CN102389723B - Organic/inorganic composite membrane for use in oil gas recovery and preparation method thereof - Google Patents

Organic/inorganic composite membrane for use in oil gas recovery and preparation method thereof Download PDF

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CN102389723B
CN102389723B CN201110306016.1A CN201110306016A CN102389723B CN 102389723 B CN102389723 B CN 102389723B CN 201110306016 A CN201110306016 A CN 201110306016A CN 102389723 B CN102389723 B CN 102389723B
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CN102389723A (en
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黄维秋
王卫卿
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Liyang Chang Technology Transfer Center Co., Ltd.
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Changzhou University
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Abstract

The invention belongs to the technical field of oil gas recovery and particularly relates to an oil gas recovery organic/inorganic composite membrane and a preparation method thereof. In the invention, the composite membrane is formed by combining and overlapping polyether block amide (PEBA) and titanium dioxide (TiO2); and the composite membrane uses compact membrane PEBA as a strippable skin layer and uses ceramic membrane TiO2 as a supporting layer and has a good separation effect and high efficiency.

Description

A kind of organic/inorganic compound film reclaiming for oil gas and preparation method thereof
Technical field
The invention belongs to Investigation of Petroleum Vapor Recovery Technology field, be specifically related to a kind of organic/inorganic compound film reclaiming for oil gas and preparation method thereof.
Background technology
Fast development along with national economy, the demand of oil product is growing, but, the light-end products such as gasoline are very easy to volatilization and give off high-concentration oil vapor in the processes such as production, storage, transportation, sale, use, thereby cause serious energy loss and Quality Down, and can seriously pollute atmospheric environment and leave great disaster hidden-trouble; It is generally to utilize the feature of film to the preferential permeability of organic vapor that membrane separation process reclaims oil gas, allow organic vapor under certain pressure reduction promotes, " filtration " through film makes the organic vapor in gaseous mixture preferentially see through film, be able to " removing " and reclaim, air is optionally held back, and the advantage of membrane separation process is that energy consumption is low, efficiency is high, easy and other isolation technics combine, and facility compact is light and handy, are easy to produce and safeguard.
The composite membrane that is generally used for oil gas recovery is mainly organic/organic hybrid films; Perforated membrane as end liner provides mechanical support, and material comprises polysulfones (PSF), the sub-acid amides (PEI) of polyethers, polyacrylonitrile (PAN), vinylidene (PVDF); Using macromolecule dense material as separating layer, be coated on end liner film, main material kind has dimethyl silicone polymer (PDMS), poly-octyl group methylsiloxane (POMS) etc., but these materials or there is high osmosis, low selective, or there is hypotonicity, high selectivity, make to apply and be restricted in oil gas recovery field with the gas separation membrane of these developing materials.
It is good that inorganic ceramic membrane has chemical stability, acidproof, alkaline-resisting, organic solvent-resistant; Mechanical strength is high, high temperature resistant, the feature that permeability is high, and this is the not available excellent properties of some organic films.
Organic/inorganic compound film combines organic film material and inorganic ceramic material advantage separately, improves resistance to swelling and the crushing resistance of organic high molecular layer, overcomes organic/organic composite membrane structure is single, permeation flux is low problem.
Existing patent application 200810234509.7 discloses a kind of preparation method of tube type organic inorganic composite permeable membrane, be mainly used in infiltration evaporation and remove the water in organic solvent, described organic polymer membrane material is a kind of in polyvinyl alcohol, polyethylene glycol, carboxymethyl cellulose, sodium alginate, shitosan or more than one mixture, and described inorganic ceramic backing material is mullite, Al 2o 3, ZrO 2in a kind of or more than one composite; Existing patent application 200910035877.3 discloses the compound SiO of a kind of organic-inorganic 2the preparation method of gas separation membrane, be with 1,2-bis-(triethoxy is silica-based) ethane (be called for short BTESE) as precursor, under acid catalysis condition, two step synthesis SiO 2organic-inorganic film, relates to water vapor atmosphere separation, and as water gas shift reaction, steam reforming reaction etc., above-mentioned document shows in existing patent, there is no the report of organic/inorganic compound film aspect oil gas recovery.
