CN106032349A - Alkylation reaction method for isoparaffin and alkene with liquid acid for catalysis - Google Patents
Alkylation reaction method for isoparaffin and alkene with liquid acid for catalysis Download PDFInfo
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Abstract
The invention provides an alkylation reaction method for isoparaffin and alkene with liquid acid for catalysis. The method is characterized in that the method comprises the following steps: alkylation reaction raw materials are fed from a side surface of a static mixer in one stream or several streams, the raw materials and an acid hydrocarbon emulsion which is in a main runner of the static mixer are mixed and contacted, after the mixture is reacted and contacted for 0.2-15 minutes, pressure reduction is carried out for the mixture, the mixture enters a separator, the pressure of the separator is controlled at 0.005-0.18MPa, butane is vaporized in order to take away reaction heat, the acid phase below the separator is supercharged by an acid circulation pump and recycled to the main runner of the static mixer; gas phase components which are separated from an upper part of the separator enter a compressor system, and the components are compressed and condensed by a compressor in order to cool the alkylation reaction raw materials; a hydrocarbon phase which is partially separated from the separator enters a coalescer, most of the hydrocarbon phase which is separated from the coalesce is supercharged by a hydrocarbon circulation pump and mixed with the raw materials, and the mixture enters the side surface of the static mixer for feeding; an acid phase which is separated from the lower part of the coalesce returns an inlet of the circulation pump; a small part of a hydrocarbon phase which is extracted from the upper part of the coalescer enters a deisobutanizer, isobutane which is obtained from the top of the deisobutanizer is circulated and returns to the static mixer, and alkylation products are obtained from the bottom of the deisobutanizer.
Description
Technical field
The present invention relates to a kind of liquid acid alkylation reaction method, particularly relate to a kind of acid catalyzed isomery of liquid
Alkane and the alkylation reaction method of alkene.
Background technology
Isoparaffin and the alkylated reaction of alkene, be primarily referred to as the alkylated reaction of isobutane and butene, and it is anti-
The essence answered is in the presence of acidic catalyst, and organic addition that alkane molecule is added on olefin hydrocarbon molecules is anti-
Should.Alkylated reaction is an important technical process in petrochemical industry.Isobutane and butene is at strong acid catalyst
The isomery C of generation is reacted under agent effect8Alkane, referred to as gasoline alkylate.Gasoline alkylate has high-octane rating
(RON94～96) and low Reid vapour pressure, sulfur content, olefin(e) centent are extremely low, without benzene and aromatic hydrocarbons, are excellent
Good gasoline blend component.Use reformulated gasoline as petrolic fuel, it will significantly relax by
The urban air pollution caused is discharged in Extract from Gasoline-fueled Vehicle.For this meaning, gasoline alkylate is a kind of environment
Friendly petrochemicals.
The catalyst that current industrial alkylated reaction is used is mainly the liquid strong acid such as concentrated sulphuric acid or Fluohydric acid..
Typical alkylation reaction technique still uses horizontal agitated vessel reactor, and iso-butane and butene alkylation
Being the reaction of typical Two Liquid Phases, interphase mass transfer speed determines Global reaction Rate.In this type of reaction system,
In the case of biphase fully dispersed mixing, alkene can quickly realize converting completely, if response time mistake
Long, initially form has high-octane trimethylpentane (TMP) and will continue with highly acid catalyst
Contact, can cause TMP to the isomerization of low-octane DMH.Therefore, use convention stir reactor difficult
To realize obtaining high-octane product while obtaining high conversion.
Isoparaffin belongs to immiscible liquid-liquid two phase reaction with the alkylated reaction of alkene, and immiscible liquid-liquid is biphase
Mixed effect conversion ratio and the selectivity of liquid-liquid reactions are had material impact.Current existing liquid-liquid two
Phase mixing reactor mainly has stirred tank, static mixer, impinging streams mixer and ejector mixing etc..
CNZL200520078557.3 discloses the horizontal reactor in a kind of sulfuric acid process alkylation process, main body
It is a horizontal pressure vessel, has at an interior circulating sleeve, shell and tube heat removing tube bundle, an end socket
Propeller.Reaction feed and recycle acid enter the suction side of stirring paddle, under the driving of stirring paddle,
Reaction mass spread rapidly and with acid formed emulsion, emulsion in reactor ceaselessly high-speed circulating concurrent
Raw reaction.In the discharge side of reactor, a part of emulsion is discharged to acid settler, carries out the separation of acid.
Acid is sunk to bottom settling tank owing to proportion is relatively big, then returnes to the suction side of stirring paddle.Reactant mixes
Process completes in whole horizontal reactor, and the bulk of mixing is whole reactor, and time appropriateness exists
20-30 minute, belong to the category of micromixing.Back-mixing in this reactor is relatively big, is unfavorable for improving instead
The selectivity answered.
