阅读说明：本技术 一种表面金属离子改性的硅橡胶脱硫膜及其制备方法和应用 (A kind of silicon rubber desulfurizing film and its preparation method and application that surface metal ion is modified ) 是由 韩小龙 高健 樊晓涛 蔡采彬 于 2019-07-23 设计创作，主要内容包括：本发明属于渗透汽化脱硫技术领域,具体涉及一种表面金属离子改性的硅橡胶脱硫膜及其制备方法和应用,本发明通过化学反应的方法在聚二甲基硅氧烷(PDMS)复合膜表面接枝含有活性环氧官能团的硅烷偶联剂,再在碱性条件下使环氧基开环,将多齿螯合剂以共价键力结合在膜上,通过螯合剂的多齿螯合性将金属离子螯合到PDMS复合膜表面,制备出金属离子改性的PDMS复合膜,该方法制备出的渗透汽化脱硫膜,制备方法简单,机械性能、热稳定性和溶胀性能均提升明显,膜的脱硫性能明显提高。(The invention belongs to infiltration evaporation technical field of desulfurization, more particularly to a kind of modified silicon rubber desulfurizing film and its preparation method and application of surface metal ion, the present invention is grafted the silane coupling agent containing active epoxy functional group in dimethyl silicone polymer (PDMS) composite film surface by the method for chemical reaction, make epoxy ring-opening under alkaline condition again, multiple tooth chelating agent is incorporated on film with covalent bonding forces, pass through the multiple tooth sequestering by metal ion-chelant to PDMS composite film surface of chelating agent, prepare metal ion-modified PDMS composite membrane, the infiltration evaporation desulfurizing film that this method is prepared, preparation method is simple, mechanical performance, thermal stability and swelling behavior are promoted obviously, the desulfurization performance of film significantly improves.)

1. a kind of modified silicon rubber desulfurizing film of surface metal ion, it is characterised in that: including supporting layer and be arranged in supporting layer On separating layer, wherein supporting layer be the porous bottom membrane of Kynoar, the separating layer be pass through activator, chelating agent and gold Belong to the dimethyl silicone polymer layer of ion modification.

2. according to a kind of silicon rubber desulfurizing film that surface metal ion is modified described in claim 1, which is characterized in that the activation Agent be 3- (2,3- the third oxygen of epoxy) propyl-triethoxysilicane, ethyoxyl dimethyl [3- (ethylene oxide oxygroup) propyl] silane, One or more of 3- glycidyloxypropyl trimethoxy silane, is connected on film by the method for chemical reaction.

3. according to a kind of silicon rubber desulfurizing film that surface metal ion is modified described in claim 1, which is characterized in that the chelating Agent be one or more of iminodiacetic acid, two (carboxymethyl) ethylenediamines, carboxymethyl asparagic acid, five amine of tetraethyl alkene, It reacts with the active function groups of film surface, is incorporated on film with covalent bonding forces.

4. a kind of modified silicon rubber desulfurizing film of surface metal ion according to claim 1, which is characterized in that the gold Category ion is one of copper ion, zinc ion, manganese ion, and metal ion is sequestered in poly dimethyl by chemical grafting method Silicone film surface.

5. a kind of modified silicon rubber desulfurizing film of surface metal ion according to claim 1, which is characterized in that the branch Layer is supportted with a thickness of 20-50 μm, separating layer with a thickness of 20-30 μm.

6. a kind of preparation side of the modified silicon rubber desulfurizing film of surface metal ion according to claim 1-5 Method, it is characterised in that: the following steps are included:

S1. the porous counterdie of Kynoar and dimethyl silicone polymer composite membrane are prepared；

S2. dimethyl silicone polymer composite membrane is immersed in the activator of ethyl alcohol dissolution, by the silicon containing active epoxy functional group After alkane coupling agent is grafted on PDMS membrane, it is taken out from solution, deionized water rinsing, drying obtains table Contain the PDMS film of active function groups in face；

S3. the PDMS film that active function groups are contained on surface is immersed in alkaline chelate solution, chelation group is introduced on film, by it From solution take out and use deionized water rinsing, drying, obtain drying the PDMS film with chelating function；

S4. the PDMS film with chelating function is immersed into metal salt solution, makes metal ion-chelant on dimethyl silicone polymer And with deionized water rinsing, drying, the modified dimethyl silicone polymer composite membrane of dry surface metal ion, i.e. silicon rubber are obtained Rubber desulfurizing film.

