CN108070400A - A kind of alkylation - Google Patents
A kind of alkylation Download PDFInfo
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- CN108070400A CN108070400A CN201611002425.1A CN201611002425A CN108070400A CN 108070400 A CN108070400 A CN 108070400A CN 201611002425 A CN201611002425 A CN 201611002425A CN 108070400 A CN108070400 A CN 108070400A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of alkylations, include the following steps：（1）Hydrocarbon raw material is dehydrated；（2）The alkylated reaction of hydrocarbon raw material is carried out using sulfuric acid as catalyst；（3）Alkylation reaction product separates；Wherein step（1）Hydrocarbon raw material dewatering is as follows：Using hitting, eddy flow is primary to separate depth separation process.Compared with prior art, alkylation of the present invention is more efficient, handles raw material for alkylation and alkylate in an energy-saving and environment-friendly manner, is of great significance for the advance for improving alkylated reaction integrated artistic.
Description
Technical field
The invention belongs to petrochemical industry, be specifically it is a kind of using sulfuric acid be catalyst as alkylation, particularly collect
Into material depth purification and the separated alkylation of product depth.
Background technology
In recent years, as countries in the world are to the most attention of environmental protection, the octane number and cleannes of motor petrol are carried
Higher and more strict requirements are gone out so that the overall standard of world's clean gasoline is towards low-sulfur, low fragrant, low alkene, higher octane
The direction of value is developed, thus alkylate oil and alkylation process become current focal point.Alkylation process is production Gao Pin
Matter gasoline blend component is that the generation under acid catalyst effect has high octane gasoline component to iso-butane with C3-C5 alkene
Reaction, the content of the harmful constituents such as alkene, aromatic hydrocarbons, sulphur can be reduced by being called in gasoline, while improve the octane number of gasoline
And the capability of antidetonance, it is very good cleaning motor petrol component.
In existing sulfuric acid alkylation technique, iso-butane and olefin feedstock and sulfuric acid catalyst are delivered to alkyl first
Change reactor, sour hydrocarbon emulsion is formed in reactor so as to complete alkylated reaction, sour hydrocarbon mixed emulsion enters sedimentation point afterwards
From device, sulfuric acid phase is mutually separated with hydrocarbon under density contrast effect, obtains hydrocarbon phase and sulfuric acid phase, the sulfuric acid isolated is supplementing
Fresh sulfuric acid Posterior circle uses.Still contain a certain amount of sulfuric acid using a sedimentation separation, in hydrocarbon phase, it is necessary to further follow-up point
From processing.
In addition, reaction raw materials（C4 hydrocarbon）In water water content is generally 300mg/kg or so in operational conditions, work as upstream
The water that device operation shakiness can carry raw material reaches 1000mg/kg or so, and even more high, Water entrainment in the feedstock so seriously can be to sulphur
The dilution rate of acid increases, due to there are certain requirements in alkylated reaction to the concentration of sulfuric acid catalyst, when recycle sulfuric acid concentration
It is required supplementation with when being required less than this and replaces new sulfuric acid, therefore water amount conference increases the replacement frequency of sulfuric acid in raw material, causes
The problems such as dilute sulfuric acid that system acid consumption is high, spent acid discharge capacity is big, generates quickly is big to equipment corrosion.
CN104109067A proposes a kind of purification method of alkylate, is by the way that alkylate is first cold
But mixed again with lye after, to neutralize organic acid, faintly alkaline reaction object is then introduced into level-one oil water separator-water successively
Cleaning of evaporator-two level oil water separator；CN103772097A proposes a kind of alkylate processing method, is by vapor-phase alkylation
Product is sent into the adsorbent bed of filling oil adsorbent, and adsorbent therein is solid base adsorbent, and gas phase reaction product is after cooling
Oil water separator, isolated oil-phase product and water-phase product are sent into, oil-phase product is sent into subsequent fractionation system, and water-phase product is sent
Start with processing system.The purpose of above two method is all to solve to take caused by alkylate separation thoroughly in the prior art
With organic acid to the etching problem of follow-up equipment, but ask there are still separating technology complexity, material consumption high energy consumption, quantity of wastewater effluent are big etc.
Topic.
