CN102389723A - 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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CN102389723A
CN102389723A CN2011103060161A CN201110306016A CN102389723A CN 102389723 A CN102389723 A CN 102389723A CN 2011103060161 A CN2011103060161 A CN 2011103060161A CN 201110306016 A CN201110306016 A CN 201110306016A CN 102389723 A CN102389723 A CN 102389723A
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tio
composite membrane
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peba
oil gas
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CN102389723B (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 composite membrane that is used for the oil gas recovery and preparation method thereof
Technical field
The invention belongs to oil gas recovery technology field, be specifically related to a kind of organic/inorganic composite membrane that is used for the oil gas recovery and preparation method thereof.
Background technology
Along with fast development of national economy; The increasing demand of oil product increases; But; Light-end products such as gasoline are very easy to volatilization and give off high-concentration oil vapor in processes such as production, storage, transportation, sale, use, thereby cause serious energy loss and quality to descend, and can seriously pollute atmospheric environment and stay great disaster hidden-trouble; It generally is to utilize the characteristics of film to the penetrated preferably property of organic vapor that membrane separation process reclaims oil gas, lets organic vapor under certain pressure reduction promotes, and makes the organic vapor penetrated preferably film in the gaseous mixture through " filtration " of film; Be able to " removing " and reclaim, air is then optionally held back, and the advantage of membrane separation process is that energy consumption is low; Efficient 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 generally is used for the oil gas recovery mainly is organic/organic hybrid films; Perforated membrane as end liner provides mechanical support, and material comprises polysulfones (PSF), the inferior acid amides (PEI) of polyethers, polyacrylonitrile (PAN), vinylidene (PVDF); With the macromolecule dense material as separating layer; Be coated on the end liner film; The main material kind has dimethyl silicone polymer (PDMS), gathers octyl group methylsiloxane (POMS) etc., but these materials or have high osmosis, low selectivity; Or have hypotonicity, high selectivity, make the gas separation membrane of using these developing materials use and be restricted in oil gas recovery field.
It is good that inorganic ceramic membrane has chemical stability, acidproof, alkaline-resisting, organic solvent-resistant; Mechanical strength is high, and is high temperature resistant, the characteristics that permeability is high, and this is the not available excellent properties of some organic films.
The organic/inorganic composite membrane has combined organic film material and inorganic ceramic material advantage separately, improves the resistance to swelling and the crushing resistance of organic high molecular layer, overcomes the organic/organic hybrid films 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 the organic solvent; Described organic polymer membrane material is a kind of in polyvinyl alcohol, polyethylene glycol, carboxymethyl cellulose, sodium alginate, the 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 is with 1, and as precursor, under the acid catalysis condition, two-step method is synthesized SiO to 2-two (triethoxy is silica-based) ethane (being called for short BTESE) 2The organic-inorganic film relates to water vapor atmosphere and separates, and like water gas shift reaction, steam reforming reaction etc., above-mentioned document shows there be not the report of organic/inorganic composite membrane aspect the oil gas recovery in the existing patent.
Summary of the invention
It is low to the objective of the invention is to improve generally organic/organic hybrid films permeation flux in the oil gas removal process; Organic solvent resistance is poor; The shortcoming that stability is not high provides a kind of novel organic/inorganic composite separating film, just based on polyether block amide (PEBA) and titanium dioxide (TiO 2) composite membrane formed of material complex superposition, this composite membrane with dense film PEBA as selective separating, with porous ceramic film TiO 2As supporting layer, has separating effect and higher efficient preferably.
PEBA/TiO of the present invention 2The preparation method of composite membrane may further comprise the steps:
(1) to porous TiO as supporter 2Pottery carries out preliminary treatment;
(2) measure quantitative PEBA particle with photoelectric analytical balance; Be dissolved in the quantitative solvent, process the PEBA polymer solution of certain mass mark, 70 ℃ of following constant temperature stir 3h; Up to forming homogeneous transparent solution; Polymer solution leaves standstill 10h in 60 ℃ of water-baths of constant temperature then, in solution, does not have bubble, and is for use;
(3) under the dustfree environment, with TiO 2Ceramic membrane places in the culture dish, adds deionized water in the culture dish, with ability infiltrating T iO 2Ceramic membrane surface is as the criterion, and leaving standstill until the water surface does not have disturbance, gets polymer solution with the capillary pipette, drops in TiO 2Ceramic membrane surface, the polymer weight of dropping is controlled at 0.01-0.06 g, avoids the polymer drop to cause the disturbance of the water surface during dropping liquid, and polymer solution is dripping to TiO 2Ceramic membrane surface moment is because TiO 2Ceramic membrane is soaked into by deionized water, and the solvent with special surface ability just begins to play a role, and this moment, polymer solution was just at TiO 2Ceramic membrane surface spontaneously spreads rapidly and comes, and in this process, solvent is certainly in evaporation, and rapid exchange has taken place for solvent and non-solvent deionized water simultaneously, like this will be at TiO 2Ceramic membrane surface forms the PEBA film, processes PEBA/TiO 2The composite membrane first product;
(4) leave standstill after the water surface does not have disturbance, with culture dish move to experiment special-purpose to have in the micro-wave oven that vacuumizes function heating predrying, promptly vacuumize with vavuum pump; Adjust suitable power and make in the stove temperature at 65 ~ 75 ℃, behind 1h ~ 2h, the removal that is dried of most of water and solvent; Then, move in the constant temperature vacuum drying chamber, under 60 ℃ ~ 70 ℃ of constant temperature, vacuum 90 ~ 95kPa condition; Keep 4 ~ 6h, continue dry and removal excessive moisture and solvent, obtain PEBA/TiO 2The composite membrane finished product.