Summary of the invention
Generally organic/organic hybrid films permeation flux in oil gas removal process is low to the object of the invention is to improvement, organic solvent resistance is poor, the shortcoming that stability is not high, provides a kind of novel organic/inorganic composite separating film, namely based on polyether block amide (PEBA) and titanium dioxide (TiO 2) composite membrane that forms of Material cladding stack, this composite membrane with dense film PEBA as selective separating, with porous ceramic film TiO 2as supporting layer, there is good separating effect and higher efficiency.
PEBA/TiO of the present invention 2the preparation method of composite membrane, comprises the following steps:
(1) to the porous TiO as supporter 2pottery carries out pretreatment;
(2) with photoelectric analytical balance, measure quantitative PEBA particle, be dissolved in quantitative solvent, make the PEBA polymer solution of certain mass mark, at 70 ℃, constant temperature stirs 3h, until form homogeneous transparent solution, then polymer solution standing 10h in 60 ℃ of water-baths of constant temperature, until in solution, there is no bubble, stand-by;
(3) under dustfree environment, by TiO 2ceramic membrane is placed in culture dish, adds deionized water in culture dish, with energy infiltrating T iO 2ceramic membrane surface is as the criterion, standing until the water surface does not have disturbance, with capillary pipette, gets polymer solution, drops in TiO 2ceramic membrane surface, the polymer weight of dropping is controlled at 0.01-0.06 g, avoids polymer drop to cause the disturbance of the water surface during dropping liquid, and polymer solution is dripping to TiO 2ceramic membrane surface moment, due to TiO 2ceramic membrane is infiltrated by deionized water, and the solvent with special surface energy just starts to play a role, and now polymer solution is just at TiO 2ceramic membrane surface spontaneously spreads and comes rapidly, and in this process, solvent is certainly in evaporation, and rapid exchange has occurred for solvent and non-solvent deionized water simultaneously, like this will be at TiO 2ceramic membrane surface forms PEBA film, makes PEBA/TiO 2composite membrane first product;
(4) the standing until water surface does not have after disturbance, by culture dish move to experiment special-purpose with vacuumizing, in the micro-wave oven of function, heat predryingly, with vavuum pump, vacuumize, adjust suitable power and make in stove temperature at 65 ~ 75 ℃, after 1h ~ 2h, the removal that is dried of most of water and solvent, then, moves in constant-temperature vacuum drying box, under 60 ℃ ~ 70 ℃ of constant temperature, vacuum 90 ~ 95kPa condition, keep 4 ~ 6h, continue dry and remove excessive moisture and solvent, obtain PEBA/TiO 2composite membrane finished product.
In culture dish of the present invention, add deionized water, with energy infiltrating T iO 2ceramic membrane surface is as the criterion and refers to the water surface and the TiO of deionized water in culture dish 2ceramic membrane thickness keeps flushing.
In above-mentioned technical scheme during dropping liquid capillary pipette apart from TiO 2ceramic membrane will be controlled within 5 millimeters.
Of the present invention to porous TiO 2it is by porous TiO that pottery carries out pretreatment 2ceramic membrane surface polishes smooth, then rinses well by deionized water.
In PEBA solution of the present invention, the mass fraction of PEBA is 5%-10%.
In PEBA solution of the present invention, solvent is isopropyl alcohol, n-butanol or mixed solvent (isopropyl alcohol and n-butanol are miscible in 3:1 ratio).
Porous TiO of the present invention 2thick 1 ~ the 2mm of ceramic supporting body.
The vacuum <1kPa vacuumizing of the present invention.
The inventive method is based on MJPZ principle, with the TiO of resistance to acids and bases, anti-swelling 2ceramic membrane is supporting layer, and permeability and selective high PEBA film are that separating layer obtains composite membrane, compared with prior art have following beneficial effect:
PEBA/TiO prepared by the present invention 2composite membrane, for the single deficiency of existing oil gas reclamation film kind, combines organic polymer membrane material and ceramic support film, and inorganic ceramic membrane material is introduced and effectively raised composite membrane resistance to elevated temperatures simultaneously, and suppresses the swelling action of film.Because polymer solution is at TiO 2phenomenon is oozed in hole slight in ceramic membrane, forms a transition zone, has effectively improved adhesion between the two, has improved the stability of composite membrane.Film-forming method is simple simultaneously, and process conditions are easy to control, widely applicable.
