CN109569321B - A kind of film and its separation method for alkane separation of olefins - Google Patents
A kind of film and its separation method for alkane separation of olefins Download PDFInfo
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- CN109569321B CN109569321B CN201811362800.2A CN201811362800A CN109569321B CN 109569321 B CN109569321 B CN 109569321B CN 201811362800 A CN201811362800 A CN 201811362800A CN 109569321 B CN109569321 B CN 109569321B
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- alkene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/144—Purification; Separation; Use of additives using membranes, e.g. selective permeation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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- Separation Using Semi-Permeable Membranes (AREA)
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Abstract
The present invention provides a kind of film for alkane separation of olefins and separates alkene from alkane and olefin stream from method, which includes that (1) provides a kind of basement membrane with porous structure;(2) basement membrane is immersed in the mixture of single polarity coated substance or various polarity coated substance, so that essentially all of hole has been filled with polarity coated substance;(3) basement membrane is taken out from polar substances composition, and removes the excessive liquid in surface, obtains the composite membrane;Separation method includes the side contacts for making stream and composite membrane containing alkane and alkene, isolated richness alkane stream and fulvene hydrocarbon flow.This method can be used by the way of multi-stage separation device series/parallel, to realize continuous, efficiently production.
Description
Technical field
The method that the present invention relates to a kind of to separate alkene from the mixture containing alkane and alkene, and in particular to one kind is adopted
The method for separating alkene with UF membrane mode.
Background technique
Alkene is a kind of basis and very important high added value industrial chemicals, synthetic fibers, synthetic rubber, synthesis modeling
Many products such as material, senior lubricant, higher alcohols, High-Density Jet are all with it for basic raw material.And high-carbon alpha-olefin
It is then a kind of important and common organic petrochemical material in alkene, can be used as detergent, oil dope, surfactant and doctor
Medicine intermediate etc., they are alternatively arranged as high-quality comonomer and produce high-grade polyolefin resin.Distillate based on F- T synthesis produces
Product not harmful substances such as sulfur-bearing, nitrogen, aromatic hydrocarbons, heavy metal, carbon number distribution is wide, mainly based on n-alkane and normal olefine, always
Content >=90%, in normal olefine content, alpha-olefin content is more than 90%.
To reduce the dependence to petroleum resources, the alkene system of Non oil-based route is concentrated mainly on for alkene research both at home and abroad
In standby technique, including MTO technology (MTO technique and MTP technique) and F- T synthesis olefin process.Based on taking
For the oil-phase product for holding in the palm synthesis, alkene and alkane usually have similar mass and close boiling point, not easily pass through traditional
The methods of rectifying is separated, because energy consumption is high by the alkane Olefin Separation Technologies of the means such as rectifying, extraction, complex process,
Equipment investment is big;Adsorptive separation technology easily causes adsorbent to inactivate with the accumulation of harmful substance in charging, causes production capacity
Decline.The separation that alkane and alkene are carried out using other separate modes is had begun in the prior art.
Patent CN102452886B discloses a kind of method that 1- octene is separated from oil from Fischer-Tropsch synthesis, and this method is to take
Support synthesis light fraction oil is raw material, cuts to obtain C8 fraction section through secondary fraction, then first passes through azeotropic distillation, with ethyl alcohol and
The agent of water binary azeotropic removes acid and other organic oxygen-containing compounds in C8 fraction simultaneously;C8 is separated by extraction fractional distillation again to evaporate
The alkane and alkene of segmentation, obtain C8 alkene, and finally C8 alkene is further purified by precise distillation, obtains meeting polymer grade
It is required that 1- octene product.Although this method realizes the separation of 1- octene in oil from Fischer-Tropsch synthesis, but there are complex process, energy
The limiting factors such as consumption is high, investment is excessive.
Patent CN101462919A discloses a kind of separation method of olefin adsorption.I.e. by making feeding flow and adsorbent bed
On adsorbent contact, selectively sub-argument goes out detersive alkene from the logistics comprising one or more alkane.But this
Method has a problem that when separating alkene: causing to poison with the adsorbent selected by the accumulation of harmful substances more in feeding flow
Effect increases, and the ability of adsorbent will decline, thus cause the decline of the production capacity of entire technique.
