CN101721924B - Process for preparing polyacrylonitrile-grafted modified cellulose membrane for gasoline desulfurization - Google Patents
Process for preparing polyacrylonitrile-grafted modified cellulose membrane for gasoline desulfurization Download PDFInfo
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- CN101721924B CN101721924B CN2009102314816A CN200910231481A CN101721924B CN 101721924 B CN101721924 B CN 101721924B CN 2009102314816 A CN2009102314816 A CN 2009102314816A CN 200910231481 A CN200910231481 A CN 200910231481A CN 101721924 B CN101721924 B CN 101721924B
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Abstract
The invention relates to a process for preparing a polyacrylonitrile-grafted modified cellulose membrane for gasoline desulfurization. The invention adopts the technical scheme that the process comprises the following steps: 1) dissolving a cellulose-polyacrylonitrile grafted copolymer into a certain amount of solvent, continuously stirring the mixture under a sealed condition to obtain even and transparent cellulose-polyacrylonitrile grafted copolymer solution, and then filtering, standing and degassing the membrane preparation solution; and 2) coating the obtained copolymer solution on a glass plate to form a membrane, volatilizing the solvent, drying the membrane, putting the membrane into deionized water to separate the membrane from the glass plate, and drying the membrane for later use. The membrane manufactured by the invention has the characteristic of obvious micro-phase separation structure, wherein the polyacrylonitrile side chain plays a role in supporting the membrane structure and the crosslinked cellulose main chain and inhibiting the swelling of the membrane; and the cellulose chain segment is a main selective permeation material of the membrane, the adjustment to permeability and selectivity depends on the change of contents of different chain segments, and the membrane shows good separation performance and mechanical stability in the permeation-evaporation separation of the gasoline desulfurization.
Description
One, technical field:
The present invention relates to a kind of infiltrating and vaporizing membrane separation technology field, particularly a kind of preparation technology of polyacrylonitrile-grafted modified cellulose membrane for gasoline desulfurization.
Two, background technology:
Infiltrating and vaporizing membrane is used for the S-Brane technology that the gasoline desulfur field starts from Grace Davison company.With traditional gasoline desulfur compared with techniques, but embrane method gasoline desulfur technology have investment and the low deep desulfuration of operating cost, lose octane number few, be easy to amplify advantages such as dilatation and construction.Since Grace Davison proposed the S-Brane technology first in the NPRA meeting in 2002, companies such as Exxon Mobil, TransIonics and Marathon Oil also dropped into the exploitation of infiltrating and vaporizing membrane gasoline desulfur project in succession.Domesticly carry out the Kong Ying that mainly contains China University Of Petroleum Beijing of this Project Study, the Li Jiding of Tsing-Hua University and the people such as Jiang Zhongyi of University Of Tianjin.Because diffusion barrier is the core component of embrane method gasoline desulfur technology, the diffusion barrier that development can efficiently remove sulfur-containing compound in the gasoline has become whole world related scientific research personnel's research focus in the nature of things.
External representative separation membrane material mainly contains the PERVAP1060 commercial membranes and the PVP film of Grace Davison company and Research and Engineering department of ExxonMobil company.With the PERVAP1060 commercial membranes is example, at first is separation system with the analog gasoline, is 297K in temperature, and the film backside pressure is under the 1346.3Pa condition, and rich thioneine of this film is 2.35, and corresponding permeation flux is 1.3kg/ (m
2H), has certain separating effect.Thereafter the naphtha that changes sulfur content and be 920 μ g/g is a raw material, and under the identical operations condition, rich thioneine of this film is 0.56, and corresponding permeation flux is 1.1kg/ (m
2H).Desulfurization performance by the PERVAP1060 film can find out that the infiltrating and vaporizing membrane desulfurized effect of early development is very little.After this many rich thioneine with the raising film of developing material are main target, and the PUU film that is all the exploitation of Grace Davison company is the desulfurization object with the naphtha, and its rich thioneine is up to 5.12, but permeation flux has only 0.085kg/ (m
2H), the expense of industrial applications is very high.The domestic Tsing-Hua University that takes the lead in carrying out the gasoline desulfur developing material is a parting material with PDMS, and analog gasoline is a separation system, and rich thioneine can reach 4.9, and corresponding permeation flux is 1.5kg/ (m
2H), has certain application prospect.The PEG composite membrane that has just waited the people to develop that stands in great numbers of hole beautiful jade seminar of China University Of Petroleum Beijing is a raw material with FCC gasoline, and rich thioneine is 3.05, and corresponding permeation flux is 1.63kg/ (m
2H).In addition, the triethanolamine of ExxonMobil company is handled Nafion.RTM.117 (H
+) polyimide composite film, the polyurethane composite membrane of PEM, Grace Davision company, the polyimide composite film of Tsing-Hua University, and the PDMS/Ni of University Of Tianjin
2+Diffusion barriers such as Y molecular sieve blend film all have certain desulfurized effect.