US6194625B1 discloses the alkylation reactor of a kind of sectional feeding, and reaction zone is divided into several string
The section of connection, is divided into a few stock not introduce each reaction section by fresh feed, and the sour hydrocarbon recycled
Emulsion is then series flow, uses churned mechanically mode to mix in each reaction section.This structure
Although overcoming the problem that back-mixing is bigger, but structure being the most complicated.It addition, both reactors all have employed
Fixing motor drives stirring paddle, it is easy to the anti-raw leakage because of poorly sealed.
CN100348559C proposes a kind of ionic liquid catalyzed alkylation reaction method i.e. reactor assembly, is
The liquid-liquid phase alkylated reaction of ionic liquid-catalyzed isoparaffin and alkene is completed in hypergravity rotary apparatus.
The rotary drill reactor device that this invention provides includes: reactor shell, and housing has charge door and discharging opening,
Reactor shell, built with the RPB being made up of rotor, packing layer, wherein has feed pipe, feed liquid to spray
Head, RPB is positioned at housing upper, and lower housing portion is fluid reservoir, and the heart is equipped with stirring dress in the reactor
Putting, can be stirred the reaction mass of fluid reservoir, fluid reservoir connects and composes revolving bed with feed liquid circulating pump and follows
Loop reactor, the suction tube porch of circulating pump is connected with blender, has alkane alkene feed liquid on the mixer and sucks
Mouth and ionic liquid import, reacted part feed liquid and ionic liquid mix at blender, going out of circulating pump
Material mouth connects the feed pipe of RPB, and circulating pump is delivered to RPB mixed feed liquid and followed
Ring reacts, and equipped with liquid level control gage on fluid reservoir, controls the time of staying of feed liquid.The reaction of this structure
Device can strengthen the mixing between reactant and acid hydrocarbon emulsion, but structure is the most complicated, it is not easy to expanding production
Scale.
US3281213 proposes a kind of vertical alkylation reactor, and its main body is a riser, riser with
One horizontal tank is connected, and horizontal tank passes through built with acid hydrocarbon emulsion, the isoparaffin and the alkene that participate in reaction
Nozzle bottom riser sprays into, and the gravitation that injection causes drives the sour hydrocarbon emulsion in horizontal tank to enter together
Riser, reaction is i.e. carried out in this root riser reactor.Riser top connects a knockout drum,
Separation for product.Sour hydrocarbon emulsion after separation is recycled into the horizontal tank bottom riser.This
Structure does not use mechanical transmission member, solves the series of problems that built-in stirring blade brings.But, carry
In riser, acid hydrocarbon emulsion is not satisfactory with the mixing of other reactants, it addition, whole reactor assembly
Have employed a riser, two horizontal tanks and a down-comer, equipment is huge, structure is the compactest.
Summary of the invention
An object of the present invention is to provide a kind of dispersion when strengthening alkene primary response in acid hydrocarbon emulsion
Intensity, and increase the mixing intensity of isoparaffin and liquid acid, be particularly well-suited to sulphuric acid, ionic liquid,
And the alkylation reaction method of isoparaffin and alkene that the mixed acid based on sulphuric acid is catalyst.
The two of the purpose of the present invention are to provide a kind of simple in construction, tight being applicable to abovementioned alkyl reaction method
Gather, invest little, operate easy to maintenance, save again the reaction unit of power.
An object of the present invention is achieved through the following technical solutions:
The acid catalyzed isoparaffin of a kind of liquid and the alkylation reaction method of alkene, it is characterised in that by alkyl
Change reaction raw materials divides one or more strands of charging to enter, with static mixer sprue from the side of static mixer
In sour hydrocarbon emulsion mixing contact 0.2-15min after through decompression enter separator, control separator pressure be
0.005-0.18MPa makes butane therein vaporize and take away reaction heat, and the acid of separator bottom is through following
Naphthenic acid pump supercharging Posterior circle returns to static mixer sprue；The isolated gaseous component in separator top enters
Compressor assembly, is used for cooling down alkylated reaction raw material after compressor compression condensation；Separate in the middle part of separator
The hydrocarbon phase that goes out enters coalescer, coalescer isolated hydrocarbon phase major part after recycle hydrocarbons pump supercharging with alkylation
Reaction raw materials is mixed into the side-fed of static mixer；The isolated acid in coalescer bottom returns circulation mutually
Pump intake；Extraction fraction hydrocarbon phase in coalescer top enters deisobutanizer, and it is different that deisobutanizer top obtains
Butane loops back static mixer, and tower reactor obtains alkylate.