7. a kind of preparation method of the modified silicon rubber desulfurizing film of surface metal ion according to claim 6, feature Be: in S1, the preparation of dimethyl silicone polymer composite membrane includes the following steps:

Dimethyl silicone polymer is dissolved in organic solvent B under room temperature, crosslinking agent is added after stirring and catalyst is quiet after mixing It sets deaeration and obtains casting solution, casting solution is cast on Kynoar counterdie and knifing is crosslinked after the solvent is volatilized, Dimethyl silicone polymer layer is formed on Kynoar counterdie, so that dimethyl silicone polymer infiltration evaporation desulfurizing film be made； Wherein, dimethyl silicone polymer, organic solvent, crosslinking agent, catalyst mass ratio be 30: 60: 3: 1；

Organic solvent B is normal heptane or toluene；

The crosslinking agent is ethyl orthosilicate or 3- aminopropyl trimethoxysilane；The catalyst is di lauric dibutyl Tin；

The time of the solvent volatilization is 12h；The temperature of the crosslinking is 80 DEG C, time 5h.

8. a kind of preparation method of the modified silicon rubber desulfurizing film of surface metal ion according to claim 6, feature Be: activator proportion is ethyl alcohol, the silane coupling agent containing active epoxy functional group, water according to mass ratio 165: 1 in S2: The mixed solution formed after 1 mixing, reaction temperature are 60 DEG C, react 12 hours.

9. a kind of preparation method of the modified silicon rubber desulfurizing film of surface metal ion according to claim 6, feature Be: the concentration of chelating agent solution is 0.1-0.3mol/L in S3, and adjusting pH value is 9-11, and reaction temperature is 60-80 DEG C, reaction Time 9-12h.

10. a kind of preparation method of the modified silicon rubber desulfurizing film of surface metal ion according to claim 6, feature Be: the concentration of metal salt solution is 0.2mol/L in S4, and reaction temperature is 20-30 DEG C.

Technical field

The present invention relates to infiltration evaporation desulfuration fields, more particularly to the modified poly dimethyl silicon in a metal ion species surface Compound desulfurizing film of oxygen and its preparation method and application.

Background technique

With the development of process of industrialization, people are to the energy with increasing, and gasoline is as currently the most important ones energy One of source is measured, while bringing convenient, also brings huge pollution environmentally, the sulphur oxidation after gasoline combustion Object (SOx) is even more that can form acid rain and second particle substance, seriously pollutes environment.Current many countries and regions strictly limit Sulfur content in motor vehicle fuel processed.In China, the sulfur content that gasoline is strict in the implementation of " state's V gasoline standard " will be controlled In 10ppm hereinafter, and China oil product source it is single, catalytically cracked gasoline accounting is huge, so economical, efficient gasoline is de- Sulphur method is a big problem of Chinese Enterprises urgent need to resolve.Desulfurization most conventional methods are catalytic hydrogenations at present, but this biography Process requirement high temperature and pressure of uniting and high hydrogen consumption and expensive noble metal catalyst.Infiltration evaporation membrane separation technique is low with its Energy consumption, environmental-friendly, easy to operate, being easy to the advantages that amplifying may be implemented the deep desulfuration of FCC gasoline and attracts extensive attention.

Infiltration evaporation process is in liquid mixture under the promotion of component steam pressure difference, using component to be separated organic Or solubility behavior, the different of diffusion velocity realize the processes separated in inorganic infiltrating and vaporizing membrane, core element is infiltration Membrane material is vaporized, permeation flux and the sulfur-rich factor are to measure two important indicators of membrane material, so exploitation high osmosis and height The infiltrating and vaporizing membrane of selectivity is the key that Membrane Desulphurization.The membrane material for being usually used in infiltration evaporation desulfurization at present has poly dimethyl silicon Oxygen alkane, polyethylene glycol, cellulose etc..Dimethyl silicone polymer has cheap and easy to get, and free volume is big, good organophilic etc. Characteristic is used as infiltration evaporation material extensively.Although pure PDMS membrane permeation flux is big, due to intermolecular work It is firmly small, and in the presence of easily swelling, the disadvantages such as selectivity is lower, and mechanical performance is low.Therefore, a kind of pair of dimethyl silicone polymer is needed The technical solution that film is modified is to overcome it to be easily swollen, the disadvantages such as selectivity is lower, and mechanical performance is low.