CN201010524543.5 discloses a kind of method of alkylation reaction product depickling, concretely comprises the following steps：Alkyl
Change reaction product（Hydrocarbon-type oil）Mix emulsion fluid with sulfuric acid passes through dress after gravitational settling, with the crossflow velocity of 0.01 ~ 5m/s
The component for having hydrophobically modified ceramic membrane is separated, and is 0.01 ~ 0.3MPa in operating pressure, operation temperature is 0 DEG C ~ 40 DEG C of model
In enclosing, oil product deacidification is realized in a manner of cross-flow filtration.Under pressure promotion, by ceramic membrane, acid therein is trapped oil,
Acid content is less than 100mg/kg in obtained oil.Ceramic membrane（0.01~1.4 μm of aperture）Surface is hydrophobically modified, and water droplet is in film table
The contact angle in face is 70 ° ~ 160 °.This method utilizes the characteristic of hydrophobic ceramic film so that sulfuric acid microlayer model not by ceramic membrane,
But limited for the emulsified particles removal effect of hydrocarbon bag acid, particularly the emulsified particles diameter of hydrocarbon bag acid is less than ceramic membrane aperture
When, deacidification effect is undesirable.Meanwhile in order to obtain acid content relatively low in per-meate side hydrocarbon phase, retaining can contain in the sour phase of side
Higher hydrocarbons.
In terms of pretreatment of raw material, free water content in control principle is wanted under normal circumstances in≤10mg/kg, using existing
There is technology to be difficult to realize, so that sulfuric acid is diluted faster, acid consumption is caused to increase, the spent acid amount of generation is big, spent acid processing pressure
Increase, and the dilute sulfuric acid generated quickly to equipment corrosion increase, by the moisture in C4 raw materials control effectively to≤
10mg/kg, this plays an important roll for the efficient stable operation of alkyl plant.
In conclusion a kind of more efficient, energy-saving and environment-friendly raw material for alkylation of exploitation and alkylate isolation of purified work
Skill with overcome the deficiencies in the prior art, is of great significance for the advance for improving alkylated reaction integrated artistic.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of new alkylation process, right using cost-effective method
Raw material for alkylation and alkylate carry out effectively stablizing processing.
Alkylation of the present invention includes the following steps：
（1）Hydrocarbon raw material is dehydrated；
（2）The alkylated reaction of hydrocarbon raw material is carried out using sulfuric acid as catalyst；
（3）Alkylation reaction product separates；
Wherein step（1）Hydrocarbon raw material dewatering is as follows：Using eddy flow-primary separation-depth separation process is hit, will be alkylated
The moisture removal in hydrocarbon raw material is reacted to≤10mg/kg, and stable charging is provided for alkylation process.Hydrocarbon raw material is isobutyl
Alkane and C3-C5 alkene.
Step（1）In hydrocarbon raw material dewatering, the shock eddy flow operation the small water droplet in hydrocarbon raw material is collided,
Coalescence and cyclonic separation.Impingement region in cyclone separator at material inlet is set, i.e., material is divided into two strands, two strands of materials
It is opposite to introduce cyclone separator, form the effect of impact of material in impingement region.Material after shock enters eddy flow area, carries out eddy flow
Operation separates the water in hydrocarbon raw material.Hitting the general structure of cyclonic unit body construction includes being located at forepart（When horizontally disposed,
Or top when vertically setting, similarly hereinafter）Top closure circular cylindrical chamber and positioned at rear portion inverted conical separate cavity, wherein,
The bottom of circular cone cavity is provided with discharge port, and the side wall of circular cylindrical chamber is equipped with feed inlet, and feed inlet is arranged symmetrically for two groups；
The opposite feed inlet for hitting eddy flow component forms percussion flow after charging, for fluid to be accelerated to rotate speed in conical cavity body
Rate, so as to accelerate the separating effect of moisture in hydrocarbon raw material.