Accompanying drawing explanation
Fig. 1 PEBA/TiO 2composite membrane preparation method schematic diagram;
The process chart of Fig. 2 composite membrane separation oil and gas;
1-N 2bottle; 2-mass flow controller; 3-material liquid tank; 4-membrane module; 5-cold-trap; 6-vavuum pump; 7-soap film flowmeter; 8-chromatograph; P-pressure (vacuum) table; C-measurement of concetration.
The specific embodiment
Embodiment 1
(1) to porous TiO 2ceramic supporting body polishes smooth, then rinses well by deionized water;
(2) with photoelectric analytical balance, measure the PEBA particle of 1g, be dissolved in the n-butanol of 19g, configuration quality mark is 5% PEBA film forming liquid, on thermostatic electromagnetic agitator, at 70 ℃, constant temperature stirs 3h, until form homogeneous transparent solution, then polymer solution rests on 10h in 60 ℃ of water-baths of constant temperature, until in solution, there is no bubble, and stand-by;
(3) as accompanying drawing 1, under dustfree environment, by TiO 2ceramic membrane is placed in culture dish, adds deionized water in culture dish, with energy infiltrating T iO 2ceramic membrane surface is as the criterion, the water surface and TiO 2ceramic membrane thickness keeps flushing, standing until the water surface does not have disturbance, with capillary pipette, drips 1 solution at TiO 2ceramic membrane surface, solution weight 0.015g, when dropping liquid, pipette is from TiO 2ceramic membrane will, within 5 millimeters, drop in TiO solution lightly 2ceramic membrane surface, TiO 2ceramic membrane surface, by forming very thin PEBA film, is made PEBA/TiO 2composite membrane first product;
(4) the standing until water surface does not have after disturbance, by culture dish move to experiment special-purpose with vacuumizing, in the micro-wave oven of function, heat predryingly, with vavuum pump, vacuumize, vacuum <1kPa, adjust suitable power and make in stove temperature at 70 ℃, after 1.5h, the removal that is dried of most of water and solvent, then, move in constant-temperature vacuum drying box, under 60 ℃ of constant temperature, vacuum 90kPa condition, keep 4h, continue dry and remove excessive moisture and solvent, obtaining PEBA/TiO 2composite membrane finished product.
Obtain PEBA/TiO 2composite membrane, PEBA diffusion barrier thickness is 0.016mm, effective film area is 4.916cm 2, utilize this film to carry out permeability and separation hexane/nitrogen mixture, when hexane mole fraction is 10%, at 20 ℃ of system temperatures, hexane infiltration rate is 113(molcm -2s -1pa -1), separating degree is 27.
Embodiment 2
(1) to porous TiO 2ceramic supporting body polishes smooth, then rinses well by deionized water;
(2) with photoelectric analytical balance, measure the PEBA particle of 1g, be dissolved in the n-butanol of 19g, configuration quality mark is 5% PEBA film forming liquid, on thermostatic electromagnetic agitator, at 70 ℃, constant temperature stirs 3h, until form homogeneous transparent solution, then polymer solution rests on 10h in 60 ℃ of water-baths of constant temperature, until in solution, there is no bubble, and stand-by;
(3) as accompanying drawing 1, under dustfree environment, by TiO 2ceramic membrane is placed in culture dish, adds deionized water in culture dish, with energy infiltrating T iO 2ceramic membrane surface is as the criterion, the water surface and TiO 2ceramic membrane thickness keeps flushing, standing until the water surface does not have disturbance, with capillary pipette, gets trace polymer solution at every turn, drops in TiO 2ceramic membrane surface drips 1 at every turn, drips twice, and solution weight 0.035g during dropping liquid, want light, and pipette is apart from TiO 2ceramic membrane will be controlled within 5 millimeters, avoids polymer drop to cause the disturbance of the water surface, and polymer solution is dripping to TiO 2ceramic membrane surface moment, due to TiO 2ceramic membrane is infiltrated by deionized water, and the solvent with special surface energy just starts to play a role, and now polymer solution is just at TiO 2ceramic membrane surface spontaneously spreads and comes rapidly, and in this process, solvent is certainly in evaporation, and rapid exchange has occurred for solvent and non-solvent deionized water simultaneously, like this will be at TiO 2ceramic membrane surface forms PEBA film, makes PEBA/TiO 2composite membrane first product;
(4) the standing until water surface does not have after disturbance, by culture dish move to experiment special-purpose with vacuumizing, in the micro-wave oven of function, heat predryingly, with vavuum pump, vacuumize, vacuum <1kPa, adjust suitable power and make in stove temperature at 75 ℃, after 2h, the removal that is dried of most of water and solvent, then, move in constant-temperature vacuum drying box, under 65 ℃ of constant temperature, vacuum 95kPa condition, keep 5h, continue dry and remove excessive moisture and solvent, obtaining PEBA/TiO 2composite membrane finished product.
