CN105670686B - The method and apparatus of alkylated reaction effluent pickling - Google Patents
The method and apparatus of alkylated reaction effluent pickling Download PDFInfo
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- CN105670686B CN105670686B CN201610123789.9A CN201610123789A CN105670686B CN 105670686 B CN105670686 B CN 105670686B CN 201610123789 A CN201610123789 A CN 201610123789A CN 105670686 B CN105670686 B CN 105670686B
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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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/10—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one acid-treatment step
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Abstract
The present invention relates to the method and apparatus of alkylated reaction effluent pickling there is provided a kind of method of alkylated reaction effluent pickling, this method comprises the following steps：(i) alkylate containing sulfuric acid droplets and sulfuric ester is contacted with mixing new sulfuric acid by forming liquid film reinforcing；And (ii) is promoted the separation of alkylated reaction effluent and sulfuric acid, sulfuric ester and sulfuric acid droplets in alkylated reaction effluent is removed completely using the demulsification coalescence for separating filler-reinforced sulfuric acid droplets.Additionally provide a kind of device of alkylated reaction effluent pickling.
Description
Technical field
The invention belongs to be alkylated spent acid process field, be related to the method for reaction effluent pickling in alkylated reaction with
Device, more specifically to the acid settler hydrocarbon phase using reactor downstream in the alkylation process of sulphur acid as catalyst
Effluent carries out the method and apparatus of pickling.
Background technology
Currently, environmental pollution is increasingly seriously China or even the big quagmire that is faced of the world, and to the producing of people, raw
Work causes strong influence, therefore environmental protection is by the most attention of countries in the world.According to China in Recent Years environmental protection
What portion was announced《China Environmental State Bulletin》Data, Vehicular exhaust pollution has accounted for 20% or so in various pollution sources, simultaneously
With the increase of car ownership, pollution of the vehicle exhaust to environment is on the rise, thus environmental protection is to the pungent of motor petrol
Alkane value and cleannes propose more harsh requirement.In the world, the overall standard of clean gasoline is towards low-sulfur, low fragrant, low alkene
In the case that high cleanliness and high-octane rating direction are developed, alkylate oil is progressively valued by people.
Alkylate oil is that the light olefin of iso-butane and C3~C5 reacts generation in the presence of strong acid catalyst, is a kind of
Isoparaffin mixture.Compared with catalytic gasoline and Reformed Gasoline, alkylate oil has octane number height, not olefin-containing aromatic hydrocarbons, sulphur
The low feature of content, the content of the harmful constituents such as alkene, aromatic hydrocarbons, sulphur can be reduced by being called in gasoline, while improving gasoline
Octane number and the capability of antidetonance, be a kind of preferably cleaning motor petrol component.Therefore the production of alkylate oil is by oil refining work
The pay attention to day by day of industry.
It is well known that alkylation process mainly includes sulfuric acid alkylation and hydrofluoric acid alkylation, the present invention is directed with
Sulfuric acid as catalyst alkylation process.Normally, in sulfuric acid alkylation technique, by iso-butane and light olefin materials and concentration
More than 90% qualified sulfuric acid catalyst is delivered to Stratco reactors, under the high-power agitator effect of the reactor, sulphur
Acid is mutually fully dispersed and mix with hydrocarbon, forms sour hydrocarbon emulsion so as to complete alkylated reaction, and acid hydrocarbon mixed emulsion is into sinking afterwards
Separator is dropped, the separation of sulfuric acid and hydrocarbon phase is realized in the presence of phase density difference, and obtain hydrocarbon phase reaction effluent and sulfuric acid.So
And, because the height of sulfuric acid in alkylation process is emulsified and generates the sulfur byproduct species such as sulfuric ester, therefore in hydrocarbon phase reaction stream
Go out in thing always to carry micro emulsification sulfuric acid droplets and sulfuric ester, they can cause serious corrosion to the process equipment in downstream
Destruction, it is therefore necessary to sulfuric acid and sulfuric ester impurity fully in removing hydrocarbon phase reaction effluent.
Pickling is the first procedure for removing impurity in hydrocarbon phase reaction effluent, subsequently also alkali cleaning, washing etc..But it is existing
Some acid washing methods and equipment can not efficiently remove sulfuric acid and sulfuric ester, still result in the etching problem to upstream device.
And in existing acid washing method, pickling sulfuric acid is disposably added in pickling tank so that part of sulfuric acid also has little time and alkyl
Change product contact just discharge pickling tank, this part of sulfuric acid could not be made full use of；Meanwhile, existing acid washing method needs follow-up alkali cleaning
Etc. process, it on the one hand can unnecessarily increase the unrelated component in alkylate oil, on the other hand can not also avoid to follow-up equipment
Corrosion failure.