Step（1）In hydrocarbon raw material dewatering, the primary separation is using corrugated plating coalescer.Corrugated plating coalescer can
To use the corrugated plating coalescer of this field routine, if a kind of specific corrugated plating coalescer includes the ripple that dried layer stacks successively up and down
Card, hydrophilic and oleophobic property and the tortuous passageway that flows back and forth using ripple plate surface are several so as to increase the expansion between droplet
Rate promotes the coalescence of small water droplet, carried in hydrocarbon raw material 5~20 μm of small water droplet collection is become flood drop, by gravity
It glides along ripple plate surface, reaches the water out of bottom and complete primary separation；Neighbouring two interlamellar spacing of corrugated plating is generally 3
~6mm is equipped with several dewatering holes at the trough of each laminate, and the big water droplet autospasy water hole assembled and isolated is fallen down；By
In the good initial distribution for being uniformly distributed component so that the negotiability of each layer corrugated plating is almost equivalent, so as to ensure just fraction
Separative efficiency from component.Material is in the residence time of corrugated plating coalescer（By empty coalescer volumeter）For 1~10 minute,
It is preferred that 1.5~3 minutes.Step（1）In hydrocarbon raw material dewatering, material before primary separation is carried out by distributor, by object
Material is evenly distributed to the separation of initial separator from component.Distributor can be various suitable material distributors.Such as it adopts
With 5~10 layers of identical but surface holes stagger arrangement placement orifice plate liquid distribution plate, hydrocarbon raw material charging is uniformly distributed, is conducive to subsequent first
Grade separation and the separated stabilization of depth, the aperture of orifice plate is 4~8mm, and hole center spacing is 20~30mm, in orifice plate liquid distribution plate
Amount up and down respectively leave certain space not perforate greatly, Bock Altitude is 30~80mm, prevents side wall and gap from flowing.
Step（1）In hydrocarbon raw material dewatering, depth separation is using fibrous coalescer.Fibrous coalescer can be
The deep dehydration fibrous coalescer of this field routine.After primary separates, the larger-size water droplet i.e. more than >=5 μm is
It is removed, the remaining small water droplet in smaller szie≤5 μm not being removed is then needed into fibre conglomerates component water-feeding deep
Separation, is separated by the effect of the material and structure of the coalescence material；Generally hollow cylindrical structure, cylindrical surface are parent
Water-based material, surface are poroid for fine and close honeycomb hexagon.Material is in the residence time of fibrous coalescer（By empty coalescer volume
Meter）For 0.5~5 minute, preferably 1.0~2.5 minutes.
Step（1）In hydrocarbon raw material dewatering, hitting eddy flow-primary separation-depth separation can use above-mentioned function
The integral device combined.
Wherein step（2）Alkylated reaction may be employed existing alkylation reaction technique, such as stirring-type alkylation
Reaction, the tower alkylated reaction of filler, micropassage type alkylated reaction etc..
Wherein step（3）Alkylated reaction separation method it is as follows：Alkylation reaction product using sulfuric acid as catalyst passes through
After initial gross separation, into membrane separation plant, the penetrating fluid that UF membrane obtains is mixed with fresh sulfuric acid, then carries out cyclonic separation,
The hydrocarbon ils that cyclonic separation obtains uses the further depickling of coalescer；Wherein the aperture of membrane separation plant film is 50~500nm, preferably
100~300nm, the absolute pressure of membrane separation plant per-meate side is 10~90kPa, preferably 30~80kPa.
Step（3）Alkylated reaction separation method in, the initial gross separation of alkylation reaction product can be sedimentation separation,
One or more of coarse separation, centrifugation, sulfuric acid content is generally 1000~8000mg/ in the material after initial gross separation
Kg is usually 2000~7000 mg/kg.The specific equipment and condition of initial gross separation are well-known to those skilled in the art.Just
The acid obtained after step separation mutually can be recycled to alkylation reactor, can also be further processed using other processing methods.
Step（3）Alkylated reaction separation method in, membrane separation plant can be tubular membrane, plate membrane etc..The present invention
Using the aperture restriction effect of membrane separation plant film, while certain deacidification effect is obtained, it is often more important that using fenestra and
The comprehensive function of per-meate side negative pressure makes the small emulsion droplet demulsification of small hydrocarbon bag acid, is conducive to subsequent depickling processing, therefore
The property of film can have hydrophobicity, can not also need to have hydrophobicity, but need with acid resistance, and preferably acidproof is inorganic
Film, such as ceramic membrane, but it is not required to complicated modification.Sulfuric acid content is generally 500~2000 in membrane separation plant penetrating fluid
Mg/kg, preferably 800~1500 mg/kg.It is mainly sulfuric acid that the concentration of membrane separation plant, which is surveyed, can partly cycle and be set with UF membrane
Standby charging mixing, the outer row in part, outer row part can be cycled for alkylated reaction, can also be further processed.UF membrane is set
Standby penetrating fluid inside and outside differential pressure is generally 0.1~5.0MPaG, preferably 0.5~2.0MPaG；The membrane tube pipe side material of membrane separation plant
Flow velocity is generally 0.5~3.5m/s, preferably 1.0~2.0m/s.