Obtain PEBA/TiO 2composite membrane, wherein PEBA diffusion barrier thickness is 0.029mm, utilizes this film to carry out permeability and separation hexane/nitrogen mixture, when hexane mole fraction is 10%, at 20 ℃ of system temperatures, hexane infiltration rate is 106(molcm -2s -1pa -1), separating degree is 34.
Embodiment 3
According to the operation of embodiment 1, only changing PEBA mass fraction in PEBA film forming liquid is 8%, obtains PEBA/TiO 2composite membrane, utilizes this film to carry out permeability and separation hexane/nitrogen mixture, and when hexane mole fraction is 10%, at 20 ℃ of system temperatures, hexane infiltration rate is 103(molcm -2s -1pa -1), separating degree is 30.
Embodiment 4
According to the operation of embodiment 1, only changing solvent in PEBA film forming liquid is isopropyl alcohol, obtains PEBA/TiO 2composite membrane, utilizes this film to carry out permeability and separation hexane/nitrogen mixture, and when hexane mole fraction is 10%, at 20 ℃ of system temperatures, hexane infiltration rate is 102(molcm -2s -1pa -1), separating degree is 30.
Embodiment 5
According to the operation of embodiment 1, only changing solvent in PEBA film forming liquid is mixed solvent (isopropyl alcohol and n-butanol are miscible in 3:1 ratio), obtains PEBA/TiO 2composite membrane, utilizes this film to carry out permeability and separation hexane/nitrogen mixture, and when hexane mole fraction is 10%, at 20 ℃ of system temperatures, hexane infiltration rate is 107(molcm -2s -1pa -1), separating degree is 29.
patent of invention application example
As accompanying drawing 2, N 2bottle 1 outlet connects mass flow controller 2, and material liquid tank 3 is linked in mass flow controller 2 outlets, and the entrance of membrane module 4 is linked in the outlet of material liquid tank 3, and membrane module 4 per-meate side gas outlets are connected to cold-trap 5, in the another port of cold-trap 5, connect vavuum pump 6.
(1) N 2n out in bottle 1 2through mass flow controller 2, then enter material liquid tank 3, advertise gasoline or other volatile organic matter (VOC) in material liquid tank 3, thereby form certain density oil gas-N 2gaseous mixture.
(2) from material liquid tank 3 oil gas-N out 2gaseous mixture, and directly from N 2n out in bottle 1 2by setting after concentration proportioning, enter membrane module 4.
(3) oil gas-N 2gaseous mixture, in membrane module 4, provides infiltration side pressure, oil gas-N by vavuum pump 6 2gaseous mixture is realized permeability and separation at composite membrane, and most of oil gas penetrates from composite membrane, and N 2only have microdialysis, the large I of the infiltration side pressure of membrane module 4 is by regulating vavuum pump 6 to realize.
(4) high-concentration oil vapor infiltrating from membrane module 4, through cold-trap 5, condenses into liquid, is convenient to reclaim, measure.
(5) outside the direct drain chamber of low concentration residual air of the not infiltration of membrane module 4.
(6) utilize 8 pairs of feeding gas of chromatograph and do not permeate residual air and carry out measurement of concetration; Utilize the not infiltration residual air of 7 pairs of membrane modules 4 of soap film flowmeter carry out flow measurement.

