the treatment of acidic ion liquid, the described acidic ion liquid gross weight comprised based on this acidic ion liquid is the solid of at least 0.1 % by weight, in the process, and removing by acidic ion liquid at least partially of described solid.

Accompanying drawing explanation

Fig. 1 provides the schematic diagram of method of the present invention.

Embodiment

In the method for the invention, by making isoparaffin and olefine reaction prepare alkylate oil.The alkylate oil obtained is particularly suitable for the object of gasoline mixing or produces for aviation spirit.In the method for the invention, isoparaffin and alkene are supplied to reaction zone.The hydrocarbon mixture making to comprise isoparaffin and alkene in described reaction zone be suitable for alkylating catalyst exposure.Described hydrocarbon mixture comprises the alkene usually provided by outside, that is, fresh alkene, and comprises isoparaffin.Described isoparaffin can be the isoparaffin provided by outside, that is, fresh alkene, and/or the isoparaffin of any other part recirculation by the method.Fresh isoparaffin and alkene separately can be supplied to the method, but normally fresh isoparaffin and fresh alkene be supplied to described reaction zone as the mixture comprising isoparaffin and alkene.In the present invention, described catalyzer is acidic ion liquid or the compounding mixture comprising this ionic liquid (hereinafter also referred to catalyzer).

The ability of known ion liquid catalyst alkylated reaction in this area.It is the cationic compound ion liquid of the hydrogen halide comprised derived from the amine containing alkyl, imidazole salts or pyridine for catalyzer of the present invention.Preferably, described positively charged ion comprises by the saturated nitrogen-atoms of four substituting groups, has a hydrogen atom and an alkyl in described substituting group at least.It is further preferred that described alkyl substituent is at least one group be 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 preferably the halogenide based on the Lewis acid, particularly aluminium of aluminium, preferred aluminum chloride (III).Because the acidity of chloride Lewis acid is very high, therefore the preferred halogenide by aluminum chloride or other aluminium is combined to form coordination anion with metal halide, vitriol or the nitrate of another kind or more, particularly derived from the coordination anion of two or more metal halides, wherein at least one metal halide is the halogenide of aluminium.Suitable other metal halide, vitriol or nitrate can be selected from the halogenide of following metal, vitriol or nitrate, and described metal is selected from the group be made up of the IB race element of the periodic table of elements, the IIB race element of the periodic table of elements and the transition element of the 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, such as, muriate, the muriate of copper (II), the muriate of nickel (II), the muriate of iron (II) of copper (I).Preferably, the scope of the mol ratio of the compound of aluminium and other metallic compounds is 1: 100 ~ 100: 1, is more preferably 1: 1 ~ 100: 1, or and then is more preferably 2: 1 ~ 30: 1.By using the coordination anion comprising aluminium and another kind of metal, the alkylate oil product that can be improved.Method for the preparation of this catalyzer is such as described in US7285698.Particularly preferred catalyzer is the acidic ionic liquid catalysts comprised derived from aluminum chloride (III) and the muriate of copper (II) or the muriatic coordination anion of aluminum chloride (III) and copper (I).

As mentioned above, in reaction zone, comprise hydrocarbon mixture and the catalyst exposure of isoparaffin and alkene.Described hydrocarbon mixture in the reaction region with described catalyst mix with forming reactions 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 by having come for any suitable means (comprising dynamic mixer and static mixer) mixing two or more liquid with mixing of catalyzer.When with catalyst exposure, isoparaffin and alkene react under alkylating conditions, thus form alkylate oil.The alkylate oil formed is obtained by reaction zone with the form of the effluent comprising alkylate oil.The effluent comprising alkylate oil still comprises the unreacted isoparaffin of suitable volume.Therefore, a part for the effluent comprising alkylate oil can be recycled to reaction zone to maintain the higher isoparaffin/alkene ratio in the hydrocarbon mixture in reaction zone.In reaction zone comprise the effluent of alkylate oil in separator unit, be separated into the phase being rich in hydrocarbon and the phase being rich in acidic ionic liquid catalysts at least partially.Mention herein be rich in hydrocarbon refer to that the total mole number based on hydrocarbon and acidic ionic liquid catalysts comprises the phase of the hydrocarbon more than 50 % by mole mutually.Mention herein be rich in acidic ionic liquid catalysts refer to that the total mole number based on hydrocarbon and acidic ionic liquid catalysts comprises the phase of the acidic ionic liquid catalysts more than 50 % by mole mutually.Due to the density difference that the avidity of acidic ionic liquid catalysts to hydrocarbon is lower and exist between hydrocarbon and acidic ionic liquid catalysts, described separation is applicable to example settling vessel instrument as everyone knows and carries out, wherein hydrocarbon and catalyst separating are the phase being mainly hydrocarbon on top and the phase being mainly catalyzer of bottom, also can use any other suitable liquid/liquid/gas separator.This liquid/liquid/gas separator is that those skilled in the art is known, comprises cyclonic separator and centrifuge separator.Catalyzer is recycled in reactor mutually usually.Because hydrocarbon phase still comprises the unreacted isoparaffin of suitable volume, therefore a part for hydrocarbon phase can be recycled to reactor to maintain the higher isoparaffin/alkene ratio in reaction zone.But, to hydrocarbon phase process at least partially and/or fractionation comprises the product of alkylate oil to reclaim.