Step（3）Alkylated reaction separation method in, penetrating fluid mixed with fresh sulfuric acid may be employed it is various mixing set
It is standby, such as the mixing of various dynamics or static mixing device, slave device structure, which simplifies, sets out, and present invention preferably employs venturi mixing
Device.It is 1 that fresh sulfuric acid, which is supplemented, with penetrating fluid mixed volume ratio:20~1:500, preferably 1:50~1:200.
Step（3）Alkylated reaction separation method in, cyclonic separation operation can be this field routine cyclonic separation
Device.It is preferred that setting material impingement region in cyclone separator feed zone, i.e., mixed material is divided into two strands of materials, two strands of materials are revolving
Inlet is positive in stream separator hits, and mixed material exists after leaving impingement mix area into cyclone separator, realization sulfuric acid/hydrocarbon
It is separated under super gravity field.In the hydro carbons discharged from cyclone separator, sulfuric acid content general control is 50~500 mg/kg, preferably
100~400 mg/kg.The sulfuric acid isolated after cyclonic separation is recycled back to alkylation reactor.
Step（3）Alkylated reaction separation method in, the further coalescence depickling that hydrocarbon ils is obtained after cyclonic separation can be with
Using the coalescing separator of this field maturation, coalescing separator uses fabric filter element formula structure, and it is fine that fiber therein is selected from metal
One or more in dimension, polytetrafluoroethylene fibre, polypropylene fibre and polyester fiber are compiled after surface hydrophilic modification is handled
It knits, small sulfuric acid droplets in alkylate oil is captured by the hydrophilic and oleophobic property of fiber surface, and in fiber surface enrichment simultaneously
Gradual coalescence is grown up, and the last big droplet settling of sulfuric acid is separated.Material is in the residence time of coalescer（By empty coalescer volume
Meter）For 1.5~5 minutes, preferably 2.5~3.5 minutes.In the alkylate discharged from coalescer sulfuric acid content be generally 1~
10 mg/kg, preferably 5~9 mg/kg, have achieved the effect that depth depickling, can save subsequent alkali cleaning, washing and etc..This
Class coalescer can be commercial product, can also be manufactured by state of the art.
The alkylation of the present invention, due to the water in hydrocarbon raw material, water content is generally 300mg/kg in operational conditions,
When the water that upstream device operation shakiness can carry hydrocarbon raw material reaches >=1000mg/kg, even more high, Water entrainment in the feedstock is so serious
The dilution rate of sulfuric acid can be increased, due to there are certain requirements in alkylated reaction to the concentration of sulfuric acid catalyst, when Xun Huan sulphur
It is required supplementation with when acid concentration is required less than this and replaces new sulfuric acid, therefore water amount conference increases the replacement frequency of sulfuric acid in C4 raw materials
Rate, the problems such as equally causing system acid consumption is high, spent acid discharge capacity is big, generates quickly dilute sulfuric acid big to equipment corrosion, the present invention
Raw material C4 is subjected to deep dehydration first, using hitting eddy flow-be uniformly distributed-primary separation-depth in deep dehydration facility
Separated method is spent, by the moisture removal in raw material to≤10mg/kg.
The method of the present invention is to sulfuric acid process alkylation reaction product using initial gross separation-UF membrane-mixing eo-acid-eddy flow point
From-sour the process of coalescence, the depth depickling of alkylate is effectively realized, alkali cleaning, washing etc. in conventional method can be saved
Step.The membrane separating process of the method for the present invention utilizes the negative of small duct and per-meate side without the use of complicated Modified Membrane
Press operation so that the hydrocarbon bag acid microlayer model of small emulsified state during fenestra road by being demulsified, although the acid removal rate of itself is not
Height, but good physical property basis has been established for subsequent depickling operation, improve the efficiency of follow-up deacidifying device.Using simple
Cyclonic separation operates, and the film unit of preamble is coordinated to operate and supplement appropriate eo-acid so that be originally difficult in cyclonic separation unit
The alkylate of effective depickling realizes the depickling of greater efficiency in cyclonic separation equipment, is subsequent coalescence deacidification
Realize that physical property basis has been established in depth depickling.In short, it is only to change each unit by the organic assembling of several units by the present invention
From the mechanism used, preferable complex art effect is realized.The alkylate depth acid hydrocarbon separating technology of this method,
The deep purifying separation of alkylate can be efficiently completed, saves the processing procedure of the complexity such as alkali cleaning, washing of traditional handicraft,
Not only simplify technological process, material consumption energy consumption is greatly lowered, and make alkylate oil production process more efficiently and environmental protection, fit
It is separated together in the deep purifying of various alkylates.