Therefore, this area can effectively realize alkylated reaction effluent removing sulfuric acid and sulfuric acid in the urgent need to developing
The method and apparatus of ester, makes alkylated hydrocarbons phase product sufficiently cleaned up and reduces the corrosion failure to equipment.
The content of the invention
It is an object of the invention to provide a kind of method and apparatus of novel alkylated reaction effluent pickling, so as to fill
The sulfuric acid droplets and sulfuric ester divided in purifying alkyl product, removing alkylate, reduce the corrosion failure to system equipment.
The invention provides a kind of method and apparatus so that the sulfuric acid newly added in acid cleaning process can fully with the sulfuric acid in hydrocarbon phase
Ester and acid drop contact, reinforcing are mutually dissolved extraction, and promote sour hydrocarbon to separate by the separation filler in separator, so as to reach
The purpose of sulfuric ester and sulfuric acid droplets in full removing alkylate, solves problems of the prior art.
On the one hand, the invention provides a kind of method of alkylated reaction effluent pickling, this method comprises the following steps：
(i) alkylate containing sulfuric acid droplets and sulfuric ester is connect with mixing new sulfuric acid by forming liquid film reinforcing
Touch；And
(ii) using the demulsification coalescence for separating filler-reinforced sulfuric acid droplets, point of alkylated reaction effluent and sulfuric acid is promoted
From making sulfuric ester and sulfuric acid droplets in alkylated reaction effluent remove completely.
In one preferred embodiment, it is anti-that the sulfuric acid part separated in the step (ii) participates in alkylation
Should, another part is returned and mixed with new sulfuric acid, and participates in what the amount of the sulfuric acid of alkylated reaction was mixed equal to return with new sulfuric acid
The amount of sulfuric acid.
Another preferred embodiment in, the new sulfuric acid of mixing is divided into multiple flow and contacted respectively with alkylate,
Wherein, the new sulfuric acid of mixing is the mixing liquid of new sulfuric acid and time new sulfuric acid, and the new sulfuric acid is that additional concentration is not less than
98% fluid sulphuric acid, described time new sulfuric acid is the sulfuric acid of the participation overpickling for the return separated in the step (ii).
Another preferred embodiment in, it is described separation filler use hydrophilic and hydrophobic fibrous material weaving
Form, wherein fibre diameter is 80~500 μm, porosity is 70~85%；The thickness of the separation filler is 200~400mm.
On the other hand, the invention provides a kind of device of alkylated reaction effluent pickling, the device includes：
The pickling tank of be connected with blender including pickling section and segregation section, wherein, microchannel is set in the pickling section
Silk screen, by the alkylate containing sulfuric acid droplets and sulfuric ester with mixing new sulfuric acid on the silk screen of microchannel by forming liquid
Film reinforcing contact；Separation filler is set in the segregation section, to strengthen the demulsification coalescence of sulfuric acid droplets, promotes alkylated reaction stream
Go out the separation of thing and sulfuric acid, sulfuric ester and sulfuric acid droplets in alkylated reaction effluent is removed completely.
In one preferred embodiment, the microchannel silk screen is set to multistage, and every section mixed with certain proportion addition
New sulfuric acid is closed, the amount of sulfuric acid in flow direction is increased paragraph by paragraph；The microchannel silk screen uses polymer fiber or metallic fiber system
, the fiber is woven according to irregular arrangement mode, so as to form irregular microchannel；The microchannel silk screen
Thickness be 300~500mm, the fibre diameter used is for 20~100 μm, and porosity is 50~75%, and every section of silk screen it
Between distance be not less than 200mm.
Another preferred embodiment in, pickling section includes alkylated reaction effluent entrance, mixes new sulphur
Sour entrance, reaction effluent liquid distribution trough, the new sulfate liquid distributor of mixing and microchannel silk screen；The segregation section includes dividing
From filler, the outlet of hydrocarbon phase net outflow thing and sulfuric acid outlet.
Another preferred embodiment in, the quantity of the new sulfuric acid entrance of the mixing is 2 or more, spacing by
The thickness of microchannel silk screen is determined.
Another preferred embodiment in, the reaction effluent liquid distribution trough and mix the distribution of new sulfate liquid
Utensil has identical structure, including calandria, spiral, triadius type or grid type.
Another preferred embodiment in, the segregation section include one section or multistage separation filler, in segregation section
Bottom is that pickling pot bottom sets sulfuric acid to export, and the place apart from bottom at least 400mm on segregation section sets hydrocarbon phase net outflow
Thing is exported.