Observe and in reaction zone, defined solid in the process of alkylated reaction.The solid herein mentioned is undissolved solid particulate.Described solid is formed primarily of the metal be included at first in acidic liquid catalysts, metallic compound and/or metal-salt.Preferably, described solid comprise based on total weight of solids be at least 10 % by weight metal, that is, in a metallic form, the form of covalently bound form or ion, wherein said metal is a part as acidic ionic liquid catalysts and the metal be incorporated in described method.Described solid can also comprise the composition be incorporated in reaction mixture as the pollutent in hydrocarbon mixture or acidic ion liquid.Alternatively, described solid can relate to the product of the chemical reaction of any above-claimed cpd.

Described solid can have any size, but has been found that the mean sizes that solid has is generally 0.1 μm ~ 10 μm.Particularly, based on total number of solid particulate, the solid of at least 50% has the particle diameter being less than 5 μm, and more especially the solid of 80% has the particle diameter being less than 5 μm.

Although mixing process in these solid dispersal in whole reaction mixture, but be separated comprise the effluent of alkylate oil time have been found that solid, that is, accumulate in a great extent be rich in acidic ionic liquid catalysts mutually in.This is because solid has higher density.The phase being rich in catalyzer is recycled to the part that reaction zone becomes the reaction mixture in reaction zone subsequently.As a result, in the reaction region, cause solids content very high in the reaction region, this is disadvantageous to buildup of solids.Due to solid precipitation caused by, highly filled in reaction zone such as can cause the path in reaction zone or valve and lead to the pipeline of separating unit and leave the blocking of pipeline of separating unit.In addition, when being in highly filled, solid can be coalescent and form large aggregation, causes the danger blocked to increase.

In the present invention, being removed by reaction zone at least partially of solid.Preferably, solid is removed by reaction zone, reach solid that reaction mixture (that is, comprising the mixture of hydrocarbon reaction thing, acidic ion liquid and product) comprises be the gross weight of acidic ion liquid in reactor at the most 5 % by weight, preferably at the most 2 % by weight degree.Do not need to remove all solids from reaction zone, preferably, remove solid by reaction zone, reach the degree that solid that reaction zone comprises based on the gross weight of the acidic ion liquid in reaction zone is 0.05 % by weight ~ 5 % by weight, more preferably 0.1 % by weight ~ 2 % by weight.

Described solid can any time in the method or position be removed by reaction zone.Directly in reaction zone, solid can be removed from reaction mixture.But, preferably, being collected as the effluent comprising solid by reaction zone at least partially using reaction mixture.This effluent comprising solid is except comprising solid, and also comprise hydrocarbon and acidic ion liquid, wherein said hydrocarbon generally includes isoparaffin and alkylate oil.Subsequently, to the processing at least partially, to remove solid at least partially of effluent comprising solid.The effluent that solid reduces is obtained after the process of removing solid.

Preferably, by solid reduce effluent be recycled to reactor at least partially.

Can be treated to remove solid by reacting the effluent comprising solid collected.But preferably, first the effluent comprising solid is separated into the phase being rich in catalyzer and the phase being rich in hydrocarbon, then to be rich in catalyzer process mutually remove solid.As described hereinabove, what buildup of solids was formed in typical separator unit be rich in catalyzer mutually in.