In short, after the present invention provides a kind of raw material pre-treatment for ensureing the reaction process high efficiency and stability and product
The novel technique of reason for overcome the deficiencies in the prior art, solves problems existing in the prior art, it is anti-to improve alkylation
The integrated artistic for answering technology is advanced.
Description of the drawings
Fig. 1 is present invention process flow diagram.
Wherein 1 is C4 raw materials, and 2 be C4 material depth dehydrators, and 3 be removing water, and 4 be C4 raw material surge tanks, and 5 be C4 raw materials
Feed pump, 6 be C4 raw materials into micro passage reaction material, and 7 be cryogen, and 8 be cryogen surge tank, and 9 be cryogen feed pump, and 10 be cold
Agent is into micro passage reaction material, and 11 be mixing circulation sulfuric acid, and 12 be micro passage reaction, and 13 be reaction product three phase separation
Device, 14 is isolate residual gas, and 15 is isolate sulfuric acid phase, and 16 be thick alkylate oil drawing pump, and 17 feed for membrane separator,
18 be membrane separator, and 19 restrain for membrane tube, and 20 be concentrate, and 21 be outer row's concentrate, and 22 be Xun Huan concentrate, and 23 be infiltration
Liquid, 24 be supplement fresh sulfuric acid, and 25 be sour hydrocarbon mixer, and 26 be sour hydrocarbon depth separator charging, and 27 be sour hydrocarbon depth separator,
28 is isolate sulfuric acid, and 29 be alkylate oil after depth separation, and 30 be mixing circulation sulfuric acid pump.
Specific embodiment
The process and effect of method are further illustrated the present invention by the following examples.
Embodiment 1（Hydrocarbon raw material is dehydrated）
The hydrocarbon raw material of certain alkylated reaction, 326 mg/kg of water content.
" shock eddy flow-be uniformly distributed-primary separation-depth separation " equipment concrete structure and operating condition are as follows：（1）It hits
It hits inverted conical cyclonic separation cavity of the cyclonic unit structure by top closure circular cylindrical chamber and positioned at rear portion to form, wherein round
Barrel chamber body symmetrically feeds for both sides, and inside forms impingement region, and shock flow velocity is 1.5m/s；The cone of inverted conical cyclonic separation cavity
Angle is 45 °；（2）It is the orifice plate that 5 layers of aperture are 8mm, hole center spacing is 30mm to be uniformly distributed component；（3）Primary separation equipment
Using stainless steel corrugated board structures, wherein neighbouring two interlamellar spacing of corrugated plating is 6mm, and open pore size is 2.5mm on plate, perforate
Rate is 14.5%；（4）Depth separation assembly is hollow circuit cylinder filter cartridge construction, and cylindrical surface is hydrophily viscose material, and surface is
Fine and close honeycomb hexagon is poroid, and material is in the residence time of fibrous coalescer（By empty coalescer volumeter）For 1.2 minutes.
After aforesaid operations separate, the water content of hydrocarbon raw material is 6.7 mg/kg after dehydration.
Embodiment 2（Hydrocarbon raw material is dehydrated）
The water content of alkylated reaction hydrocarbon raw material in embodiment 1 is adjusted, analysis result is 713 mg/kg.Dewatering is with implementing
Example 1 is identical.
（1）It is by top closure circular cylindrical chamber and the inverted conical cyclonic separation chamber positioned at rear portion to hit cyclonic unit structure
Body forms, and wherein circular cylindrical chamber symmetrically feeds for both sides, and inside forms impingement region, and shock flow velocity is 2.1m/s；Inverted conical revolves
The cone angle of flow separation cavity is 30 °；（2）It is the orifice plate that 8 layers of aperture are 6mm, hole center spacing is 25mm to be uniformly distributed component；
（3）Primary separation equipment uses stainless steel corrugated board structures, and wherein neighbouring two interlamellar spacing of corrugated plating is 4mm, perforate on plate
Aperture is 2.0mm, percent opening 13.8%；（4）Depth separation assembly is hollow circuit cylinder filter cartridge construction, and cylindrical surface is hydrophily vinegar
Sour fibrous material, surface is poroid for fine and close honeycomb hexagon, and material is in the residence time of fibrous coalescer（Hold by empty coalescer
Product meter）For 1.8 minutes.