The two of the purpose of the present invention are achieved through the following technical solutions:
A kind of device of the reaction method for claim 1, it is characterised in that include static mixer (1),
Separator (2), coalescer (3), cyclic acid pump (4), recycle hydrocarbons pump (5), deisobutanizer (6),
Compressor (7), the iso-butane line of return (8), recycle acid line (9), fresh feed feeding line (10), mixing
Hydrocarbon discharge pipe (11), gas phase discharge line (12), the coalescence acid line of return (13), recycle hydrocarbons line (14),
The coalescence hydrocarbon phase line of return (15), the separating acid phase line of return (16), separate hydrocarbon phase extraction line (17), circulate different
Butane line (18), deisobutanizer feeding line (19), normal butane extraction line (20), alkylate extraction
Line (21).Wherein, described static mixer (1) is connected with separator (2) through pipeline (11), point
From device (2) bottom, the separated acid phase line of return (16) is connected with acid circulating pump (4), separator (2) warp
Separating hydrocarbon phase extraction line (17) to be connected with coalescer (3), coalescer (3) bottom is returned by coalescence acid
Line is connected with cyclic acid pump (4), and cyclic acid pump (4) is again by recycle acid line (9) and static mixer (1)
Connecting, coalescer (3) middle part is connected with recycle hydrocarbons pump (5) through the coalescence hydrocarbon phase line of return (15), circulation
Hydrocarbon pump (5) is connected with fresh feed feeding line (10) through the coalescence hydrocarbon phase line of return (15) again, and gas is discharged
Pipe (12) is used for discharging gaseous component, and gaseous component is mixed into reaction raw materials line (10) after compressor compression condensation
For cooling down in alkylated reaction raw material, coalescer (3) isolated alkylation effluent through deisobutanizer
Feeding line (19) enters deisobutanizer (6), returns through iso-butane after the gas phase iso-butane condensation that tower top separates
Loop line (18) is incorporated to fresh feed feeding line (10), and tower middle and upper part is through normal butane extraction line (20) extraction just
Butane, tower reactor is through alkylate extraction line (21) extraction alkylate.
Advantages of the present invention and effect be:
1. utilize static mixer to enhance alkene rapid dispersion in acid hydrocarbon emulsion, improve liquid phase initial
Microcosmic mixed-level, accelerates alkylated reaction speed macroscopically, thus improve reaction conversion ratio and
The selectivity of product, this reactor is more suitable for plant-scale course of reaction simultaneously.
2. the mode using static mixer and separator to combine, makes static mixing reaction zone mixture out
Expecting vacuum flashing in the separator, a large amount of vaporizations of the iso-butane of fast vaporizing enhance and accelerate reaction heat
Remove.
3. use the mode that static mixer and separator combine, it is to avoid liquid and wall in stirred autoclave
The energy loss clashed into, capacity usage ratio is high.
4. the mode circulated respectively after acid hydrocarbon phase separation in employing reaction effluent, is conducive to controlling the acid of reaction
Hydrocarbon ratio, strengthens the stability of operation.
5. in the reactor provided, inner member is few, and frame for movement is simple, it is simple to processes, clean, and equipment is thrown
Money saves.
6. the reactor provided all uses static seal, it is to avoid rotary part in traditional stirred tank reactor
The shortcoming weakening sealing property, sealing property is more preferable, is particularly well-suited to inflammable, explosive and corrosive materials
Mixing and reaction.
Accompanying drawing explanation
Accompanying drawing is the schematic diagram of the reaction unit of the present invention.
In figure, 1-static mixer, 2-separator, 3-coalescer, 4-cyclic acid pump, 5-recycle hydrocarbons pump,
6-deisobutanizer, 7-compressor, the 8-iso-butane line of return, 9-recycle acid line, 10-fresh feed feeding line,
11-hydrocarbon mixture discharge pipe, 12-gas phase discharge line, 13-coalescence the acid line of return, 14-recycle hydrocarbons line, 15-
Coalescence the hydrocarbon phase line of return, the 16-separating acid phase line of return, 17-separate hydrocarbon phase extraction line, 18-recycle isobutane line,
19-deisobutanizer feeding line, 20-normal butane extraction line, 21-alkylate extraction line.
Detailed description of the invention
The acid catalyzed isoparaffin of a kind of liquid and the alkylation reaction method of alkene, it is characterised in that by alkane
Glycosylation reaction raw material divides one or more strands of charging to enter, with static mixer main flow from the side of static mixer
Entering separator through decompression after sour hydrocarbon emulsion mixing contact 0.2-15min in road, controlling separator pressure is
0.005-0.18MPa makes butane therein vaporize and take away reaction heat, and the acid of separator bottom is through following
Naphthenic acid pump supercharging Posterior circle returns to static mixer sprue；The isolated gaseous component in separator top enters
Compressor assembly, is used for cooling down alkylated reaction raw material after compressor compression condensation；Separate in the middle part of separator
The hydrocarbon phase that goes out enters coalescer, coalescer isolated hydrocarbon phase major part after recycle hydrocarbons pump supercharging with alkylation
Reaction raw materials is mixed into the side-fed of static mixer；The isolated acid in coalescer bottom returns circulation mutually
Pump intake；Extraction fraction hydrocarbon phase in coalescer top enters deisobutanizer, and it is different that deisobutanizer top obtains
Butane loops back static mixer, and tower reactor obtains alkylate.