Preferably, the effluent comprising solid be comprise alkylate oil effluent or be at least the part of the effluent comprising alkylate oil, it is admitted to separating unit.In this case, the effluent comprising alkylate oil can be treated to remove solid before separating unit.But, due to buildup of solids be rich in catalyzer mutually in, preferably first the effluent comprising alkylate oil is separated into the first part that comprises the phase being rich in catalyzer and comprises the second section of the phase being rich in hydrocarbon, then by be rich in catalyzer mutually in removing solid.Subsequently, preferably the catalyzer that solid reduces can be introduced into reaction zone again.

Described solid can, by for being removed by any suitable means removing solid in liquid, include but not limited to filter, precipitate and centrifugal method.These methods are well-known in the art.

Due to the special property that ionic liquid has, be preferably the removal carrying out solid at the temperature of liquid in acidic ionic liquid catalysts.Particularly, preferably at 5 DEG C ~ 80 DEG C, be more preferably the temperature removing solid of 20 DEG C ~ 60 DEG C, guarantee that temperature is the temperature making ionic liquid remain liquid simultaneously.By removing solid at a higher temperature, falling, the low-density viscosity of ionic liquid that simultaneously makes is lower, and this realizes solid with the angle being separated required time and energy input of liquid from minimizing is useful.

Solid can be removed by process in any form, solid removes with the form of slurry of solids usually.Such slurry, except comprising solid, only comprises more residual acidic ion liquid.Described slurry can also process to extract residual acidic ion liquid further.Preferably by using the liquid-liquid extraction of carrying out with suitable solvent to complete this extraction.Owing in fact there is not ionic liquid vapour pressure, therefore such as can easily recycling design by evaporation and condensation subsequently.Recovered solvent can recycle.

Have lost partially catalyzed agent although it is believed that when forming solid, but the alkylation performance of catalyzer is not subject to obvious impact.The loss of the catalyzer caused due to the formation of solid only means sub-fraction inactivation or the loss of total catalyst levels, and remaining catalyzer is uninfluenced.

Optionally, catalyzer can contact to make described catalyst regeneration with acid, preferred hydrogen halide, more preferably hydrogenchloride.This can come in this process by hydrogenchloride being introduced (that is, adding).Preferably, the regeneration at least partially comprising the acidic ionic liquid catalysts in the effluent of solid is made.Preferably, reaction zone is recycled at least partially by the acidic ionic liquid catalysts of regeneration.Preferably, first the effluent that acidic ionic liquid catalysts reduces from the effluent and/or solid that comprise solid is separated, then regenerates.

The phase being rich in acidic ionic liquid catalysts that the effluent reduced with the effluent and/or solid that comprise solid is separated still can comprise some hydrocarbon dissolved.These hydrocarbon can be removed, but this and unnecessary.Contacting with hydrogenchloride with making catalyzer after hydrocarbon phase separation, decrease the disadvantageous chlorination of hydrocarbon.Hydrogenchloride and acidic ionic liquid catalysts are reacted.Add hydrogenchloride until hydrogenchloride is no longer consumed, that is, until reach capacity.The consumption of hydrogenchloride is followed the trail of by monitoring pressure.Preferably, complete the interpolation of hydrogenchloride with the step of aturegularaintervals, measure the pressure between each interpolation step simultaneously.By adding hydrogenchloride in little step, the generation of unwelcome hydrogenchloride pneumatic jack when decreasing saturated.

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

As described hereinabove, although can accept the hydrogenchloride having some gaseous states in the reaction region, but the unreacted gaseous hydrogen chloride caused because acidic ion liquid is chlorinated hydrogen supersaturation gathers and remains unwelcome in reactive system.Residual gaseous hydrogen chloride can be removed from reactive system, such as, by carrying out purge with rare gas elementes such as nitrogen.But, the extra means of such process need are for providing nitrogen and being chlorinated the follow-up Storage and Processing of nitrogen of hydrogen contamination.In addition, have lost a part of hydrogenchloride being provided for regenerating.Preferably, make other spent acid ionic-liquid catalyst (such as, to comprise the form of the stream of used catalyst) to be mixed in the effluent of the recirculation of the acidic ionic liquid catalysts comprising regeneration (namely, comprise in the effluent of institute's recirculation of added hydrogenchloride), thus decrease this hydrogenchloride and gather.The spent acid ionic-liquid catalyst herein mentioned is the acidic ionic liquid catalysts being used as catalyzer but still not being chlorinated hydrogen regeneration in chemical reaction.By making this spent acid ionic liquid react with the gaseous hydrogen chloride existed due to initial supersaturation, remaining hydrogenchloride can be consumed.Can be introduced by external source with the ionic-liquid catalyst crossed, but, the effluent of recirculation that also can make a part of ionic-liquid catalyst phase or comprise catalyzer without regeneration and subsequently mixed regeneration with the stream of bypass.