The membrane separation process also reported separation for alkane alkene, still, most of separation of alkane and alkene limitation
In the feed stream of gas phase, such as in EP0311903, the liquid film that the fused salt hydrate as liquid coating solution loads is used for
From the alkane separation alkene in gaseous feed composition;Chem.Commun., 2000,1261-1262 and Chem.Commun.,
By the inclusion of the method for the polymer film of copper and silver salt separation gaseous olefin and alkane reported in 2000,195-196.Existing film
Partition method feed stream phase is gas phase, is only applicable to separation low carbon number alkane alkene, be not suitable for separating high carbon number alkane and
Alkene.
Patent CN100378045C discloses a kind of side of ionic liquid UF membrane liquid alkane alkene using load
Method, this method can realize the separation of liquid alkane alkene effective and rapidly, but ionic liquid price is costly, does not refer to film
Regeneration technology, industry amplification there are certain restrictions.And gas-phase olefin alkane stream is concentrated mainly on by the technique of UF membrane
Separation, it is less for the wide in range liquefied olefines separating technology of carbon number range
Although in the presence of the method that can separate liquid olefin and liquid alkane in current technology, it is also desirable to provide more
Add the improved method for separating alkene from alkane.It is high-efficient and be able to satisfy present invention particularly provides a kind of simple process
Alkene different purity and carbon number distribution require the separation of olefins composite membrane and separation method of (such as C5-C40) in the market.
Summary of the invention
The problem to be solved in the present invention is efficiently, quickly to be divided alkene from the mixture containing alkane and alkene
From, it obtains and meets the olefin product of purity requirement, be especially to provide a kind of simple process, it is high-efficient and be able to satisfy alkene in the market
Different purity and carbon number distribution require the separation of olefins composite membrane and separation method of (such as C5-C40).
To achieve the object of the present invention, used technical solution is:
A kind of composite membrane for the separation alkene from the liquid stream containing alkane and alkene, preparation method include such as
Lower step:
(1) a kind of basement membrane with porous structure is provided;
(2) basement membrane is immersed in the mixture of single polarity coated substance or various polarity coated substance, so that
Essentially all of hole has been filled with polarity coated substance;
(3) basement membrane is taken out from polar substances composition, and removes the excessive liquid in surface, obtains the composite membrane;
The polarity coated substance is the benign organic solvent of alkene, and is not ionic liquid.
Herein, term " essentially all " refers to that 95% or more fenestra is filled with polar object liposomal composition, preferably
99% or more, more preferably 100% fenestra is filled with polar substances composition.
In general,
Polarity coated substance is polyalcohols, ketone, amides, imidazole and its derivants, one in lactone compound
Kind is a variety of.
Basement membrane is selected from mesoporous and macroporous polymer film, ceramic membrane, zeolite membrane, porous aluminas and steel membrane, and preferably basement membrane is
Mesoporous or macroporous polymer film.
Basement membrane is selected from mesoporous and macroporous polymer film, ceramic membrane, zeolite membrane, porous aluminas and steel membrane, and preferably basement membrane is
Mesoporous or macroporous polymer film.Polysulfones, polyethersulfone ketone, acetate fiber can be selected from suitable for the material for preparing polymer film
Element, polyamide, polycarbonate, polyimides, Kynoar, polysulfones, polyether sulfone, polypropylene, nylon, gathers regenerated cellulose
One of acrylate, polyetherimide, polyvinyl chloride, polyacrylonitrile, polymethacrylates are a variety of.The structure of basement membrane
For one of plain film shape, tubulose, spiral wound or doughnut structure.Basement membrane pore-size distribution is 2-5000nm;Further preferably
Basement membrane pore-size distribution is 50-4000nm;Most preferably basement membrane aperture 100-3000nm.
Polarity coated substance is polyalcohols, ketone, amides, imidazole and its derivants, one in lactone compound
Kind is a variety of.Specifically, polarity coated substance is ethylene glycol (EG), methyl ethyl ketone (MEK), N-Methyl pyrrolidone (NMP), N- first
One of morpholide (NFM), 1- methylimidazole (1-MI), gamma-butyrolacton (γ-BL) are a variety of, preferably ethylene glycol (EG), first
One of ethyl ketone (MEK) and N- N-formyl morpholine N (NFM) are a variety of.
Meanwhile the present invention also provides a kind of to separate alkene from the liquid stream containing alkane and alkene using above-mentioned composite membrane
The method of hydrocarbon, comprising the following steps:
(1) stream is made to connect the side of composite membrane;
(2) rich alkane stream is collected by the side of raw material in composite membrane, collects rich olefins in the other side of separation unit
Stream.