The purpose of generally most alkylations is by isoparaffin (or aromatic hydrocarbons) and light olefin and acidic catalyst
Agent is in close contact, and reaction generates alkylate.In petroleum refining industry, the acid of aliphatic hydrocarbon and alkene is urged
Changing alkylation is well-known method.Indication alkylation of the present invention refers to that isoparaffin is urged at strong acid with alkene
The course of processing that under change, generation such as octane number is higher than raw material, boiling range is gasoline-range fraction.Involved by the present invention
And alkylation be generally iso-butane and C3～C5The reaction of olefine fraction, is particularly well-suited to iso-butane and carbon four
The reaction of alkene.
Described liquid acid is concentrated sulphuric acid, strong acidic ion liquid or the mixed acid based on concentrated sulphuric acid, described
Liquid acid preferably employ concentrated sulphuric acid that concentration is 90%-99.2% and the mixed acid based on concentrated sulphuric acid.
In alkylation reaction method, acid hydrocarbon volume ratio 0.8～1.5:1, preferably 1～1.2:1, more preferably:
1～1.1:1.In the specific embodiment of the invention, the typical case of the alkylated reaction raw material containing alkene of employing
Composition can be, but not limited to: propane 0.098%, iso-butane 39.36%, normal butane 13.51%, isobutene.
1.39%, 1 butylene 14.70%, maleic 14.92%, anti-butylene 16.0%, pentane 0.022%.Containing alkene
The alkylated reaction raw material of hydrocarbon component is allocated with the recycle isobutane in device, obtains suitable alkane alkene and rubs
The alkylated reaction raw material of your ratio enters reactor.The alkane alkene mol ratio of described alkylated reaction raw material refers to
The molar ratio of isobutane and olefins component in deployed reaction mass, can be 5～15:1, is preferably
6～12:1, more preferably 8～10:1.
Described alkylated reaction raw material is divided into the one or more strands of different parts entrance from static mixer.Many
Stock feeds and can dilute feed olefin concentration, raising product octane number, such as 2-10 stock, preferably 2～6 strands,
More preferably 24 strands；If it exceeds number of share of stock is too many, such as the charging more than 3 strands, can cause and feed below
The time of staying in reactor is inadequate, causes reaction not exclusively, affects product quality, therefore, most preferably
Alkylated reaction raw material divides 2～3 strands of entrance static mixers.The material direction entering static mixer is preferably
Angle perpendicular with static mixer sprue.Described alkylated reaction raw material is from static mixer side surface part
Position enters, and mixes with the sour hydrocarbon emulsion in static mixer sprue and contacts, and mixture reaction contacts
After 0.5-15min, preferred 0.5-5min, decompression enters separator, controls separator pressure and is
0.005-0.18MPa, preferred 0.01-0.18MPa make butane vaporize and take away reaction heat, under separator
The major part acid intensified Posterior circle of hydrocarbon emulsion in portion returns to static mixer sprue；I.e. the present invention have employed
The self-evaporating refrigeration modes of isoparaffin.The isolated gaseous component in separator top enters compressor assembly,
It is used for cooling down alkylated reaction raw material after compressor compression condensation.In the middle part of separator, extraction fraction hydrocarbon phase enters
Entering coalescer, the acid coalesced out returns static mixer mutually, and hydrocarbon phase enters deisobutanizer, and tower top obtains
Iso-butane loops back static mixer, and tower reactor obtains alkylate.
The alkylation reaction method that the present invention provides, reaction temperature is-7～10 DEG C.
The present invention still further provides the device being applicable to above-mentioned alkylation reaction method, it is characterised in that
Including static mixer (1), separator (2), coalescer (3), cyclic acid pump (4), recycle hydrocarbons pump (5),
Deisobutanizer (6), compressor (7), the iso-butane line of return (8), recycle acid line (9), fresh feed
Feeding line (10), hydrocarbon mixture discharge pipe (11), gas phase discharge line (12), the coalescence acid line of return (13),
Recycle hydrocarbons line (14), the coalescence hydrocarbon phase line of return (15), the separating acid phase line of return (16), separate hydrocarbon phase extraction
Line (17), recycle isobutane line (18), deisobutanizer feeding line (19), normal butane extraction line (20),
Alkylate extraction line (21).Wherein, described static mixer (1) through pipeline (11) with separate
Device (2) connects, and separator (2) the bottom separated acid phase line of return (16) is connected with acid circulating pump (4),
Separator (2) separated hydrocarbon phase extraction line (17) is connected with coalescer (3), and coalescer (3) bottom leads to
Cross coalescence acid the line of return is connected with acid circulating pump (4), acid circulating pump (4) again pass through recycle acid line (9) and
Static mixer (1) connects, and coalescer (3) middle part is through the coalescence hydrocarbon phase line of return (15) and recycle hydrocarbons pump
(5) connecting, recycle hydrocarbons pump (5) is again through the coalescence hydrocarbon phase line of return (15) and fresh feed feeding line (10)
Connecting, gas outlet pipe (12) is used for discharging gaseous component, and gaseous component is mixed after compressor compression condensation
Enter reaction raw materials line (10) to be used for cooling down isolated alkylation in alkylated reaction raw material, coalescer (3)
Effluent enters deisobutanizer (6), the gas phase isobutyl that tower top separates through deisobutanizer feeding line (19)
Being incorporated to fresh feed feeding line (10) through the iso-butane line of return (18) after alkane condensation, tower middle and upper part is through normal butane
Extraction line (20) extraction normal butane, tower reactor is through alkylate extraction line (21) extraction alkylate.