Beneficial effect：
Beneficial effects of the present invention mainly include two aspects：One is that segmentation adds new sulphur in the pickling section of pickling tank
Acid, by forming liquid film, strengthens new sulfuric acid and is contacted with the sulfuric acid droplets in alkylate oil and the mixing of sulfuric ester, make sulfuric acid droplets
Fully extracted by new sulfuric acid with sulfuric ester；Two be the segregation section of pickling tank so that the acid drop fully coalescence not being extracted, reinforcing
Demulsification, promotes the separation of sulfuric acid and alkylate oil.Specifically：
(1) liquid distribution trough makes new sulfuric acid and alkylated reaction effluent fully uniform point on the cross section of pickling tank
Cloth, and in the top certain space of every section of microchannel silk screen, new sulfuric acid can be made to be mixed in advance with alkylated reaction effluent
Close, then flow to microchannel silk screen simultaneously again.
(2) in the microchannel silk screen, because hydrocarbon phase is different to the close and distant property of web material with sulfuric acid, wherein one
Liquid film is formed on silk screen, the time of contact of two-phase can be increased, increases the contact area of two-phase, the extraction effect of new sulfuric acid is improved
Rate；More than 99% sulfuric acid droplets are extracted on the microchannel silk screen, while sulfuric ester is entered in sulfuric acid by complete extraction.
(3) invention increases the refluxing portion of secondary new sulfuric acid, described new sulfuric acid is from the mutually outlet discharge of segregation section acid
Participation overpickling sulfuric acid, these new sulfuric acid are the sour phase effluents of pickling system, its export concentration all more than 96%；
The new sulfuric acid of mixing is that new sulfuric acid is mixed with time new sulfuric acid；Backflow and the shape of the new sulfuric acid of mixing due to secondary new sulfuric acid
Into improving the utilization ratio of sulfuric acid.
(4) segregation section of the pickling tank is the separation in the device that alkylate is separated with sulfuric acid, the segregation section
Filler is interlocked using hydrophilic and hydrophobic fibrous material works out, and can promote the coalescence of sulfuric acid droplets so that through peracid
The sulfuric acid droplets coalescence remained after washing in alkylate, reinforcing demulsification improves the separative efficiency of sour hydrocarbon, makes alkylate
In alkylate oil be completely separated from sulfuric ester and sulfuric acid droplets, the alkylate oil being purified.
Brief description of the drawings
Accompanying drawing is provided for a further understanding of the present invention, and it simply forms the part of this specification to enter one
Step explains the present invention, is not construed as limiting the invention.
Fig. 1 is the alkylated reaction effluent acid cleaning process schematic flow sheet according to an embodiment of the invention.
Embodiment
Present inventor, can not for traditional pickling tank and its acid washing method by in-depth study extensively
Corrosion failure of the alkylate containing sulfuric acid droplets and sulfuric ester to upstream device is solved well, and once in pickling
The impurity such as sulfuric acid droplets and sulfuric ester can not be effectively removed in tank, then will increase the use of alkali lye in follow-up alkali cleaning link
Amount, and be difficult by impurity removal it is clean the problem of, by pickling tank be divided into pickling section and segregation section, pickling section in be set to multistage
Microchannel silk screen, these microchannel silk screens are brokenly woven and formed using polymer fiber or metallic fiber, due to alkane
Base carburetion is different to the close and distant property of microchannel silk screen with sulfate liquid so that liquid film is formed on the silk screen of microchannel, is thus strengthened
Extraction of the sulfuric acid to sulfuric acid droplets and sulfuric ester in alkylated reaction effluent；In addition further through many on flow direction in pickling tank
The microchannel silk screen of section so that alkylate often can all have the new sulfuric acid of mixing to add by one section of microchannel silk screen, so carry
The high contact area and contacting efficiency of sulfuric acid and alkylate, enhance contact effect of extracting；And in segregation section, pass through
Separate using so that the acid drop being still present in after pickling in alkylate can fully be coalesced as larger acid for filler
Drop, strengthens demulsification, promotes sedimentation separation, so that the sulfuric ester and sulfuric acid that are effectively stripped of in alkylated reaction effluent
Drop, simplifies follow-up link, reduces cost of investment.