Two critical index of diffusion barrier are sulfur enrichment factor and permeation flux.Desulfurization is both at home and abroad at present paid close attention to the sulfur enrichment factor that improves film with the relevant exploitation of infiltrating and vaporizing membrane more, the problem that the ubiquity permeation flux is not enough.If permeation flux is too little; Even film has very high sulfur enrichment factor; In commercial production, do not have application prospect because but lower permeation flux need remedy with very large membrane area usually, thereby cause the equipment investment expense huge; Operation energy consumption is too high, makes the embrane method desulfur technology not have too big economy advantage to say with respect to other desulfur technologies.
Therefore; Exploitation has more high permeating flux, and the high-performance diffusion barrier that can keep or improve simultaneously rich thioneine again reduces investment cost to reducing membrane area; Cut down the consumption of energy, have conclusive effect thereby embrane method gasoline desulfur technology is really moved towards the industrialization use.
Cellulose pervaporation membrane has good desulfurization performance, and University of Petroleum had developed the cellulose crosslinked film with independent intellectual property right already, and the patent No. is CN1974729, and this film is tested through pilot scale at present.The trial of this seminar utilizes the method for graft modification to have the polymer of good mechanical properties and solvent resistance at the cellulose side chain graft.The objective of the invention is the good and lower polyacrylonitrile side chain of modification expense, in the hope of promoting the industrial applications of this film fast at cellulose side chain graft solvent resistance.
Three, summary of the invention:
The object of the invention is exactly the above-mentioned defective that exists to prior art; A kind of preparation technology of polyacrylonitrile-grafted modified cellulose membrane for gasoline desulfurization is provided; The characteristics of this film activity cortex are to have tangible micro phase separation structure; Polyacrylonitrile side chain wherein plays the function of support membrane structure and cross-linked cellulose main chain simultaneously, suppresses the swelling of film; Cellulose chain segment then is the main selective permeation material of this film, permeability with optionally regulate the variation depend on different segment content.This film shows good separating property and mechanical stability in the gasoline desulfur infiltration evaporation separates.
Technical scheme of the present invention may further comprise the steps:
1) cellulose-polyacrylonitrile graft copolymers is dissolved in the certain amount of solvent; Under air-proof condition, continue to stir 1～2 day; Finally obtain homogeneous, transparent cellulose-polyacrylonitrile graft copolymers solution, then preparation liquid is filtered and leave standstill the degassing 1～2 day with 300 order stainless (steel) wires;
2) with the cellulose that obtains-polyacrylonitrile graft copolymers solution coating filmform on as the polypropylene of supporting layer or polyvinylidene fluoride (PVDF) ultrafiltration membrane; And 40～80 ℃ of following solvent flashings 2～3 hours; After this vacuum drying 2～3 hours under 40～80 ℃ of conditions, subsequent use.
Wherein, above-mentioned steps 1) cellulosic mass fraction is 40%～80% in cellulose-polyacrylonitrile graft copolymers.
Said step 1) cellulose-polyacrylonitrile graft copolymers is synthetic through the solution free radical polymerization method.
In the said step 1) casting solution process for preparation, solvent for use is N, dinethylformamide, N, any one in N-dimethylacetylamide, N-methyl pyrrolidone and the dimethyl sulfoxide (DMSO).
In the said step 1) casting solution process for preparation, the mass fraction of cellulose-polyacrylonitrile graft copolymers in solution is 10%～15%.
Described cellulose is meant a kind of in hydroxypropyl methylcellulose, hydroxypropyl cellulose, CMC, hydroxyethylcellulose or the cellulose acetate, also can be above two or more cellulosic mixtures arbitrarily.