In the device that the present invention provides, the form of described static mixer (1) is preferably selected from SMX, SK
Or one or more of the static mixer of SV type are used in mixed way.Described coalescer (3) can be one-level
Or what serial or parallel connection is used in mixed way, it is preferred to use 2～3 grades are used in series.
In described separator, isolated acid hydrocarbon phase circulates respectively, and acid circulates through cyclic acid pump (4), hydrocarbon
Circulated by recycle hydrocarbons pump (5) after coalescer (3).Acid hydrocarbon circular route is preferably respectively adopted a road circulation.
Above-mentioned concrete structure and quantity can be designed by this area general knowledge according to reactor scale and material properties
Determine.
Carbon tetra-alkylation reaction raw materials containing alkene is vertically into the sideway stance of static mixer (1), instead
Answer raw material point multiply to spray into static mixer (1) sprue and with recycle acid emulsion, strong immixture occurs, instead
Answer the entrance separator (2) after a period of time.
Normally control liquid level reaction acid arranged below phase outlet at separator (2), be located at separator (2)
Bottom, hydrocarbon phase outlet is preferably in liquid level middle and upper part separated hydrocarbon phase extraction line (17) with coalescer (3) even
Connecing, separator (2) bottom acid connects through cyclic acid pump (4), and cyclic acid pump (4) passes through recycle acid again
Line (9) is connected with static mixer (1).
Gas outlet pipe (12) is used for discharging gaseous component, and gaseous component is mixed into after compressor compression condensation
Reaction raw materials line (10) is used for cooling down alkylated reaction raw material.
The acid of coalescer (3) bottom returns to cyclic acid pump entrance through the coalescence acid line of return (13).Coalescence
Device (3) middle and upper part is connected with recycle hydrocarbons pump (5) through the coalescence hydrocarbon phase line of return (15), recycle hydrocarbons pump (5)
It is connected with fresh feed feeding line (10), for diluting reaction raw material through the coalescence hydrocarbon phase line of return (15) again.
The isolated alkylation in coalescer (3) top effluent enters de-through deisobutanizer feeding line (19)
Iso-butane tower (6), is incorporated to fresh through the iso-butane line of return (18) after the gas phase iso-butane condensation that tower top separates
Feedstock line (10), tower middle and upper part is through normal butane extraction line (20) extraction normal butane, and tower reactor is through alkylation
Product extraction line (21) extraction alkylate.
Assembly of the invention enhances alkene initial microcosmic mixing dispersion effect in recycle acid hydrocarbon emulsion, suppression
The carrying out of alkylation side reaction, thus ensure reaction after product have under high-octane premise reduce into
Enter the circulating load of iso-butane in material, reduce the energy consumption of device, there is the strongest industrial applicibility.
The acid catalyzed isoparaffin of liquid and the alkylation reaction method of alkene to the present invention below in conjunction with the accompanying drawings
Method and apparatus is specifically described.
In embodiment, the alkylated reaction raw material (i.e. carbon 4 liquid gas) containing alkene uses carbon four after MTBE ether
Alkane gaseous mixture, in gaseous mixture, weight/mass percentage composition is propane 0.098%, iso-butane 39.36%, normal butane
13.51%, isobutene. 1.39%, 1-butylene 14.70%, maleic 14.92%, anti-butylene 16.0%, pentane
0.022%.
Embodiment 1
As it can be seen, the present embodiment provides a kind of method and apparatus with concentrated sulphuric acid as alkylation catalyst.
Alkylation catalyst concentrated sulphuric acid (concentration is 98.5%, lower same) and recycle acid are squeezed into through cyclic acid pump 4
One group of static mixer 1 (Sulzer construction machinery production company limited SMVTMType, lower with) sprue,
Recycle hydrocarbons returns to alkylated reaction raw material through pipeline 10 (raw material line divides 2 tunnels) through recycle hydrocarbons pump 5, and joins
The alkane alkene made mixes than the fresh feed for 8.3:1, vertically into the sideway stance of static mixer 1,
There is strong immixture in acid hydrocarbon phase in static mixer, makes alkene reach microcosmic mixing in mixed material
State.After uniform mixed mixed material reacts a period of time, decompression enters separator 2, in the middle part of separator
Reaction heat is taken in the iso-butane evaporation dividing vaporization in time away.In separator, isolated major part acid is through pipeline 9
Static mixer sprue is returned by cyclic acid pump 4.The gas phase that separator top is discharged through gas outlet pipe 12
Component (predominantly iso-butane) returns on recycle isobutane line 18 after compressor 7 compression condensation.Control
Separator pressure, at about 0.035MPa, controls the temperature of static mixer reaction zone at 2-3 DEG C；Separator
In isolated hydrocarbon phase separated hydrocarbon phase extraction line 17 enter coalescer 3.The acid of coalescer 3 bottom is passed through mutually
Recycle acid line 9 returns to static mixer entrance, and the hydrocarbon phase of coalescer middle and upper part is through the coalescence hydrocarbon phase line of return 15
Return to on fresh feed feeding line.The isolated alkylation in coalescer top liquid product enters de-isobutyl
Alkane tower 6, is incorporated to fresh feed feeding line through the iso-butane line of return 18 after the gas phase iso-butane condensation that tower top separates
On, tower reactor is through alkylate extraction line 21 extraction alkylate.