The technical concept of the present invention is as follows：
(1) it is alkylated the method for pickling：Microchannel silk screen in pickling tank is set to multi-segment structure, and new sulphur will be mixed
Acid is divided into multiple flow, and blended new sulfuric acid entrance is added in the pickling section of pickling tank respectively, by making alkylate micro- logical
Liquid film is formed on road silk screen, and adds new sulfuric acid paragraph by paragraph, the contact area of increase pickling sulfuric acid and alkylate, increase both
Time of contact, reinforcing pickling sulfuric acid to sulfuric acid droplets in alkylate and the extraction of sulfuric ester；In point of pickling tank
From in section, using the sulfuric acid liquid in hydrophilic and hydrophobic fiber material weaving separation filler, reinforcing alkylate
The demulsification of drop, makes the abundant coalescence of droplet-like sulfuric acid, improves the effect of sour hydrocarbon separation.
(2) device of alkylated reaction effluent pickling includes pickling tank, blender etc..The pickling tank is vertical pressure
Force container, and it is divided into pickling section and segregation section.The blender is used for new sulfuric acid and is returned from time new sulphur of pickling pot bottom
Acid is mixed, and each section of microchannel silk screen is then delivered to respectively.
(3) the pickling section of pickling tank is by the import of alkylated reaction effluent, sulfuric acid entrance, liquid distribution trough and microchannel silk
Net composition.Wherein, the alkylated reaction effluent import containing sulfuric acid droplets and sulfuric ester is arranged on the top of pickling tank；New sulphur
After sour and its with return blender time new sulfuric acid is mixed, the sulfuric acid entrance through pickling tank enters system, and sulfuric acid entry number is
Two or more, and the pickling microchannel silk screen of multistage is set in pickling tank；Liquid distribution trough has hydrocarbon phase liquid distribution
Device and sulfate liquid distributor, both construct it is identical, its act on mainly make the alkylate containing sulfuric acid and sulfuric ester and
New sulfuric acid is uniformly distributed on the cross section of pickling tank, it is to avoid bias current；Microchannel silk screen is fine using polymer fiber or metal
Dimension is made, and less flow channels are formed between every fiber, and ensures there are enough porositys, makes to be formed on the silk screen of microchannel
Liquid film, strengthens new sulfuric acid and the sulfuric ester in alkylate and the contact of sulfuric acid droplets, promotes new sulfuric acid extraction acid drop and sulphur
Acid esters.
(4) segregation section of pickling tank is mainly mutually exported including fiber separation filler, hydrocarbon and acid is mutually exported.Wherein, separation is filled out
Material is formed using hydrophilic and hydrophobic fibrous material weaving, and has appropriate porosity, on the one hand promotes sulfuric acid droplets
Further coalescence, on the other hand will also consider to be unlikely to cause excessive pressure drop；Hydrocarbon, which is mutually exported, is arranged on distance separation section bottom
Position no less than 400mm, upstream device is flowed to for the alkylate through being stripped of sulfuric acid and sulfuric ester；Sour mutually outlet is set
In pickling pot bottom, a part time new sulfuric acid in the outlet enters alkylation reactor and participates in alkylated reaction, and another part enters
Blender is mixed with new sulfuric acid.
In the first aspect of the present invention there is provided a kind of method of alkylated reaction effluent pickling, this method includes：
Alkylate containing sulfuric acid droplets and sulfuric ester is led to mixing new sulfuric acid in the micro- of pickling section of pickling tank
By forming liquid film reinforcing contact on road silk screen, specifically, microchannel silk screen is set to multistage, every section is added with certain proportion
New sulfuric acid is mixed, the amount of sulfuric acid in flow direction is increased paragraph by paragraph, the new sulfuric acid of reinforcing mixing is to sulfuric acid droplets in alkylate and sulphur
The extraction of acid esters；And
By the coalescence of the filler-reinforced sulfuric acid droplets of separation in the segregation section of pickling tank, promote alkylate oil and sulfuric acid
Separation, makes sulfuric ester and sulfuric acid droplets in alkylated reaction effluent remove completely.
In the present invention, the new sulfuric acid of mixing is divided into the new sulfuric acid entrance of mixing of the multiple flow respectively through pickling tank and is added to acid
In cleaning of evaporator, the new sulfuric acid of mixing is liquid acid of the concentration more than 97%, and this method can strengthen new sulfuric acid to alkylation
The extraction of sulfuric acid droplets and sulfuric ester in product, and improve the utilization ratio of pickling sulfuric acid.
In the present invention, when the alkylate after pickling flows through the separation filler in the segregation section of pickling tank, filled out at this
The a small amount of acid drop demulsification coalescence remained in the lower reinforcing alkylate of material effect, is realized in the sedimentation separation region of pickling pot bottom
Sour hydrocarbon separation.