After aforesaid operations separate, the water content of hydrocarbon raw material is 5.4mg/kg after dehydration.
Embodiment 3（Hydrocarbon raw material is dehydrated）
The water content of alkylated reaction hydrocarbon raw material in embodiment 1 is adjusted, analysis result is 1245 mg/kg.Dewatering is with implementing
Example 1 is identical.
（1）It is by top closure circular cylindrical chamber and the inverted conical cyclonic separation chamber positioned at rear portion to hit cyclonic unit structure
Body forms, and wherein circular cylindrical chamber symmetrically feeds for both sides, and inside forms impingement region, and shock flow velocity is 2.5m/s；Inverted conical revolves
The cone angle of flow separation cavity is 15 °；（2）It is the orifice plate that 10 layers of aperture are 4mm, hole center spacing is 20mm to be uniformly distributed component；
（3）Primary separation equipment uses stainless steel corrugated board structures, and wherein neighbouring two interlamellar spacing of corrugated plating is 4mm, perforate on plate
Aperture is 1.5mm, percent opening 14.0%；（4）Depth separation assembly is hollow circuit cylinder filter cartridge construction, and cylindrical surface is hydrophily day
Right fiber blend material, surface is poroid for fine and close honeycomb hexagon, and material is in the residence time of fibrous coalescer（It is coalesced by sky
Device volumeter）For 2.5 minutes.
After aforesaid operations separate, the water content of hydrocarbon raw material is 4.2mg/kg after dehydration.
Embodiment 4（Alkylation reaction product separates）
Certain stirring-type sulfuric acid process alkylation reaction product, sulfuric acid content is in the alkylate oil after preliminary sedimentation separates
6367mg/kg。
Alkylate oil UF membrane using the present invention-eo-acid mixing-cyclonic separation-coalescence deacidification, each unit
Operating condition and result are as follows：
1. film separation unit.Ceramic pipe type film of the aperture for 300nm is used, ceramic pipe type film surface is not required to modification.Tubular type
The shell-side of film is penetrating fluid, and pipe side is concentrate.The membrane tube pipe side material flow of membrane separation plant is 0.95m/s, and UF membrane is set
Standby penetrating fluid inside and outside differential pressure is 0.7MPaG, and shell-side connects vacuum system, and shell-side absolute pressure is 75 kPa.Sulfuric acid contains in penetrating fluid
It measures as 1065mg/kg.Concentrate part is cycled, the outer row in part, and the concentrate of outer row can also be recycled to alkane as spent acid processing
Glycosylation reaction system.
2. eo-acid mixed cell.Using venturi mixer, fresh sulfuric acid is the fresh sulphur of supplement of alkylated reaction system
The mixed volume ratio of acid, fresh sulfuric acid and penetrating fluid is 1:185.
3. cyclonic separation unit.Cyclonic separation unit intake section hits mode, eo-acid mixing using two bursts of material convection current
Unit effluent is divided into two strands of materials, and inlet, which is formed, in cyclonic separation unit hits, subsequently into cyclonic separation section, super
Sour hydrocarbon separation is carried out under gravity field action.Sulfuric acid content is 179 mg/kg in the hydrocarbon phase of cyclonic separation unit outlet.Cyclonic separation
The sulfuric acid of unit outlet is recycled to alkylated reaction unit.
4. coalesce depth depickling unit.Deacidification equipment, the fiber table of fabric filter element are coalesced using conventional fabric filter element formula
Face uses the material with hydrophilic and oleophobic performance to be made.Material is in the residence time of coalescer（By empty coalescer volumeter）For
2.75 minute.It is 5.0 mg/kg to coalesce unit outlet material sulfuric acid content.
Comparative example 1
For the alkylation reaction product described in embodiment 1, the place twice of the same terms is carried out using the coalescence unit of step 4
Reason, sulfuric acid content is 1375 mg/kg in product after single treatment, and sulfuric acid content is 1068 mg/kg in product after after-treatment.
Comparative example 2
For the alkylation reaction product described in embodiment 1, the film process unit of step 1 is replaced using the coalescence unit of step 4,
Other processes and condition are the same as embodiment 1.For the first time coalescence deacidified product in sulfuric acid content be 1375 mg/kg, cyclonic separation unit
Sulfuric acid content is 952 mg/kg in outlets products, and it is 367mg/kg that second, which coalesces sulfuric acid content in deacidified product,.