In general,
During separation, the pressure that preferably control olefin stream collects side is less than the pressure of feed side, can use
Vacuumize mode.Compound both sides differential pressure of membrane is discharged the critical pressure differential of fenestra no more than polarity coated substance.Basement membrane pore-size distribution
It is 2-5000nm;Further preferably basement membrane pore-size distribution is 50-4000nm;Most preferably basement membrane aperture 100-3000nm.Film pressure at both sides
Difference is advisable with the critical pressure differential for being discharged fenestra no more than polarity coated substance.
Alkane and alkene are a for 5-40 containing carbon number in stream, and preferably 6-30, further preferably 6-18.
The stream is made by MTO technology or F- T synthesis olefin process, it is preferred to use F- T synthesis system
Olefin process is made.
According to product purity and carbon number distribution requirement, the separation assembly with composite membrane is using in parallel and/or concatenated side
Formula setting, series connection are preferably provided with 2-6 grades, are further preferably arranged 2-4 grades.
Beneficial effect
In alkane alkene mixture, alkene is polar substances, and alkane is that nonpolarity or low pole substance, the present invention mix alkane alkene
Close object characteristic combined with membrane separation process, principle is equably to be supported on polar substances on stephanoporate framework, film it is another
Side vacuumizes, alkene can polarity coating absorption on preferential envelope by film, and taken away by negative pressure;Apolar substance alkane simultaneously
Film is not easily passed through, to just reach separating effect.It compares using ionic liquid, this method is at low cost, the production of film and again
Raw simple process, is suitable for large-scale production.
It can be isolated from alkane olefin liquid mixture using this method and meet market different purity and carbon number distribution
It is required that olefin product, than using gas separation method compare, have many advantages, such as separative efficiency height, product purity it is high.Tradition
Technique can only generally separate C8 hereinafter, method of the invention can separate the component of C5-C40, including odd number carbon.Traditional handicraft energy
Consumption is high, and separation purity is limited by the saturated capacity of adsorbent, and low energy consumption for method of the invention, can be using multistage UF membrane group
Part series connection, separation purity are high;Traditional handicraft needs periodically to regenerate adsorbent, continuous production and low efficiency, this
The method of invention can be in parallel using more set membrane separation assemblies, and single device can cut out maintenance, continuous production and efficiency at any time
It is high.
Detailed description of the invention
Fig. 1 is the alkane and olefin separation schematic diagram for being provided with single composite membrane.
Specific embodiment
This method is using device as shown in Figure 1, it includes membrane separation assemblies 1, condenser 2, collectors 3, vacuum evacuation device
4, composite membrane 5, alkane alkene stream import 6 and alkane outlet 7 are provided in membrane separation assemblies, olefin stream outlet connects with condenser 2
It connects, membrane separation assemblies are divided into mutual disconnected feed space and discharge chamber by composite membrane, and the indoor alkene that discharges is in vacuum evacuation device 4
Under the suction function of generation, enter in collector 3 after being condensed by condenser 2.
Compound membrane preparation method and alkene separation method are as follows:
(1) basement membrane is immersed in the mixture of single polarity coated substance or various polarity coated substance, so that
Essentially all of hole has been filled with polarity coated substance, film is then taken out from polar substances composition, and remove surface
Excessive liquid, obtains composite membrane;
(2) composite membrane is mounted in separation chamber 1, is connected to two sides mutually not.
(3) mixture flow of alkane and alkene is passed through to the side of membrane separation assemblies, is separated under certain operating conditions
Alkane and alkene, obtained olefin stream are collected in collector 3 after the condensation of condenser 2.
The present invention is as follows by the average flux calculation formula of film:
Wherein, the group component of film, units/kg are penetrated through in the Q--t time;
A-- film surface product, unit m2;
T-- disengaging time, unit h;
P-- passes through the average flux (kgm of time t-2h-1)。
Gas selectivity α calculation formula is as follows: α=P1/P2, and wherein P1 is the average value of the normalized flux of alkene, and P2 is
The average value of the normalized flux of alkane.
Comparative example
Charging parameter: Fischer-Tropsch synthesis oil material composition see the table below
Compound | The weight percentage wt% of feed composition |
1- hendecene | 12.9 |
Hendecane | 35.3 |
1- laurylene | 14.1 |
Dodecane | 37.7 |
Basement membrane is polyethersulfone ketone, average pore size 300nm, separated contact surfaces product 80cm2, coated substance is benzene operating parameter:
50 DEG C of operation temperature, 10 bars of pressure, disengaging time is for 24 hours.
Embodiment 1-11
Other parameters condition is identical as comparative example, and polarity coated substance replaces with substance shown in table 1.