In the present invention, a part of sulfuric acid of sulfuric acid that the segregation section sedimentation separation through pickling tank comes out enters alkylated reaction
Device participates in alkylated reaction, and another part sulfuric acid returns to blender and mixed with concentration for 98% new sulfuric acid, and enters reaction
The amount of the sulfuric acid of device is equal to the amount for being newly added to the concentration of blender for 98% new sulfuric acid.
In the second aspect of the present invention there is provided a kind of device of alkylated reaction effluent pickling, the device includes：With
The pickling tank of blender connection, the pickling tank is made up of pickling section and segregation section, and the pickling section includes alkylated reaction stream
Go out thing entrance, mix new sulfuric acid entrance, reaction effluent liquid distribution trough, mix new sulfate liquid distributor and microchannel silk
Net, the segregation section includes separation filler, the outlet of hydrocarbon phase net outflow thing and sulfuric acid outlet.
In the present invention, mix the quantity of new sulfuric acid entrance for two and more than, entrance spacing by microchannel silk screen thickness
Degree is determined；The new vitriolic acid flux of mixing of each entrance is determined by on-site actual situations；The new sulfuric acid of the mixing for new sulfuric acid and
The mixing liquid of secondary new sulfuric acid, the new sulfuric acid is the fluid sulphuric acid of additional concentration more than 98%, described time new sulfuric acid be from
The sulfuric acid for the participation overpickling that the sulfuric acid outlet of pickling tank is returned.
In the present invention, the reaction effluent liquid distribution trough and the new sulfate liquid distributor of mixing have identical knot
Structure, can be one kind in calandria, spiral, triadius type or grid type.
In the present invention, the microchannel silk screen is made using polymer fiber or metallic fiber, the fiber according to
Irregular arrangement mode is woven, so as to form irregular microchannel.The thickness of the microchannel silk screen be 300~
500mm, the fibre diameter used is 20~100 μm, and porosity is 50~75%, and the distance between every section of silk screen is not less than
200mm。
In the present invention, the segregation section is made up of one section or multistage separation filler, and particular number can make according to scene
It is that the bottom of pickling tank sets sulfuric acid to export in segregation section bottom, apart from bottom at least 400mm on segregation section with being adjusted
Place the outlet of hydrocarbon phase net outflow thing is set.
In the present invention, the separation filler is formed using hydrophilic and hydrophobic fibrous material weaving, fibre diameter
For 80~500 μm, porosity is 70~85%；The thickness of the separation filler is 200~400mm.
Below referring to accompanying drawing.
Fig. 1 is the alkylated reaction effluent acid cleaning process schematic flow sheet according to an embodiment of the invention.Such as
Shown in Fig. 1, the device of the alkylated reaction effluent pickling includes pickling tank 3 and blender 1, wherein, the pickling tank 3 by
Pickling section and segregation section composition, the pickling section include alkylated reaction effluent entrance 4, mix new sulfuric acid entrance 2, reaction stream
Go out thing liquid distribution trough 5, mix new sulfate liquid distributor 6 and microchannel silk screen 7；Wherein described alkylated reaction effluent enters
Mouth 4 is arranged on the top of pickling tank 3, and the new sulfuric acid entrance 2 of mixing is arranged on the side of pickling tank 3, and quantity is 3, spacing
Determined by the thickness of microchannel silk screen, the new sulfuric acid of mixing is new sulfuric acid and time mixed liquor of new sulfuric acid, and its concentration is 97%
More than, described new sulfuric acid is the sulfuric acid of the participation overpickling returned from the segregation section sulfuric acid outlet 10 of pickling tank 3；Described time new
Sulfuric acid part discharge pickling system enters reactor and participates in alkylated reaction, and another part returns to blender 1 and mixed with new sulfuric acid
Close, and amount of the amount equal to the new sulfuric acid for adding blender 1 of time new sulfuric acid of discharge system；
The reaction effluent liquid distribution trough 5 is identical with the construction for mixing new sulfate liquid distributor 6, and it acts on main
It is alkylate and new sulfuric acid containing sulfuric acid and sulfuric ester is uniformly distributed on the cross section of pickling tank 3, it is to avoid bias current；
The microchannel silk screen 7 is formed using polymer fiber or weaving metallic fibers, and fibre diameter is 20~100 μm, and fiber
Between form less flow channels, and ensure there are enough porositys, general porosity is 50~75% oil in microchannel silk
Liquid film is formed on net 7, strengthens new sulfuric acid contact with sulfuric acid and sulfuric ester in alkylate, promotes new sulfuric acid extraction acid drop