Add deionized water in the culture dish of the present invention, with ability infiltrating T iO 2Ceramic membrane surface is as the criterion and refers to the water surface and the TiO of deionized water in the culture dish 2Ceramic membrane thickness keeps flushing.
In the 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 with porous TiO that pottery carries out preliminary treatment 2Ceramic membrane surface polishes smooth, and rinses well with deionized water again.
In the PEBA solution of the present invention, the mass fraction of PEBA is 5%-10%.
In the PEBA solution of the present invention, solvent is isopropyl alcohol, n-butanol or mixed solvent (isopropyl alcohol and n-butanol are miscible in the 3:1 ratio).
Porous TiO of the present invention 2Thick 1 ~ the 2mm of ceramic supporting body.
Vacuum < the 1kPa that vacuumizes of the present invention.
The inventive method is based on the MJPZ principle, with the TiO of resistance to acids and bases, anti-swelling 2Ceramic membrane is a supporting layer, and the PEBA film that permeability and selectivity are high is that separating layer obtains composite membrane, compared with prior art has following beneficial effect:
The PEBA/TiO of the present invention's preparation 2Composite membrane combines organic polymer membrane material and ceramic support film to the existing single deficiency of oil gas reclamation film kind, and the inorganic ceramic membrane material is introduced and effectively raised the 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 the 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, and are widely applicable.
Description of drawings
Fig. 1 PEBA/TiO 2Composite membrane preparation method sketch map;
The process chart of Fig. 2 composite membrane separation oil and gas;
1-N 2Bottle; The 2-mass flow controller; The 3-material liquid tank; The 4-membrane module; The 5-cold-trap; The 6-vavuum pump; The 7-soap film flowmeter; The 8-chromatograph; P-pressure (vacuum) table; The C-measurement of concetration.
The specific embodiment
Embodiment 1
(1) to porous TiO 2Ceramic supporting body polishes smooth, and rinses well with deionized water again;
(2) measure the PEBA particle of 1g with photoelectric analytical balance; Be dissolved in the n-butanol of 19g, the configuration quality mark is 5% PEBA film forming liquid, and 70 ℃ of following constant temperature stir 3h on the constant temperature magnetic stirrer; Up to forming homogeneous transparent solution; Polymer solution rests on 10h in 60 ℃ of water-baths of constant temperature then, in solution, does not have bubble, and is for use;
(3) like accompanying drawing 1, under the dustfree environment, with TiO 2Ceramic membrane places in the culture dish, adds deionized water in the culture dish, with ability infiltrating T iO 2Ceramic membrane surface is as the criterion, the water surface and TiO 2Ceramic membrane thickness keeps flushing, and leaving standstill until the water surface does not have disturbance, drips 1 solution at TiO with the capillary pipette 2Ceramic membrane surface, solution weight 0.015g, when dropping liquid, pipette is from TiO 2Ceramic membrane will be within 5 millimeters, lightly drips of solution at TiO 2Ceramic membrane surface, TiO 2Ceramic membrane surface will form extremely thin PEBA film, process PEBA/TiO 2The composite membrane first product;
(4) leave standstill after the water surface does not have disturbance, with culture dish move to experiment special-purpose to have in the micro-wave oven that vacuumizes function heating predrying, promptly vacuumize vacuum with vavuum pump<1kPa adjusts suitable power and makes in the stove temperature at 70 ℃, behind the 1.5h, and the removal that is dried of most of water and solvent; Then, move in the constant temperature vacuum drying chamber, under 60 ℃ of constant temperature, vacuum 90kPa condition; Keep 4h, continue dry and removal excessive moisture and solvent, obtain PEBA/>TiO 2The composite membrane finished product.
Obtain PEBA/TiO 2Composite membrane, PEBA diffusion barrier thickness is 0.016mm, the effective film area is 4.916cm 2, utilize this film to come permeability and separation hexane/nitrogen mixture, when the hexane mole fraction is 10%, under 20 ℃ of the system temperatures, the hexane infiltration rate is 113 (molcm -2S -1Pa -1), separating degree is 27.