Alkylation reaction product through distillation removing carbon four component, it is thus achieved that alkylate oil do 195 DEG C, RON
Value 96.31, MON value 93.8.
Embodiment 2
As it can be seen, a kind of method and apparatus with concentrated sulphuric acid as alkylation catalyst that the present embodiment provides.
Alkylation catalyst concentrated sulphuric acid (concentration is 98.5%, lower same) and recycle acid are squeezed into through cyclic acid pump 4
One group of static mixer 1 (Sulzer construction machinery production company limited SMVTMType, lower with) sprue,
Recycle hydrocarbons returns to alkylated reaction raw material through pipeline 10 (raw material line divides 4 tunnels) through recycle hydrocarbons pump 5, and joins
The alkane alkene made mixes than the fresh feed for 9.5:1, vertically into the sideway stance of static mixer 1,
There is strong immixture in acid hydrocarbon phase in static mixer, makes alkene reach microcosmic mixing in mixed material
State.After uniform mixed mixed material reacts a period of time, decompression enters separator 2, in the middle part of separator
Reaction heat is taken in the iso-butane evaporation dividing vaporization in time away.In separator, isolated major part acid is through pipeline 9
Static mixer sprue is returned by cyclic acid pump 4.The gas phase that separator top is discharged through gas outlet pipe 12
Component (predominantly iso-butane) returns on recycle isobutane line 18 after compressor 7 compression condensation.Control
Separator pressure, at about 0.025MPa, controls the temperature of static mixer reaction zone at-4 DEG C；In separator
Isolated hydrocarbon phase separated hydrocarbon phase extraction line 17 enters coalescer 3.The acid of coalescer 3 bottom is mutually by following
Naphthenic acid line 9 returns to static mixer entrance, and the hydrocarbon phase of coalescer middle and upper part is through the coalescence hydrocarbon phase line of return 15
Return to on fresh feed feeding line.The isolated alkylation in coalescer top liquid product enters de-isobutyl
Alkane tower 6, is incorporated to fresh feed feeding line through the iso-butane line of return 18 after the gas phase iso-butane condensation that tower top separates
On, tower reactor is through alkylate extraction line 21 extraction alkylate.
Alkylation reaction product through distillation removing carbon four component, it is thus achieved that alkylate oil do 193 DEG C, RON
Value 96.7, MON value 94.5.
Embodiment 3
As it can be seen, the one that the present embodiment provides is with highly acid AlCl3Type ionic liquid is alkylation catalyst
Method and apparatus.
Alkylation catalyst highly acid AlCl3Type ionic liquid (concentration is 95.0%, lower same) and recycle acid warp
Cyclic acid pump 4 squeezes into one group of static mixer 1 (Sulzer construction machinery production company limited SMVTMType, under
Sprue together), recycle hydrocarbons returns to alkylated reaction raw material through pipeline 10 (raw material line through recycle hydrocarbons pump 5
Divide 3 tunnels), mix than the fresh feed for 7.5:1, vertically into static mixer with the alkane alkene prepared
The sideway stance of 1, there is strong immixture in acid hydrocarbon phase in static mixer, makes alkene at mixed material
In reach microcosmic admixture.After uniform mixed mixed material reacts a period of time, decompression enters separator
2, reaction heat is taken in the iso-butane evaporation of part vaporization in separator in time away.Isolated major part in separator
Acid is returned static mixer sprue through pipeline 9 by cyclic acid pump 4.Separator top is through gas outlet pipe
12 gaseous components (predominantly iso-butane) discharged return to recycle isobutane after compressor 7 compression condensation
On line 18.Control separator pressure to exist in about 0.035MPa, the temperature controlling static mixer reaction zone
2-3℃；In separator, isolated hydrocarbon phase separated hydrocarbon phase extraction line 17 enters coalescer 3.Coalescer 3
The acid of bottom returns to static mixer entrance by recycle acid line 9 mutually, and the hydrocarbon phase of coalescer middle and upper part is through poly-
Knot the hydrocarbon phase line of return 15 return to on fresh feed feeding line.The isolated alkylation in coalescer top liquid phase
Product enters deisobutanizer 6, is incorporated to through the iso-butane line of return 18 after the gas phase iso-butane condensation that tower top separates
On fresh feed feeding line, tower reactor is through alkylate extraction line 21 extraction alkylate.