And sulfuric ester；The distance between described every section of microchannel silk screen 7 is not less than 200mm；
The segregation section of the pickling tank 3 includes fiber separation filler 8, hydrocarbon phase net outflow thing outlet 9 and sulfuric acid outlet 10, its
In, the separation filler 8 is interlocked using hydrophilic and hydrophobic fibrous material works out, and has appropriate porosity, general hole
Gap rate is the further coalescence of 70~85% sulfuric acid droplets, on the other hand also to consider to be unlikely to cause excessive pressure drop；It is described
Separation filler 8 can actually use one or more snippets according to scene, if multistage is then not less than 300mm for the distance between every section；Institute
State hydrocarbon phase net outflow thing outlet 9 and be arranged on the position that 400mm is no less than apart from the bottom of pickling tank 3, for through being stripped of sulfuric acid and sulphur
The alkylate of acid esters flows to upstream device (dereaction device)；The sulfuric acid outlet 10 is arranged on the bottom of pickling tank 3；
Concrete technology flow process is as follows：
A) come acid deposition groove after autoreactor, the alkylated reaction effluent containing sulfuric acid droplets and sulfuric ester passes through
The reaction effluent liquid distribution trough 5 that alkylated reaction effluent entrance 4 enters in pickling tank 3, in reaction effluent liquid point
In the presence of cloth device 5, reaction effluent is evenly distributed on the cross section of pickling tank 3, is flowed downward；
B) concentration of blender 1 is come from micro- to each through multiple branch circuit pipeline for more than the 97% new sulfuric acid of mixing
The new sulfate liquid distributor 6 of mixing corresponding to passage silk screen 7, mixes new in the presence of new sulfate liquid distributor 6 is mixed
Sulfuric acid is uniformly distributed on the cross section of pickling tank 3；
C) the new sulfuric acid of mixing that blended new sulfate liquid distributor 6 is sent out with from 30~50mm on its vertical direction away from
From alkylate be pre-mixed, then mix new sulfuric acid and alkylate and flow to microchannel silk screen 7 jointly；
D) on microchannel silk screen 7, due to close and distant reason of the web material used to oil and water, wherein one meets micro- logical
Liquid film is formed on road silk screen 7, so as to strengthen contact, the contact area of sulfuric acid and alkylate is greatly increased, improves
Contacting efficiency, enhances sulfuric acid to sulfuric acid droplets in alkylate and the effect of extracting of sulfuric ester；
E) sulfuric acid and the mixing liquid of alkylate oil after the pickling of multistage microchannel silk screen 7 enters pickling tank 3
Segregation section, in the segregation section, alkylate oil flows through together with sulfuric acid separates filler 8 so that in alkylate oil still compared with
Small acid produces coalescence effect in the presence of dropping in separation filler 8；And
F) after separation filler 8, in the bottom of pickling tank 3, namely segregation section bottom due to density contrast, alkylate oil
It is layered rapidly with sulfuric acid, the sulfuric acid droplets and sulfuric ester in alkylate are removed, the alkylate oil being purified.
Main advantages of the present invention are：
The liquid film that the present invention is formed by microchannel silk screen is acted on, and increase pickling sulfuric acid connects with alkylated reaction effluent
Time, contact area are touched, contacting efficiency is improved, strengthens extraction of the new sulfuric acid to sulfuric acid droplets in alkylate and sulfuric ester and makees
With；The demulsification of smaller acid drop, promotes sour hydrocarbon in the filler-reinforced alkylate of separation woven further through fibrous material
Separation.By the implementation of the present invention, sulfuric acid droplets and sulfuric ester in alkylated reaction effluent etc., letter can be fully removed
Change pickling process, eliminate the corrosion failure to system equipment.
Embodiment
The present invention is expanded on further with reference to specific embodiment.It should be appreciated, however, that these embodiments are only used for
It is bright the present invention and be not meant to limit the scope of the invention.The test method of unreceipted actual conditions in the following example, generally
According to normal condition, or according to the condition proposed by manufacturer.Unless otherwise indicated, all percentage and number be by weight
Meter.
Embodiment 1：
Carried out according to the flow of the alkylated reaction effluent pickling shown in Fig. 1, wherein, microchannel silk screen is using a diameter of
100 μm of 316L woven wires, which irregularly weave, to be formed, and its thickness is 400mm, and porosity is 70%, sets 3 sections of silk screens, often
The distance between section silk screen is 300mm, and the top distance of every section of silk screen mixes new sulfate liquid distributor 80mm；Using 2 sections points
From filler, it is 350mm that every section, which separates the distance between filler, and the porosity of separation filler is 75%.