In addition, the making step of solution free radical polymerization method synthetic cellulose-polyacrylonitrile graft copolymers of the present invention is following:
At ambient temperature a certain amount of cellulose and paraformaldehyde are dissolved in the dimethyl sulfoxide solvent, this mixed solution stirred 30～60 minutes under 90～100 ℃ of conditions fast, under 130 ℃ of conditions, stirred at a slow speed about 10 minutes then, cooled off subsequent use; Cooled dimethyl sulphoxide solution adds a certain proportion of radical initiator and fed nitrogen at ambient temperature 30～60 minutes, adds a certain proportion of acrylonitrile monemer and stirs 3～10 hours, and reaction temperature is 20～80 ℃; Reaction system adds the hydroquinones cessation reaction; Reaction finishes to precipitate the precipitated product dry for standby in the deionized water that afterreaction liquid slowly splashes into quick stirring.
The ratio of cellulose and paraformaldehyde is about 1: 1.2 in the solution free radical polymerization process.
Radical initiator is any one in ammonium persulfate, azodiisobutyronitrile and the benzoyl peroxide in the solution free radical polymerization process.
The modification of membrane material is through improving its mechanical performance and solvent resistance at cellulose side chain graft polyacrylonitrile.Cellulosic material is cheap and easy to get; Solution free radical polymerization method graft polypropylene nitrile technical maturity, easy realization and method of modifying are feasible economically in actual production.
The invention has the beneficial effects as follows: the active cortex of the infiltrating and vaporizing membrane that the present invention produces is the plain film of a kind of graft copolymer fibre; Main body in the polymer is the cellulosic polymer that sulfur-containing compound in the gasoline is had good selectivity and separating property, and the side chain polyacrylonitrile has very strong solvent resistance and the mechanical performance of cellulose membrane is strengthened.This film had both had good desulfurization performance and the permeation flux that possesses industrial applications, can tolerate comparatively harsh operating condition and pollution again.The solution free radical polymerization method is ripe, the higher and economically feasible of percent grafting, and the new type gasoline film material for desulfuration that has commercial value for exploitation provides new approach.
Four, the specific embodiment:
Embodiment 1: at ambient temperature 5g CMC and 6g paraformaldehyde are dissolved in the 200ml dimethyl sulfoxide solvent; This mixed solution stirred 30 minutes under 90～100 ℃ of conditions fast; Under 130 ℃ of conditions, stir at a slow speed about 10 minutes then, cool off subsequent use; Cooled dimethyl sulphoxide solution adds the 0.8g ammonium persulfate and under 20 ℃ of conditions, fed nitrogen about 30 minutes, adds the 5g acrylonitrile monemer and stirs 3 hours, and reaction temperature is 40 ℃; Reaction system adds the hydroquinones cessation reaction; Reaction finishes to precipitate in the deionized water that afterreaction liquid slowly splashes into quick stirring, and the post precipitation product is dry for standby under 50 ℃ of conditions.
The cellulose that obtains-polyacrylonitrile graft copolymers 5g is dissolved in 45ml N; In the dinethylformamide; Under air-proof condition, continue to stir 2 days; Finally obtain homogeneous, transparent cellulose-polyacrylonitrile graft copolymers solution, then preparation liquid is filtered and leave standstill the degassing 2 days with 300 order stainless (steel) wires; With the cellulose that obtains-polyacrylonitrile graft copolymers solution coating filmform on the polypropylene milipore filter, and 50 ℃ of following solvent flashings 3 hours, vacuum drying 3 hours under 50 ℃ of conditions after this, the cortex thickness is 10 μ m.
Implementation result: the separating property of made film is following; Adopting FCC gasoline is separate object; In feed sulphur content is that 800～1200 μ g/g, feeding temperature are that 100～120 ℃, film backside pressure are not more than under the condition of 500Pa; The diffusion barrier sulfur enrichment factor of preparing is greater than 4.2, and permeation flux is greater than 1.4kg.m
-2.h
-1
Embodiment 2: at ambient temperature 5g hydroxyethylcellulose and 6g paraformaldehyde are dissolved in the 200ml dimethyl sulfoxide solvent; This mixed solution stirred 30 minutes under 90～100 ℃ of conditions fast; Under 130 ℃ of conditions, stir at a slow speed about 10 minutes then, cool off subsequent use; Cooled dimethyl sulphoxide solution adds the 0.4g azodiisobutyronitrile and under 20 ℃ of conditions, fed nitrogen about 30 minutes, adds the 5g acrylonitrile monemer and stirs 3 hours, and reaction temperature is 40 ℃; Reaction system adds the hydroquinones cessation reaction; Reaction finishes to precipitate in the deionized water that afterreaction liquid slowly splashes into quick stirring, and the post precipitation product is dry for standby under 50 ℃ of conditions.