Embodiment 2
(1) to porous TiO 2Ceramic supporting body polishes smooth, and rinses well with deionized water again;
(2) measure the PEBA particle of 1g with photoelectric analytical balance; Be dissolved in the n-butanol of 19g, the configuration quality mark is 5% PEBA film forming liquid, and 70 ℃ of following constant temperature stir 3h on the constant temperature magnetic stirrer; Up to forming homogeneous transparent solution; Polymer solution rests on 10h in 60 ℃ of water-baths of constant temperature then, in solution, does not have bubble, and is for use;
(3) like accompanying drawing 1, under the dustfree environment, with TiO 2Ceramic membrane places in the culture dish, adds deionized water in the culture dish, with ability infiltrating T iO 2Ceramic membrane surface is as the criterion, the water surface and TiO 2Ceramic membrane thickness keeps flushing, and leaving standstill until the water surface does not have disturbance, gets trace polymer solution with the capillary pipette at every turn, drops in TiO 2Ceramic membrane surface drips 1 at every turn, drips twice, and solution weight 0.035g want light during dropping liquid, and pipette is apart from TiO 2Ceramic membrane will be controlled within 5 millimeters, avoids the polymer drop to cause the disturbance of the water surface, and polymer solution is dripping to TiO 2Ceramic membrane surface moment is because TiO 2Ceramic membrane is soaked into by deionized water, and the solvent with special surface ability just begins to play a role, and this moment, polymer solution was just at TiO 2Ceramic membrane surface spontaneously spreads rapidly and comes, and in this process, solvent is certainly in evaporation, and rapid exchange has taken place for solvent and non-solvent deionized water simultaneously, like this will be at TiO 2Ceramic membrane surface forms the PEBA film, processes PEBA/TiO 2The composite membrane first product;
(4) leave standstill after the water surface does not have disturbance, with culture dish move to experiment special-purpose to have in the micro-wave oven that vacuumizes function heating predrying, promptly vacuumize vacuum with vavuum pump<1kPa adjusts suitable power and makes in the stove temperature at 75 ℃, behind the 2h, and the removal that is dried of most of water and solvent; Then, move in the constant temperature vacuum drying chamber, under 65 ℃ of constant temperature, vacuum 95kPa condition; Keep 5h, continue dry and removal excessive moisture and solvent, obtain PEBA/>TiO 2The composite membrane finished product.
Obtain PEBA/TiO 2Composite membrane, wherein PEBA diffusion barrier thickness is 0.029mm, utilizes this film to come permeability and separation hexane/nitrogen mixture, when the hexane mole fraction is 10%, under 20 ℃ of the system temperatures, the hexane infiltration rate is 106 (molcm -2S -1Pa -1), separating degree is 34.
Embodiment 3
According to the operation of embodiment 1, only change that the PEBA mass fraction is 8% in the PEBA film forming liquid, obtain PEBA/TiO 2Composite membrane utilizes this film to come permeability and separation hexane/nitrogen mixture, when the hexane mole fraction is 10%, under 20 ℃ of the system temperatures, the hexane infiltration rate is 103 (molcm -2S -1Pa -1), separating degree is 30.
Embodiment 4
According to the operation of embodiment 1, only change that solvent is an isopropyl alcohol in the PEBA film forming liquid, obtain PEBA/TiO 2Composite membrane utilizes this film to come permeability and separation hexane/nitrogen mixture, when the hexane mole fraction is 10%, under 20 ℃ of the system temperatures, the hexane infiltration rate is 102 (molcm -2S -1Pa -1), separating degree is 30.
Embodiment 5
According to the operation of embodiment 1, only change that solvent is mixed solvent (isopropyl alcohol and n-butanol is miscible in the 3:1 ratio) in the PEBA film forming liquid, obtain PEBA/TiO 2Composite membrane utilizes this film to come permeability and separation hexane/nitrogen mixture, when the hexane mole fraction is 10%, under 20 ℃ of the system temperatures, the hexane infiltration rate is 107 (molcm -2S -1Pa -1), separating degree is 29.
The patent of invention application example
Like 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 inlet 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, connect vavuum pump 6 in the another port of cold-trap 5.
(1) N 2The N that comes out in the bottle 1 2Through mass flow controller 2, get into material liquid tank 3 again, advertise gasoline or other volatile organic matter (VOC) in the material liquid tank 3, thereby form certain density oil gas-N 2Gaseous mixture.
(2) oil gas-N that comes out from material liquid tank 3 2Gaseous mixture is and directly from N 2The N that comes out in the bottle 1 2After setting concentration proportioning, get into membrane module 4.