The major parameter of alkylated reaction effluent acid cleaning process：The operating pressure of pickling tank is 0.55MPa；New sulfuric acid is dense
Spend for 98% (WT), flow is 2.5m3/h；Alkylated reaction effluent treating capacity is 100m3/ h, its sulfuric acid content is
2000ppm, total sulfur content is 990ppm.
Experimental result：
After method and apparatus pickling by the present invention, sulfuric acid content is reduced to 8ppm, total sulfur during pickling tank hydrocarbon is mutually exported
Content is 4ppm.
Embodiment 2：
Carried out according to the flow of the alkylated reaction effluent pickling shown in Fig. 1, wherein, microchannel silk screen is using 80 μm
Metallic fiber material irregularly weaves, and screen thickness is 300mm, and porosity is 70%, sets 3 sections of silk screens, every section of silk screen it
Between distance be 320mm, the top distance of every section of silk screen mixes new sulfate liquid distributor 70mm；The segregation section of pickling tank is used
2 sections of separation fillers, it is 300mm that every section, which separates the distance between filler, and the porosity of separation filler is 80%.
The major parameter of alkylated reaction effluent acid cleaning process：The operating pressure of pickling tank is 0.55MPa；New sulfuric acid is dense
Spend for 98% (WT), flow is 20m3/h；Alkylated reaction effluent treating capacity is 600m3/ h, its sulfuric acid content is 1800ppm,
Total sulfur content is 1000ppm.
Experimental result：
After method and apparatus pickling by the present invention, sulfuric acid content is reduced to 7ppm, total sulfur during pickling tank hydrocarbon is mutually exported
Content is 3ppm.
Embodiment 3：
Carried out according to the flow of the alkylated reaction effluent pickling shown in Fig. 1, wherein, microchannel silk screen is using 60 μm
Fibrous material weaves, and its thickness is 400mm, and porosity is 55%, sets 3 sections of silk screens, and the distance between every section of silk screen is
300mm, the top distance of every section of silk screen mixes new sulfate liquid distributor 80mm；Using 1 section of separation filler, the hole of filler is separated
Gap rate is 75%, and thickness is 250mm, is formed using 316L metallic fibers and the braiding of polytetrafluoroethylene fibre material.
The major parameter of alkylated reaction effluent acid cleaning process：The operating pressure of pickling tank is 0.55MPa；New sulfuric acid is dense
Spend for 98% (WT), flow is 30m3/h；Alkylated reaction effluent treating capacity is 1000m3/ h, its sulfuric acid content is
2000ppm, total sulfur content is 870ppm.
Experimental result：
After method and apparatus pickling by the present invention, sulfuric acid content is reduced to 7ppm, total sulfur during pickling tank hydrocarbon is mutually exported
Content is 4ppm.
From three above-mentioned embodiments, by the method and apparatus using the present invention, in the segregation section hydrocarbon of pickling tank
Sulfuric acid content falls below below 10ppm in mutually exporting, and total sulfur content also falls below below 5ppm.The method and apparatus of the present invention
Fully meet the requirement of subsequent production technique.
Above-mentioned listed embodiment is only presently preferred embodiments of the present invention, not for limiting the implementation model of the present invention
Enclose.Equivalence changes and modification that i.e. all contents according to scope of the present invention patent are made, all should be the technology model of the present invention
Farmland.
All documents referred in the present invention are all incorporated as reference in this application, independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after the above-mentioned instruction content of the present invention has been read, those skilled in the art can
To be made various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Claims (9)
1. a kind of method of alkylated reaction effluent pickling, this method comprises the following steps：
(a) the alkylated reaction effluent containing sulfuric ester and sulfuric acid droplets from acid deposition groove is passed into pickling tank,
In the presence of liquid distribution trough, reaction effluent is uniformly distributed on pickling tank cross section, is flowed downward and with mixing new sulphur
Acid is contacted on pickling section silk screen in the form of liquid film, realizes abundant extraction of the sulfuric acid to sulfuric acid droplets in hydrocarbon phase and sulfuric ester；
(b) in the top pickling section of pickling tank, by mixing new sulfuric acid point of the concentration for coming from blender for more than 97 weight %
It is delivered to respectively for multiple flow above each pickling microchannel silk screen, and each section of pickling microchannel silk screen and is provided with liquid
Distributor, is uniformly distributed with to mix new sulfuric acid on pickling tank cross section, and is mutually fully contacted with hydrocarbon；
(c) the new sulfuric acid of mixing and the hydrocarbon of 30~50mm distances on its vertical direction sent out through liquid distribution trough are mutually mixed in advance
Close, then mix new sulfuric acid and pass through pickling microchannel silk screen with hydrocarbon phase cocurrent；
(d) on the silk screen of pickling microchannel, liquid film can be formed on the silk screen of microchannel, greatly increase acid is alternate with hydrocarbon contacts
Area, so as to strengthen sulfuric acid to sulfuric acid droplets in alkylate and the effect of extracting of sulfuric ester；
(e) sulfuric acid and the mixing liquid of alkylate oil after the silk screen pickling of multistage microchannel enters the separation of pickling tank
Section, in the segregation section, alkylate oil with sulfuric acid cocurrent by separating filler so that still less sulphur in alkylate oil
Acid droplet produces coalescence effect in the presence of separation filler；And
(f) after separation filler, in the bottom of pickling tank, alkylate oil is layered rapidly and by different outlet stream from sulfuric acid
Go out, the sulfuric acid droplets and sulfuric ester in alkylate are removed, the alkylate oil being purified.