The solid removed in process can be dropped, but preferably recycles the composition in solid, such as, for the preparation of fresh acidic ionic liquid catalysts.

In the method for the invention, make the hydrocarbon mixture and the catalyst exposure that comprise isoparaffin and alkene under alkylating conditions, thus make isoparaffin and olefine reaction 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 comprises the alkene with 2 to 8 carbon atoms, more preferably 3 to 6 carbon atoms and then more preferably 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 more preferably 1: 1 ~ 20: 1 mol ratio be fed in process.When 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 depend on but are not limited to the accurate composition of hydrocarbon mixture and catalyzer.

Temperature in reactor is preferably-20 DEG C ~ 100 DEG C, is more preferably 0 DEG C ~ 50 DEG C.In any situation, temperature is all sufficiently high to guarantee that ionic-liquid catalyst is for liquid state.

In order to steam in inhibited reaction device is formed, described method is carried out under stress, and the pressure in preferred reactor is 0.1MPa ~ 1.6MPa.

Preferably, the acidic ionic liquid catalysts in reaction zone and the ratio of hydrocarbon are at least 0.5, are preferably 0.9, are more preferably at least 1.Preferably, the acidic ionic liquid catalysts in reaction zone and the ratio of hydrocarbon are 1 ~ 10.

Hydrocarbon mixture can in any suitable alkylation reactor with catalyst exposure.Described hydrocarbon mixture can in semicontinuous or successive processes with catalyst exposure.

The effluent comprising alkylate oil is separated for after the phase that is rich in hydrocarbon and the phase being rich in catalyzer, the obtained part being rich in the phase of hydrocarbon can be recycled to reaction zone, or by its with hydrocarbon mixture or fresh isoparaffin and/or alkene be combined, then deliver to reaction zone.The effluent being rich in hydrocarbon still comprises the isoparaffin of suitable volume.Going back to reaction zone by a part of recirculation of the phase by being rich in hydrocarbon, the high molar ratio of the isoparaffin/alkene of reaction zone can be maintained.

The effluent comprising alkylate oil is separated for after the phase that is rich in hydrocarbon and the phase being rich in catalyzer, can to obtained be rich in the phase of hydrocarbon process the phase being rich in hydrocarbon with fractionation at least partially, and the alkylate oil reclaimed in hydrocarbon phase and optional other compositions (as unreacted isoparaffin or normal paraffin).

Be rich in can being processed by any suitable mode (such as, distilling) to make hydrocarbon stream fractionation mutually of hydrocarbon.

After fractionation, the alkylate oil obtained or the product comprising alkylate oil can be used for preparing aviation spirit or the mixing element as gasoline.As mentioned above, the phase being rich in hydrocarbon also can comprise isoparaffin.Preferably, this isoparaffin is reused to be formed a part for the isoparaffin charging being supplied to described method at least in part.This by recirculation isoparaffin at least partially or fractionation be rich in the phase of hydrocarbon and the stream comprising isoparaffin obtained, and make it be combined with being supplied to the isoparaffin of described method.

On the other hand, the present invention also provides a kind of method for the treatment of acidic ion liquid, the described acidic ion liquid gross weight comprised based on this acidic ion liquid is the solid of at least 0.5 % by weight, preferably 0.1 % by weight, in described method, removing by acidic ion liquid at least partially of described solid.The acidic ion liquid comprising solid is preferably used as the catalyzer of chemical reaction, more preferably alkylated reaction and then the more preferably alkylated reaction of isoparaffin/alkene.Preferably, described acidic ion liquid is the ionic liquid of the preparation method for alkylate oil of the present invention as above herein.Preferably, solid is via with the method identical for the preparation method of alkylate oil of the present invention as above herein and remove at that same temperature.

The schematic diagram of the inventive method is given in Fig. 1.