Embodiment 5（Alkylation reaction product separates）
Certain material filling type sulfuric acid process alkylation reaction product, sulfuric acid content is in the alkylate oil after preliminary sedimentation separates
3543mg/kg。
Alkylate oil UF membrane using the present invention-eo-acid mixing-cyclonic separation-coalescence deacidification, each unit
Operating condition and result are as follows：
1. film separation unit.Ceramic pipe type film of the aperture for 200nm is used, ceramic pipe type film surface is not required to modification.Tubular type
The shell-side of film is penetrating fluid, and pipe side is concentrate.The membrane tube pipe side material flow of membrane separation plant is 1.16m/s, and UF membrane is set
Standby penetrating fluid inside and outside differential pressure is 1.2MPaG, and shell-side connects vacuum system, and shell-side absolute pressure is 60 kPa.Sulfuric acid contains in penetrating fluid
It measures as 821mg/kg.Concentrate part is cycled, the outer row in part, and the concentrate of outer row can also be recycled to alkane as spent acid processing
Glycosylation reaction system.
2. eo-acid mixed cell.Using venturi mixer, fresh sulfuric acid is the fresh sulphur of supplement of alkylated reaction system
The mixed volume ratio of acid, fresh sulfuric acid and penetrating fluid is 1:110.
3. cyclonic separation unit.Cyclonic separation unit intake section hits mode, eo-acid mixing using two bursts of material convection current
Unit effluent is divided into two strands of materials, and inlet, which is formed, in cyclonic separation unit hits, subsequently into cyclonic separation section, super
Sour hydrocarbon separation is carried out under gravity field action.Sulfuric acid content is 143 mg/kg in the hydrocarbon phase of cyclonic separation unit outlet.Cyclonic separation
The sulfuric acid of unit outlet is recycled to alkylated reaction unit.
4. coalesce depth depickling unit.Deacidification equipment, the fiber table of fabric filter element are coalesced using conventional fabric filter element formula
Face uses the material with hydrophilic and oleophobic performance to be made.Material is in the residence time of coalescer（By empty coalescer volumeter）For
3.0 minute.It is 5.7 mg/kg to coalesce unit outlet material sulfuric acid content.
Embodiment 6（Alkylation reaction product separates）
Certain micropassage type sulfuric acid process alkylation reaction product, sulfuric acid content is in the alkylate oil after preliminary sedimentation separates
2938mg/kg。
Alkylate oil UF membrane using the present invention-eo-acid mixing-cyclonic separation-coalescence deacidification, each unit
Operating condition and result are as follows：
1. film separation unit.Ceramic pipe type film of the aperture for 100nm is used, ceramic pipe type film surface is not required to modification.Tubular type
The shell-side of film is penetrating fluid, and pipe side is concentrate.The membrane tube pipe side material flow of membrane separation plant is 1.72m/s, and UF membrane is set
Standby penetrating fluid inside and outside differential pressure is 1.8MPaG, and shell-side connects vacuum system, and shell-side absolute pressure is 40 kPa.Sulfuric acid contains in penetrating fluid
It measures as 675mg/kg.Concentrate part is cycled, the outer row in part, and the concentrate of outer row can also be recycled to alkane as spent acid processing
Glycosylation reaction system.
2. eo-acid mixed cell.Using venturi mixer, fresh sulfuric acid is the fresh sulphur of supplement of alkylated reaction system
The mixed volume ratio of acid, fresh sulfuric acid and penetrating fluid is 1:75.
3. cyclonic separation unit.Cyclonic separation unit intake section hits mode, eo-acid mixing using two bursts of material convection current
Unit effluent is divided into two strands of materials, and inlet, which is formed, in cyclonic separation unit hits, subsequently into cyclonic separation section, super
Sour hydrocarbon separation is carried out under gravity field action.Sulfuric acid content is 129 mg/kg in the hydrocarbon phase of cyclonic separation unit outlet.Cyclonic separation
The sulfuric acid of unit outlet is recycled to alkylated reaction unit.
4. coalesce depth depickling unit.Deacidification equipment, the fiber table of fabric filter element are coalesced using conventional fabric filter element formula
Face uses the material with hydrophilic and oleophobic performance to be made.Material is in the residence time of coalescer（By empty coalescer volumeter）For
3.5 minute.It is 5.2 mg/kg to coalesce unit outlet material sulfuric acid content.
Alkylate depth separation method using the present invention is can be seen that from the present embodiment result, it can be effective
Thick alkylate oil is carried out to force demulsification and depth separation, the sulfuric acid that alkylate oil carries is reduced, saves alkali cleaning and washing unit,
Sulfuric acid content≤6mg/kg in alkylate oil after this treatment has significant economy.