2. the method as described in claim 1, it is characterised in that the new sulfuric acid of mixing is the mixing of new sulfuric acid and time new sulfuric acid
Liquid, the new sulfuric acid is the fluid sulphuric acid that additional concentration is not less than 98 weight %, and described time new sulfuric acid is the step (f)
In the sulfuric acid of participation overpickling separated.
3. the method as described in claim 1, it is characterised in that the sulfuric acid part separated in the step (f) is sent back to
Reactor participates in alkylated reaction, and another part is returned and mixed with new sulfuric acid, and the amount of the sulfuric acid of participation alkylated reaction is equal to
Return to the amount of the sulfuric acid mixed with new sulfuric acid.
4. a kind of device of alkylated reaction effluent pickling, the device includes：
Pickling tank (3) being connected with blender (1), including pickling section and segregation section, it is anti-for will be fed into alkylation therein
Effluent is answered to carry out pickling and separation, to remove the sulfuric acid droplets and sulfuric ester impurity contained by hydrocarbon phase；
Multistage microchannel silk screen (7) is set in the pickling section, and every section is equipped with the new sulfuric acid entrance (2) of mixing and liquid distribution
Device (6) simultaneously adds the new sulfuric acid of mixing with certain proportion so that hydrocarbon mutually often has new mixing sulfuric acid to add simultaneously by one section of silk screen
With its cocurrent by silk screen, intensified acid is alternate with hydrocarbon contacts in the form of liquid film on silk screen；
Separation filler (8) is set in the segregation section, for coalescing the sulfuric acid liquid not yet extracted in hydrocarbon phase in pickling section by sulfuric acid
Drop, to strengthen the demulsification coalescence of sulfuric acid droplets, promotes the separation of alkylated reaction effluent and sulfuric acid, flows out alkylated reaction
Sulfuric ester and sulfuric acid droplets in thing are substantially completely removed in the sedimentation layering of pickling tank (3) bottom.
5. device as claimed in claim 4, it is characterised in that the pickling section include alkylated reaction effluent entrance (4),
Mix new sulfuric acid entrance (2), reaction effluent liquid distribution trough (5), mix new sulfate liquid distributor (6) and microchannel silk screen
(7)；The segregation section includes separation filler (8), hydrocarbon phase net outflow thing outlet (9) and sulfuric acid outlet (10).
6. the device as described in claim 4 or 5, it is characterised in that the quantity of the new sulfuric acid entrance (2) of mixing be 2 or
More, spacing is determined by the thickness of microchannel silk screen (7).
7. the device as described in claim 4 or 5, it is characterised in that the reaction effluent liquid distribution trough (5) and mixing are new
Sulfate liquid distributor (6) has identical structure, using one kind in calandria, spiral, triadius type or grid type.
8. device as claimed in claim 4, it is characterised in that the segregation section includes one section or multistage separation filler (8),
It is that pickling tank (3) bottom sets sulfuric acid to export (10) in segregation section bottom, apart from bottom at least 400mm place on segregation section
Hydrocarbon phase net outflow thing outlet (9) is set.
9. device as claimed in claim 4, it is characterised in that pickling microchannel silk screen uses polymer fiber and metal
Fiber mixed weaving is formed, 20~100 μm of fibre diameter, porosity 50%~75%；The thickness of pickling microchannel silk screen
For 300~500mm；The separation filler is formed using hydrophilic and hydrophobic fibrous material weaving, fibre diameter for 80~
500 μm, porosity is 70~85%；The thickness of the separation filler is 200~400mm.
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| CN102021016B (en) * | 2010-10-29 | 2014-02-26 | 南京工业大学 | Deacidifying method for alkylation reaction product |
| CN104927907B (en) * | 2015-07-01 | 2017-02-01 | 华东理工大学 | Alkylation product desulphurization and deacidifying method and device |
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