In Fig. 1, the mixture comprising alkene and isoparaffin is supplied to reactor 100 by pipeline 105.Acidic ionic liquid catalysts is also supplied to reaction zone 100 by pipeline 110.In reaction zone 100, hydrocarbon mixture and catalyzer mix under alkylating conditions.By pipeline 115, collected the effluent comprising solid comprising hydrocarbon and acidic ion liquid by reaction zone.A part for this effluent can directly be recycled in described reactor, or is combined with pipeline 105 via recirculation line (not shown).Effluent is at least partially supplied to liquid/liquid separating unit 120, as settler unit.In liquid/liquid separating unit 120, the phase being rich in hydrocarbon be rich in being separated under the impact of gravity or centrifugal force of catalyzer.The phase that a part is rich in hydrocarbon can be directly recycled to reactor, or is combined with pipeline 105 via recirculation line (not shown).Fractionator 125 is supplied to by pipeline 130 at least partially by what be rich in the phase of hydrocarbon.The product comprising alkylate oil is reclaimed by the bottom of pipeline 135 by fractionator 125.The product comprising alkylate oil such as can be used for the object of fuel mix.In addition, the stream comprising isoparaffin is reclaimed by fractionator 125, then via pipeline 140 recirculation, thus becomes a part for the mixture in pipeline 105.Other the stream (not shown) comprising hydrocarbon also can be reclaimed by fractionator 125.

Acidic ionic liquid catalysts can be recycled to reactor 100 via pipeline 145 mutually.From pipeline 145, part or all of catalyzer can be transferred to whizzer 155 by pipeline 150.In whizzer 155, under the influence of the centrifugal force by acidic ionic liquid catalysts middle removing solid mutually, then reclaim solid via pipeline 160.Remaining acidic ionic liquid catalysts is discharged by whizzer 155 through pipeline 165.Optionally, hydrogen chloride gas is supplied to acidic ionic liquid catalysts phase by gas container 175 through pipeline 170.Optionally, mixing device (not shown), such as Venturi absorber, be mixed in pipeline 165 for making hydrogen chloride gas.Avoid the regeneration carried out with hydrogenchloride through pipeline 145 by making a part for catalyzer, when pipeline 165 is together with 145 arrive, any remaining gaseous hydrogen chloride can react with the ionic-liquid catalyst in pipeline 145.Bypass (not shown) can also be set near the point of crossing of pipeline 165 and 170.Like this, solid can also be removed by the ionic-liquid catalyst without regeneration.

Described acidic ionic liquid catalysts directly returns to reaction zone 100 mutually subsequently.If desired, via pipeline 180, the spent acid ionic-liquid catalyst of other fresh acidic ionic liquid catalysts or outside supply can be supplied to reaction zone 100.

Embodiment

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

Alkylation process

Three that remove with the solid of the analog rule operations separated perform alkylation process.Between each operation, by acidic ionic liquid catalysts and hydrocarbon phase separation, and process by removing solid and adding hydrogen chloride gas.The acidic ionic liquid catalysts processed is run for rear one subsequently.

Catalyzer used is the ionic-liquid catalyst (front China University Of Petroleum Beijing, Beijing) of the muriatic coordination anion comprised derived from aluminum chloride (III) and copper (I).

The hydrocarbon mixture of isobutane and butene is supplied to alkylation reactor together with acidic ionic liquid catalysts.The volume of reactor is 0.4 liter.

The effluent of alkylation reactor is separated in settling vessel, and a part of hydrocarbon phase delivers to fractionator, and remaining hydrocarbon phase is then recycled to reactor.Alkylate oil is obtained by the bottom of fractionator, and carries out detector determination engine research method octane value (motor RON) and motor-method octane number (MON).

The stream comprising Trimethylmethane is recycled in hydrocarbon mixture by fractionator.

Acidic ionic liquid catalysts available from settling vessel is recycled to reactor mutually.Periodically, that is, between operation, the acidic ionic liquid catalysts available from settling vessel is made mutually again to return disc centrifuge, and in the temperature of 50 DEG C with 20000rpm centrifugal 1 hour.The weight of the solid that record generates.After removing solid, with the temperature of 35 DEG C hydrogen chloride gas to be added in acidic ionic liquid catalysts process at the pressure of about 5bar, until no longer consumption hydrogenchloride.The consumption of record hydrogenchloride.Reaction conditions and the results are shown in table 1 of obtaining.Obviously, when solid not occurring and removing, the solid of about 1.5kg will gather in the reactor.By removing solid, solids content significantly reduces, and alkylate oil keeps very high quality.The difference of the gained alkylation oil properties observed is caused by the difference of alkylation temperature and isoparaffin/alkene ratio.