Claims (11)
1. a kind of alkylation, includes the following steps：
（1）Hydrocarbon raw material is dehydrated；
（2）The alkylated reaction of hydrocarbon raw material is carried out using sulfuric acid as catalyst；
（3）Alkylation reaction product separates；
Wherein step（1）Hydrocarbon raw material dewatering is as follows：Using eddy flow-primary separation-depth separation process is hit, will be alkylated
The moisture removal in hydrocarbon raw material is reacted to≤10mg/kg, stable charging is provided for alkylation process, hydrocarbon raw material is isobutyl
Alkane and C3-C5 alkene.
2. according to the method for claim 1, it is characterised in that：Step（1）In hydrocarbon raw material dewatering, shock rotation
Stream operation collides the small water droplet in hydrocarbon raw material, coalescence and cyclonic separation, is set in cyclone separator at material inlet
Material is divided into two strands by impingement region, which introduces cyclone separator in opposite directions, and the shock that material is formed in impingement region is made
With；Material after shock enters eddy flow area, carries out eddy flow operation, separates the water in hydrocarbon raw material.
3. according to the method for claim 1, it is characterised in that：Step（1）In hydrocarbon raw material dewatering, the first fraction
From using corrugated plating coalescer.
4. according to the method for claim 1, it is characterised in that：Step（1）In hydrocarbon raw material dewatering, the depth point
From using fibrous coalescer.
5. according to the method described in claim 1,2,3 or 4, it is characterised in that：Step（1）In hydrocarbon raw material dewatering, hit
Eddy flow-primary separation-depth separation process uses the integral device for combining above-mentioned function.
6. according to the method for claim 1, it is characterised in that：Wherein step（2）Alkylated reaction use stirring-type alkane
The tower alkylated reaction of glycosylation reaction, filler or micropassage type alkylated reaction.
7. according to the method for claim 1, it is characterised in that：Wherein step（3）Alkylation reaction product separation method
It is as follows：Alkylation reaction product is after initial gross separation, and into membrane separation plant, penetrating fluid and fresh sulfuric acid that UF membrane obtains mix
It closes, then carries out cyclonic separation, the hydrocarbon ils that cyclonic separation obtains uses the further depickling of coalescer；Wherein membrane separation plant film
Aperture is 50~500nm, preferably 100~300nm, and the absolute pressure of membrane separation plant per-meate side is 10~90kPa, preferably 30~
80kPa。
8. according to the method for claim 7, it is characterised in that：The initial gross separation of alkylation reaction product be sedimentation separation,
One or more of coarse separation, centrifugation, sulfuric acid content is 1000~8000mg/kg in the material after initial gross separation,
Preferably 2000~7000 mg/kg.
9. according to the method for claim 7, it is characterised in that：Membrane separation plant is tubular membrane or plate membrane；The property of film
With hydrophobicity or without hydrophobicity；Sulfuric acid content is 500~2000 mg/kg in membrane separation plant penetrating fluid, preferably
800~1500 mg/kg.
10. according to the method for claim 7, it is characterised in that：Cyclone separator feed zone sets material impingement region, will
Mixed material is divided into two strands of materials, and two strands of materials inlet in cyclone separator is positive to hit, and it is mixed that mixed material leaves shock
It is separated after closing area into cyclone separator, realization sulfuric acid/hydrocarbon under super gravity field；In the hydro carbons discharged from cyclone separator, sulphur
Acid content control is 50~500 mg/kg, preferably 100~400 mg/kg.
11. according to the method for claim 7, it is characterised in that：Depickling is coalesced using fabric filter element formula structure, fibre therein
The one or more tieed up in metallic fiber, polytetrafluoroethylene fibre, polypropylene fibre and polyester fiber pass through surface hydrophilic
It is woven after modification, small sulfuric acid droplets in alkylate oil is captured by the hydrophilic and oleophobic property of fiber surface, and in fibre
Dimension surface enrichment simultaneously gradually grow up by coalescence, and the last big droplet settling of sulfuric acid is separated；The alkylate discharged from coalescer
Middle sulfuric acid content is 1~10 mg/kg, preferably 5~9 mg/kg.
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| CN112920844A (en) * | 2021-01-20 | 2021-06-08 | 华东理工大学 | Device and method for improving quality of alkylated oil product |
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