Alkylation reaction product through distillation removing carbon four component, it is thus achieved that alkylate oil do 199 DEG C, RON
Value 96.5, MON value 93.8.
Embodiment 4
As it can be seen, the present embodiment provide with concentrated sulphuric acid and trifluoromethanesulfonic acid the method as alkylation catalyst and
Device.
Alkylation catalyst concentrated sulphuric acid and trifluoromethanesulfonic acid (concentrated sulphuric acid: trifluoromethanesulfonic acid=3:1, lower with) and
Recycle acid squeezes into one group of static mixer 1 (Sulzer construction machinery production company limited through cyclic acid pump 4
SMVTMType, lower with) sprue, recycle hydrocarbons returns to alkylated reaction raw material through pipeline through recycle hydrocarbons pump 5
10 (raw material line divides 6 tunnels), mix than the fresh feed for 8.5:1 with the alkane alkene prepared, vertically into
The sideway stance of static mixer 1, there is strong immixture in acid hydrocarbon phase in static mixer, makes alkene
Microcosmic admixture is reached in mixed material.Uniform mixed mixed material reduces pressure after reacting a period of time
Entering separator 2, reaction heat is taken in the iso-butane evaporation of part vaporization in separator in time away.Separator divides
The major part acid separated out is returned static mixer sprue through pipeline 9 by cyclic acid pump 4.Separator top
The gaseous component (predominantly iso-butane) discharged through gas outlet pipe 12 returns after compressor 7 compression condensation
On recycle isobutane line 18.Control separator pressure in about 0.06MPa, control static mixer reaction
The temperature in district is at 1 DEG C；In separator, isolated hydrocarbon phase separated hydrocarbon phase extraction line 17 enters coalescer 3.
The acid of coalescer 3 bottom returns to static mixer entrance by recycle acid line 9 mutually, coalescer middle and upper part
Hydrocarbon phase through coalescence the hydrocarbon phase line of return 15 return to on fresh feed feeding line.The isolated alkane in coalescer top
Base liquid product enters deisobutanizer 6, returns through iso-butane after the gas phase iso-butane condensation that tower top separates
Line 18 is incorporated on fresh feed feeding line, and tower reactor is through alkylate extraction line 21 extraction alkylate.
Alkylation reaction product through distillation removing carbon four component, it is thus achieved that alkylate oil do 196 DEG C, RON
Value 96.3.0, MON value 93.7.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention not office
Being limited to this, any those familiar with the art, can be easily in the technical scope of present disclosure
The change expected or replacement, all should contain within the scope of the present invention.Therefore, the protection model of the present invention
Enclose and be as the criterion with scope of the claims.
Claims (21)
1. the acid catalyzed isoparaffin of liquid and the alkylation reaction method of alkene, it is characterised in that by alkyl
Change reaction raw materials divides one or more strands of charging to enter, with static mixer main flow from the side of static mixer
Enter separator through decompression after sour hydrocarbon emulsion mixing contact 0.2-15min in road, control separator pressure
Butane therein is made to vaporize and take away reaction heat for 0.005-0.18MPa, the sour phase of separator bottom
Static mixer sprue is returned to through cyclic acid pump supercharging Posterior circle；Separator top isolated gas phase group
Divide and enter compressor assembly, be used for cooling down alkylated reaction raw material after compressor compression condensation；Separator
The isolated hydrocarbon phase in middle part enters coalescer, and coalescer isolated hydrocarbon phase major part is through recycle hydrocarbons pump supercharging
It is mixed into the side-fed of static mixer afterwards with alkylated reaction raw material；Coalescer bottom is isolated
Acid returns pump entry mutually；Extraction fraction hydrocarbon phase in coalescer top enters deisobutanizer, de-isobutyl
The iso-butane that alkane tower top obtains loops back static mixer, and tower reactor obtains alkylate.
2. according to the method for claim 1, it is adaptable to iso-butane and C3-C5The alkylated reaction of olefine fraction.
3. according to the method for claim 1, it is adaptable to iso-butane and the alkylated reaction of C 4 olefin.
4. according to the process of claim 1 wherein, described alkylated reaction raw material, its alkane alkene mol ratio be 5～
15:1。
5. according to the process of claim 1 wherein, described alkylated reaction raw material, its alkane alkene mol ratio be 6～
12:1。
6. according to the process of claim 1 wherein, described alkylated reaction raw material, its alkane alkene mol ratio be 8～
10:1。
7. according to the process of claim 1 wherein, described alkylated reaction raw material and static mixer sprue
In sour hydrocarbon emulsion mixing contact, the time is 0.5-5min.
8., according to the process of claim 1 wherein, the operation pressure of described separator is 0.01-0.18MPa.
9., according to the method for claim 1, reaction temperature is-7～10 DEG C.
10. according to the process of claim 1 wherein, described liquid acid be concentrated sulphuric acid, strong acidic ion liquid or
Mixed acid based on concentrated sulphuric acid.