Table 1

* Trimethylmethane/butylene ratio, that is, fresh charging and by the Trimethylmethane in the mixture of the Trimethylmethane of fractionator recirculation/butylene ratio

* total solids: the gross weight of slurry of solids

Solid analysis

Analyze by the acidic ionic liquid catalysts middle solid removed mutually.Use laser particle size analyzer determination size-grade distribution.

Result display in table 2.

Table 2

Run 1 2 3 Diameter is less than the per-cent of the particle of 5 μm 99 99 99 Diameter is less than the per-cent of the particle of 3 μm 80 81 80

Claims (17)

1. prepare the method for alkylate oil for one kind, described method comprises the hydrocarbon mixture making at least to comprise isoparaffin and alkene under alkylating conditions in the reaction region and contacts with acidic ionic liquid catalysts thus obtain the effluent comprising alkylate oil, in the process:
-in described reaction zone, form solid;
-effluent comprising solid containing hydrocarbon and acidic ion liquid is collected from described reaction zone; With
-to described comprise the effluent of solid process at least partially remove described solid at least partially, thus obtain solid reduce effluent,
Wherein, the described effluent comprising solid is separated into the phase being rich in catalyzer and the phase being rich in hydrocarbon, and process described in be rich in catalyzer to remove solid, and remove solid by described reaction zone, reach solid that described reaction zone comprises be the gross weight of described acidic ionic liquid catalysts in described reaction zone at the most 5 % by weight degree.
2. the method for claim 1, wherein the effluent that reduces of described solid be recirculated to described reaction zone at least partially.
3. method as claimed in claim 1 or 2, wherein, described in comprise solid effluent be described in comprise the effluent of alkylate oil.
4. the method for claim 1, wherein remove solid by described reaction zone, reach solid that described reaction zone comprises be the gross weight of described acidic ionic liquid catalysts in described reaction zone at the most 2 % by weight degree.
5. the method for claim 1, wherein remove solid by described reaction zone, reach the degree that solid that described reaction zone comprises is 0.1 % by weight ~ 2 % by weight of the gross weight of described acidic ionic liquid catalysts in described reaction zone.
6. the method for claim 1, wherein described in comprise regenerating by adding hydrogenchloride at least partially of described acidic ionic liquid catalysts in the effluent of solid, and be recycled to described reaction zone.
7. method as claimed in claim 6, wherein, described add hydrogenchloride after, the described acidic ionic liquid catalysts containing the hydrogenchloride added mixes with the stream comprising spent acid ionic-liquid catalyst.
8. the method for claim 1, wherein remove solid the temperature of 5 DEG C ~ 80 DEG C by described the middle at least partially of the effluent of solid that comprise.
9. the method for claim 1, wherein remove solid the temperature of 30 DEG C ~ 60 DEG C by described the middle at least partially of the effluent of solid that comprise.
10. the method for claim 1, wherein described in fractionation, comprise the product comprising alkylate oil at least partially with acquisition of the effluent of alkylate oil.
11. the method for claim 1, wherein hydrocarbon mixture comprise Trimethylmethane and/or iso-pentane.
12. the method for claim 1, wherein described hydrocarbon mixture comprise the alkene with 3 to 6 carbon atoms.
13. the method for claim 1, wherein described hydrocarbon mixture comprise the alkene with 4 or 5 carbon atoms.
14. the method for claim 1, wherein, described acidic ionic liquid catalysts is the compound ion liquid be made up of positively charged ion, negatively charged ion, described positively charged ion is derived from containing the amine of alkyl or the hydrogen halide of pyridine, described negatively charged ion is the compound coordination anion derived from two or more metal halides, wherein at least one metal halide is the halogenide of aluminium, and any other metal halide is the halogenide of the metal being selected from the group be made up of the transition element of the periodic table of elements.
15. methods as claimed in claim 14, wherein, the transition element of the described periodic table of elements is selected from the IB race element of the periodic table of elements and the IIB race element of the periodic table of elements.
16. methods as claimed in claim 14, wherein, described catalyzer comprises the muriate of aluminum chloride and copper (I) or the muriate of copper (II).
17. the method for claim 1, wherein described solid by filtration method, the precipitator method and/or centrifuging removed from described comprising the effluent of solid.
CN201080034740.7A 2009-08-06 2010-08-05 Process for preparing an alkylate CN102666444B (en)

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