1 embodiment 1-11 parameter of table and result
Embodiment 12-17
Other parameters condition is identical as comparative example, and different parameters are basement membrane material and compound membrane aperture, referring specifically to table 2.
2 embodiment 12-17 relevant parameter of table and result
Claims (4)
1. a kind of method for separating alkene from the liquid stream containing alkane and alkene using composite membrane, which is characterized in that packet
Include following steps:
(1) liquid stream is made to connect the side of composite membrane;
(2) rich alkane stream is collected by the side of raw material in composite membrane, collects fulvene hydrocarbon flow in the other side of composite membrane;
Alkane and alkene are a for 6-30 containing carbon number in liquid stream;
The preparation method of composite membrane includes the following steps:
(1) a kind of basement membrane with porous structure is provided;
(2) basement membrane is immersed in the polarity coated substance mixture of N- N-formyl morpholine N and ethylene glycol molar ratio 1:1, so that base
All holes have been filled with polarity coated substance in sheet;
(3) basement membrane is taken out from polarity coated substance mixture, and removes the excessive liquid in surface, obtain the composite membrane;
The polarity coated substance is the benign organic solvent of alkene;
Composite membrane is applied in olefin separation, and olefin separation includes membrane separation assemblies, condenser, collector, takes out very
Empty device, composite membrane, alkane alkene stream import and alkane outlet are provided in membrane separation assemblies, and olefin stream outlet connects with condenser
It connects, membrane separation assemblies are divided into mutual disconnected feed space and discharge chamber by composite membrane, and the indoor alkene that discharges is in vacuum evacuation device
Under the suction function of generation, enter in collector after being condensed by condenser;Membrane separation assemblies with composite membrane are using in parallel
And/or concatenated mode is arranged, and is arranged in series 2-6 grades, which is characterized in that during separation, control olefin stream is collected
The pressure of side is less than the pressure of feed side, and compound both sides differential pressure of membrane is discharged the critical pressure of fenestra no more than polarity coated substance
Difference;Basement membrane pore-size distribution is 50-4000nm.
A kind of alkene is separated from the liquid stream containing alkane and alkene using composite membrane 2. according to claim 1
Method, which is characterized in that basement membrane is selected from mesoporous or macroporous polymer film.
3. a kind of described in one of -2 according to claim 1 separated from the liquid stream containing alkane and alkene using composite membrane
The method of alkene, which is characterized in that basement membrane is mesoporous or macroporous polymer film;It is selected from suitable for the material for preparing polymer film
Polysulfones, polyethersulfone ketone, cellulose acetate, regenerated cellulose, polyamide, polycarbonate, polyimides, Kynoar, polyethers
One of sulfone, polypropylene, polyacrylate, polyetherimide, polyvinyl chloride, polyacrylonitrile, polymethacrylates are more
Kind, the structure of basement membrane is one of plain film shape, tubulose, spiral wound or doughnut structure.
A kind of alkene is separated from the liquid stream containing alkane and alkene using composite membrane 4. according to claim 1
Method, which is characterized in that the liquid stream containing alkane and alkene is to pass through MTO technology or F- T synthesis system
Olefin process is made.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1898186A (en) * | 2003-12-22 | 2007-01-17 | 国际壳牌研究有限公司 | Process for the separation of olefins and paraffins |
CN102688708A (en) * | 2012-05-24 | 2012-09-26 | 北京化工大学 | Method for separating aromatic hydrocarbon from alkane by ionic liquid and membrane process coupling technology |
CN103232313A (en) * | 2013-05-06 | 2013-08-07 | 北京化工大学 | Extraction and separation method of alkane/olefin |
WO2018005164A1 (en) * | 2016-06-30 | 2018-01-04 | Uop Llc | Stable facilitated transport membranes for olefin/paraffin separations |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1898186A (en) * | 2003-12-22 | 2007-01-17 | 国际壳牌研究有限公司 | Process for the separation of olefins and paraffins |
CN102688708A (en) * | 2012-05-24 | 2012-09-26 | 北京化工大学 | Method for separating aromatic hydrocarbon from alkane by ionic liquid and membrane process coupling technology |
CN103232313A (en) * | 2013-05-06 | 2013-08-07 | 北京化工大学 | Extraction and separation method of alkane/olefin |
WO2018005164A1 (en) * | 2016-06-30 | 2018-01-04 | Uop Llc | Stable facilitated transport membranes for olefin/paraffin separations |
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