(3) oil gas-N 2Gaseous mixture provides infiltration side pressure, oil gas-N by vavuum pump 6 in membrane module 4 2Gaseous mixture is realized permeability and separation at composite membrane, and promptly most of oil gas penetrates from composite membrane, and N 2Have only microdialysis, the big I of the infiltration side pressure of membrane module 4 realizes through regulating vavuum pump 6.
(4) high-concentration oil vapor that infiltrates 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. preparation method who is used for the organic/inorganic composite membrane that oil gas reclaims may further comprise the steps:
(1) to porous TiO as supporter 2Pottery carries out preliminary treatment;
(2) measure quantitative PEBA particle with photoelectric analytical balance; Be dissolved in the quantitative solvent, process the PEBA polymer solution of certain mass mark, 70 ℃ of following constant temperature stir 3h; Up to forming homogeneous transparent solution; Polymer solution leaves standstill 10h in 60 ℃ of water-baths of constant temperature then, in solution, does not have bubble, and is for use;
(3) under the dustfree environment, with TiO 2Ceramic membrane places in the culture dish, adds deionized water in the culture dish, with ability infiltrating T iO 2Ceramic membrane surface is as the criterion, and leaving standstill until the water surface does not have disturbance, gets polymer solution with the capillary pipette, drops in TiO 2Ceramic membrane surface, the polymer weight of dropping is controlled at 0.01-0.06 g, avoids the polymer drop to cause the disturbance of the water surface during dropping liquid, processes PEBA/TiO 2The composite membrane first product;
(4) leave standstill after the water surface does not have disturbance, with culture dish move to experiment special-purpose to have in the micro-wave oven that vacuumizes function heating predrying, promptly vacuumize with vavuum pump; Adjust suitable power and make the interior temperature of stove, behind 1h ~ 2h, move in the constant temperature vacuum drying chamber at 65 ~ 75 ℃; Under 60 ℃ ~ 70 ℃ of constant temperature, vacuum 90 ~ 95kPa condition; Keep 4 ~ 6h, continue dry and removal excessive moisture and solvent, obtain PEBA/TiO 2The composite membrane finished product.
2. a kind of preparation method who is used for the organic/inorganic composite membrane of oil gas recovery as claimed in claim 1 is characterized in that: add deionized water in the described culture dish, with ability infiltrating T iO 2Ceramic membrane surface is as the criterion and refers to the water surface and the TiO of deionized water in the culture dish 2Ceramic membrane thickness keeps flushing.
3. a kind of preparation method who is used for the organic/inorganic composite membrane of oil gas recovery as claimed in claim 1, it is characterized in that: the capillary pipette is apart from TiO during dropping liquid 2Ceramic membrane will be controlled within 5 millimeters.
4. a kind of preparation method who is used for the organic/inorganic composite membrane of oil gas recovery as claimed in claim 1 is characterized in that: described to porous TiO 2It is with porous TiO that pottery carries out preliminary treatment 2Ceramic membrane surface polishes smooth, and rinses well with deionized water again.
5. a kind of preparation method who is used for the organic/inorganic composite membrane of oil gas recovery as claimed in claim 1, it is characterized in that: in the described PEBA solution, the mass fraction of PEBA is 5%-10%.
6. a kind of preparation method who is used for the organic/inorganic composite membrane of oil gas recovery as claimed in claim 1; It is characterized in that: in the 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. a kind of preparation method who is used for the organic/inorganic composite membrane of oil gas recovery as claimed in claim 1 is characterized in that: described porous TiO 2Thick 1 ~ the 2mm of ceramic supporting body.
8. a kind of preparation method who is used for the organic/inorganic composite membrane of oil gas recovery as claimed in claim 1 is characterized in that: the described vacuum < 1kPa that vacuumizes.
CN201110306016.1A 2011-10-11 2011-10-11 Organic/inorganic composite membrane for use in oil gas recovery and preparation method thereof Active CN102389723B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105536566A (en) * 2016-01-19 2016-05-04 长安大学 Composite membrane with function of separating lithium ions and cobalt ions and preparation method thereof
CN105561803A (en) * 2015-12-29 2016-05-11 合肥创想能源环境科技有限公司 Preparation method of high-flux and high-precision ceramic ultrafiltration membrane for oil removal and iron removal of high-temperature condensed water
CN108714372A (en) * 2018-05-29 2018-10-30 太原理工大学 Processing method for coal chemical industrial waste water
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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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105561803A (en) * 2015-12-29 2016-05-11 合肥创想能源环境科技有限公司 Preparation method of high-flux and high-precision ceramic ultrafiltration membrane for oil removal and iron removal of high-temperature condensed water
CN105536566A (en) * 2016-01-19 2016-05-04 长安大学 Composite membrane with function of separating lithium ions and cobalt ions and preparation method thereof
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
CN108714372A (en) * 2018-05-29 2018-10-30 太原理工大学 Processing method for coal chemical industrial waste water
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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