11. according to the process of claim 1 wherein, described alkylated reaction raw material is from the side of static mixer
Divide 2～10 bursts of chargings.
12. according to the process of claim 1 wherein, described alkylated reaction raw material is from the side of static mixer
Divide 2～6 bursts of chargings.
13. according to the method for claim 11, and wherein, described alkylated reaction raw material is from the side of static mixer
2～3 bursts of chargings are divided in face.
14. according to the process of claim 1 wherein, the dense sulfur that described liquid acid uses concentration to be 90%-99.2%
Acid and the mixed acid based on concentrated sulphuric acid.
15. according to the process of claim 1 wherein, is mixed in separator after the compressed condensation of butane of vaporization
Alkylated reaction feedstock circulation uses as supplementing raw material and as cryogen.
16. 1 kinds of devices of reaction methods for claim 1, it is characterised in that include static mixer (1),
Separator (2), coalescer (3), cyclic acid pump (4), recycle hydrocarbons pump (5), deisobutanizer (6),
Compressor (7), the iso-butane line of return (8), recycle acid line (9), fresh feed feeding line (10),
Hydrocarbon mixture discharge pipe (11), gas phase discharges line (12), the coalescence acid line of return (13), recycle hydrocarbons line
(14), the coalescence hydrocarbon phase line of return (15), the separating acid phase line of return (16), separate hydrocarbon phase extraction line (17),
Recycle isobutane line (18), deisobutanizer feeding line (19), normal butane extraction line (20), alkyl
Changing product extraction line (21), wherein, described static mixer (1) is through pipeline (11) and separator
(2) connecting, separator (2) the bottom separated acid phase line of return (16) is with acid circulating pump (4) even
Connecing, separator (2) separated hydrocarbon phase extraction line (17) is connected with coalescer (3), coalescer (3)
Bottom is connected with acid circulating pump (4) by the coalescence acid line of return, and acid circulating pump (4) passes through recycle acid again
Line (9) is connected with static mixer (1), and coalescer (3) middle part is through the coalescence hydrocarbon phase line of return (15)
Being connected with recycle hydrocarbons pump (5), recycle hydrocarbons pump (5) is former with fresh through the coalescence hydrocarbon phase line of return (15) again
Material feeding line (10) connects, and gas outlet pipe (12) is used for discharging gaseous component, and gaseous component is through pressure
It is mixed into reaction raw materials line (10) after contracting machine compression condensation to be used for cooling down alkylated reaction raw material, coalescer (3)
In isolated alkylation effluent through deisobutanizer feeding line (19) enter deisobutanizer (6),
It is incorporated to fresh feed feeding line through the iso-butane line of return (18) after the gas phase iso-butane condensation that tower top separates
(10), tower middle and upper part is through normal butane extraction line (20) extraction normal butane, and tower reactor is adopted through alkylate
Outlet (21) extraction alkylate.
17. according to the reaction unit of claim 16, and wherein, the form of described static mixer is for being selected from
The static mixer form of one of Kenics, SMX, SV, SH, SK, SX, SL, east profit Hi type.
18. according to the reaction unit of claim 16, and wherein, described blender is selected from SMX, SK or SV type
One or more of static mixer be used in mixed way.
19. according to the reaction unit of claim 16, and wherein, described coalescer can be one-level or what series connection
Or parallel connection is used in mixed way.
20. according to the device of claim 16, and wherein, in described separator, isolated acid hydrocarbon phase circulates respectively,
Acid circulates through cyclic acid pump (4), and hydrocarbon phase is circulated by recycle hydrocarbons pump (5) after coalescer (3).
21. according to the device of claim 16, and recycle acid and recycle hydrocarbons are respectively provided with a road.
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| CN111389338A (en) * | 2020-03-26 | 2020-07-10 | 北京理工大学 | Novel multi-channel reactor for toluene and isobutylene alkylation reaction |
| CN111589407A (en) * | 2020-05-20 | 2020-08-28 | 中石化南京工程有限公司 | Sulfuric acid alkylation system and method for producing isooctane by using same |
| CN111589406A (en) * | 2019-02-21 | 2020-08-28 | 中国石油化工股份有限公司 | Alkylation reaction device, reaction system and liquid acid catalyzed alkylation reaction method |
| CN112662426A (en) * | 2019-10-16 | 2021-04-16 | 中国石油化工股份有限公司 | Liquid acid alkylation reaction method and device |
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| CN109423329A (en) * | 2017-08-30 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of vertical alkylated reaction device and reaction method |
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| CN111589407B (en) * | 2020-05-20 | 2022-04-12 | 中石化南京工程有限公司 | Sulfuric acid alkylation system and method for producing isooctane by using same |
| CN114085682A (en) * | 2020-08-24 | 2022-02-25 | 中国石油化工股份有限公司 | Sulfuric acid alkylation reaction method and device and heat extraction method for sulfuric acid alkylation reaction |
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