The cellulose that obtains-polyacrylonitrile graft copolymers 5g is dissolved in the 45ml dimethyl sulfoxide (DMSO); Under air-proof condition, continue to stir 1～2 day; Finally obtain homogeneous, transparent cellulose-polyacrylonitrile graft copolymers solution, then preparation liquid is filtered and leave standstill the degassing 2 days with 300 order stainless (steel) wires; With the cellulose that obtains-polyacrylonitrile graft copolymers solution coating filmform on polyvinylidene fluoride (PVDF) ultrafiltration membrane, and 80 ℃ of following solvent flashings 3 hours, vacuum drying 3 hours under 60 ℃ of conditions after this, the cortex thickness is 10 μ m.
Implementation result: the separating property of made film is following; Adopting FCC gasoline is separate object; In feed sulphur content is that 800～1200 μ g/g, feeding temperature are that 100～120 ℃, film backside pressure are not more than under the condition of 500Pa; The diffusion barrier sulfur enrichment factor of preparing is greater than 3.8, and permeation flux is greater than 2.0kg.m
-2.h
-1
Embodiment 3: at ambient temperature 5g hydroxypropyl methylcellulose and 6g paraformaldehyde are dissolved in the 200ml dimethyl sulfoxide solvent; This mixed solution stirred 30 minutes under 90～100 ℃ of conditions fast; Under 130 ℃ of conditions, stir at a slow speed about 10 minutes then, cool off subsequent use; Cooled dimethyl sulphoxide solution adds the 0.4g benzoyl peroxide and under 20 ℃ of conditions, fed nitrogen about 30 minutes, adds the 5g acrylonitrile monemer and stirs 3 hours, and reaction temperature is 40 ℃; Reaction system adds the hydroquinones cessation reaction; Reaction finishes to precipitate in the deionized water that afterreaction liquid slowly splashes into quick stirring, and the post precipitation product is dry for standby under 50 ℃ of conditions.
The cellulose that obtains-polyacrylonitrile graft copolymers 5g is dissolved in 45ml N; In the dinethylformamide; Under air-proof condition, continue to stir 1～2 day; Finally obtain homogeneous, transparent cellulose-polyacrylonitrile graft copolymers solution, then preparation liquid is filtered and leave standstill the degassing 2 days with 300 order stainless (steel) wires; With the cellulose that obtains-polyacrylonitrile graft copolymers solution coating filmform on the polypropylene milipore filter, and 80 ℃ of following solvent flashings 3 hours, vacuum drying 2～3 hours under 60 ℃ of conditions after this, thickness is 10 μ m.
Implementation result: the separating property of made film is following; Adopting FCC gasoline is separate object; In feed sulphur content is that 800～1200 μ g/g, feeding temperature are that 100～120 ℃, film backside pressure are not more than under the condition of 500Pa; The diffusion barrier sulfur enrichment factor of preparing is greater than 4.0, and permeation flux is greater than 2.6kg.m
-2.h
-1
Claims (9)
1. the preparation technology of a polyacrylonitrile-grafted modified cellulose membrane for gasoline desulfurization is characterized in that may further comprise the steps:
1) cellulose-polyacrylonitrile graft copolymers is dissolved in the certain amount of solvent; Under air-proof condition, continue to stir 1～2 day; Finally obtain homogeneous, transparent cellulose-polyacrylonitrile graft copolymers solution, then preparation liquid is filtered and leave standstill the degassing 1～2 day with stainless (steel) wire;
2) with the cellulose that obtains-polyacrylonitrile graft copolymers solution coating filmform on as the polypropylene of supporting layer or polyvinylidene fluoride (PVDF) ultrafiltration membrane; And 40～80 ℃ of following solvent flashings 2～3 hours; After this vacuum drying 2～3 hours under 40～80 ℃ of conditions, subsequent use.