Claims (8)

1. a preparation method for the organic/inorganic compound film reclaiming for oil gas, comprises the following steps:
(1) to the porous TiO as supporter 2pottery carries out pretreatment;
(2) with photoelectric analytical balance, measure quantitative PEBA particle, be dissolved in quantitative solvent, make the PEBA polymer solution of certain mass mark, at 70 ℃, constant temperature stirs 3h, until form homogeneous transparent solution, then polymer solution standing 10h in 60 ℃ of water-baths of constant temperature, until in solution, there is no bubble, stand-by;
(3) under dustfree environment, by TiO 2ceramic membrane is placed in culture dish, adds deionized water in culture dish, with energy infiltrating T iO 2ceramic membrane surface is as the criterion, standing until the water surface does not have disturbance, with capillary pipette, gets polymer solution, drops in TiO 2ceramic membrane surface, the polymer weight of dropping is controlled at 0.01-0.06 g, avoids polymer drop to cause the disturbance of the water surface during dropping liquid, makes PEBA/TiO 2composite membrane first product;
(4) the standing until water surface does not have after disturbance, by culture dish move to experiment special-purpose with vacuumize in the micro-wave oven of function, heat predrying, with vavuum pump, vacuumize, adjusting suitable power makes temperature in stove at 65 ~ 75 ℃, after 1h ~ 2h, move in constant-temperature vacuum drying box, under 60 ℃ ~ 70 ℃ of constant temperature, vacuum 90 ~ 95kPa condition, keep 4 ~ 6h, continue dry and remove excessive moisture and solvent, obtain PEBA/TiO 2composite membrane finished product.
2. the preparation method of a kind of organic/inorganic compound film reclaiming for oil gas as claimed in claim 1, is characterized in that: in described culture dish, add deionized water, with energy infiltrating T iO 2ceramic membrane surface is as the criterion and refers to the water surface and the TiO of deionized water in culture dish 2ceramic membrane thickness keeps flushing.
3. the preparation method of a kind of organic/inorganic compound film reclaiming for oil gas as claimed in claim 1, is characterized in that: during dropping liquid, capillary pipette is apart from TiO 2ceramic membrane will be controlled within 5 millimeters.
4. the preparation method of a kind of organic/inorganic compound film reclaiming for oil gas as claimed in claim 1, is characterized in that: described to porous TiO 2it is by porous TiO that pottery carries out pretreatment 2ceramic membrane surface polishes smooth, then rinses well by deionized water.
5. the preparation method of a kind of organic/inorganic compound film reclaiming for oil gas as claimed in claim 1, is characterized in that: in described PEBA solution, the mass fraction of PEBA is 5%-10%.
6. the preparation method of a kind of organic/inorganic compound film reclaiming for oil gas as claimed in claim 1, it is characterized in that: in described PEBA solution, solvent is isopropyl alcohol, n-butanol or isopropyl alcohol and the n-butanol miscible mixed solvent of ratio of 3:1 by volume.
7. the preparation method of a kind of organic/inorganic compound film reclaiming for oil gas as claimed in claim 1, is characterized in that: described porous TiO 2thick 1 ~ the 2mm of ceramic supporting body.
8. the preparation method of a kind of organic/inorganic compound film reclaiming for oil gas as claimed in claim 1, is characterized in that: the described vacuum <1kPa vacuumizing.
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CN103752046A (en) * 2013-12-31 2014-04-30 江苏有能电力自动化有限公司 Preparation method for composite membrane pipe
CN105561803B (en) * 2015-12-29 2017-10-17 安徽名创新材料科技有限公司 A kind of big flux, high-precision condensed water in high temperature oil removing remove the preparation method of iron ceramic super-filtering film
CN105536566B (en) * 2016-01-19 2017-12-12 长安大学 A kind of composite membrane for separating lithium ion and cobalt ions and preparation method thereof
CN108714372B (en) * 2018-05-29 2021-05-18 太原理工大学 Treatment method for coal chemical industry wastewater
CN109174071A (en) * 2018-09-28 2019-01-11 常州大学 A kind of preparation method of ceramic base nano titanium dioxide film

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