2. the preparation technology of polyacrylonitrile-grafted modified cellulose membrane for gasoline desulfurization according to claim 1, it is characterized in that: above-mentioned steps 1) cellulosic mass fraction is 40%～80% in cellulose-polyacrylonitrile graft copolymers.
3. the preparation technology of polyacrylonitrile-grafted modified cellulose membrane for gasoline desulfurization according to claim 1 is characterized in that: above-mentioned steps 1) cellulose-polyacrylonitrile graft copolymers is synthetic through the solution free radical polymerization method.
4. the preparation technology of polyacrylonitrile-grafted modified cellulose membrane for gasoline desulfurization according to claim 1; It is characterized in that: above-mentioned steps 1) in the casting solution process for preparation; Solvent for use is N; Dinethylformamide, N, any one in N-dimethylacetylamide, N-methyl pyrrolidone and the dimethyl sulfoxide (DMSO).
5. the preparation technology of polyacrylonitrile-grafted modified cellulose membrane for gasoline desulfurization according to claim 1; It is characterized in that: above-mentioned steps 1) in the casting solution process for preparation, the mass fraction of cellulose-polyacrylonitrile graft copolymers in solution is 10%～15%.
6. the preparation technology of polyacrylonitrile-grafted modified cellulose membrane for gasoline desulfurization according to claim 1; It is characterized in that: described cellulose is meant hydroxypropyl methylcellulose, hydroxypropyl cellulose, CMC, hydroxyethylcellulose or cellulose acetate, also can be above two or more cellulosic mixtures arbitrarily.
7. the preparation technology of polyacrylonitrile-grafted modified cellulose membrane for gasoline desulfurization according to claim 3, it is characterized in that: the making step of described solution free radical polymerization method synthetic cellulose-polyacrylonitrile graft copolymers is following:
At ambient temperature a certain amount of cellulose and paraformaldehyde are dissolved in the dimethyl sulfoxide solvent, this mixed solution stirred 30～60 minutes under 90～100 ℃ of conditions fast, under 130 ℃ of conditions, stirred at a slow speed about 10 minutes then, cooled off subsequent use; Cooled dimethyl sulphoxide solution adds a certain proportion of radical initiator and fed nitrogen at ambient temperature 30～60 minutes, adds a certain proportion of acrylonitrile monemer and stirs 3～10 hours, and reaction temperature is 20～80 ℃; Reaction system adds the hydroquinones cessation reaction; Reaction finishes to precipitate the precipitated product dry for standby in the deionized water that afterreaction liquid slowly splashes into quick stirring.
8. the preparation technology of polyacrylonitrile-grafted modified cellulose membrane for gasoline desulfurization according to claim 7, it is characterized in that: the ratio of cellulose and paraformaldehyde is about 1: 1.2.
9. the preparation technology of polyacrylonitrile-grafted modified cellulose membrane for gasoline desulfurization according to claim 7, it is characterized in that: described radical initiator is any one in ammonium persulfate, azodiisobutyronitrile and the benzoyl peroxide.
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| CN103897726B (en) * | 2012-12-27 | 2015-08-19 | 中国石油天然气股份有限公司 | A kind of gasoline desulfurizer and preparation method thereof |
| CN107754609A (en) * | 2016-08-19 | 2018-03-06 | 上海键水科技发展有限公司 | A kind of composite nanometer filtering film and preparation method thereof |
| CN106334458A (en) * | 2016-10-20 | 2017-01-18 | 合肥创想能源环境科技有限公司 | Method for preparing crosslinking HEC pervaporation membrane for gasoline desulfurization |
| CN107118303A (en) * | 2017-05-31 | 2017-09-01 | 环境保护部南京环境科学研究所 | A kind of preparation and application of modified wheat stalk cellulose |
| CN112853525B (en) * | 2021-01-08 | 2023-01-03 | 界首市盛泰服装科技有限公司 | Preparation method and application of high-strength cellulose grafted polyacrylonitrile composite fiber |
| CN113680391B (en) * | 2021-09-07 | 2023-10-27 | 山东中移能节能环保科技股份有限公司 | Coke oven flue gas desulfurization catalyst and preparation method thereof |
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