Summary of the invention

The object of the present invention is to provide a metal ion species the surface modified compound desulfurizing films of polydimethylsiloxanes and its system Preparation Method and application, to solve the above-mentioned problems of the prior art, in the desulfurization for improving PDMS membrane composite membrane It is overcome easily to be swollen while performance, disadvantages that selectivity is lower, and mechanical performance is low etc..

One of technical solution of the present invention is that the polydimethylsiloxanes for providing metal ion species surface modification are compound de- Sulphur film, including supporting layer and the separating layer being arranged on supporting layer, wherein supporting layer is Kynoar (PVDF) porous counterdie Layer, separating layer are by activator, chelating agent and metal ion-modified dimethyl silicone polymer (PDMS) layer；

Preferably, the activator is 3- (2,3- the third oxygen of epoxy) propyl-triethoxysilicane, ethyoxyl dimethyl [3- (ethylene oxide oxygroup) propyl] silane, one or more of 3- glycidyloxypropyl trimethoxy silane；

Preferably, the chelating agent is iminodiacetic acid, two (carboxymethyl) ethylenediamines, carboxymethyl asparagic acid, tetrem One or more of five amine of base alkene；

Preferably, the metal ion is one of copper ion, zinc ion, manganese ion, and metal ion is connect by chemistry The method of branch is sequestered in PDMS membrane surface；

Preferably, the supporting layer is with a thickness of 20-50 μm, separating layer with a thickness of 20-30 μm.

The two of technical solution of the present invention are that the polydimethylsiloxanes for providing above-mentioned metal ion surface modification are compound de- Sulphur membrane preparation method, comprising the following steps:

S1. the porous counterdie of Kynoar and dimethyl silicone polymer composite membrane are prepared；

S2. dimethyl silicone polymer composite membrane is immersed in the activator of ethyl alcohol dissolution, active epoxy functional group will be contained Silane coupling agent be grafted on PDMS membrane after, it is taken out from solution, deionized water rinsing, drying obtains Contain the PDMS film of active function groups to surface；

S3. the PDMS film that active function groups are contained on surface is immersed in alkaline chelate solution, chelation group is introduced on film, It is taken out from solution and with deionized water rinsing, drying, obtains the dry PDMS film with chelating function；

S4. the PDMS film with chelating function is immersed into metal salt solution, makes metal-chelating on dimethyl silicone polymer And with deionized water rinsing, drying, the modified dimethyl silicone polymer composite membrane of dry surface metal ion is obtained.

Preferably, in S1, the preparation of the porous counterdie of Kynoar includes the following steps:

It will be dissolved in organic solvent A after the drying of Kynoar powder, is configured to the solution that mass fraction is 10-20%, mistake Filter, standing and defoaming, obtains clear Kynoar casting solution at room temperature；Kynoar casting solution is uniformly scratched in polyester On non-woven fabrics, it is placed in film-forming in deionized water coagulating bath, the porous counterdie of Kynoar is obtained, finally by Kynoar Porous counterdie immerses 5h in ethyl alcohol, takes out naturally dry；

Organic solvent A is trimethyl phosphate, triethyl phosphate, tributyl phosphate, N, N dimethyl formamide or N, N mono- The mixture of one or more of dimethyl acetamide.

Preferably, in S1, the preparation of dimethyl silicone polymer composite membrane includes the following steps:

Dimethyl silicone polymer is dissolved in organic solvent B under room temperature, crosslinking agent is added after stirring and catalyst is uniformly mixed Standing and defoaming obtains casting solution afterwards, and casting solution is cast on Kynoar counterdie and knifing is handed over after the solvent is volatilized Connection forms dimethyl silicone polymer layer on Kynoar counterdie, so that the desulfurization of dimethyl silicone polymer infiltration evaporation be made Film；Wherein, dimethyl silicone polymer, organic solvent, crosslinking agent, catalyst mass ratio be 30: 60: 3: 1；

Organic solvent B is normal heptane or toluene；Crosslinking agent is ethyl orthosilicate or 3- aminopropyl trimethoxysilane；It is described Catalyst is dibutyl tin dilaurate；The time of solvent volatilization is 12h；The temperature of the crosslinking is 80 DEG C, time 5h.

Preferably, activator described in S2 is 3- (2,3- the third oxygen of epoxy) propyl-triethoxysilicane, ethyoxyl diformazan One or more of base [3- (ethylene oxide oxygroup) propyl] silane, 3- glycidyloxypropyl trimethoxy silane.

Preferably, in S2 activator proportion be ethyl alcohol, the silane coupling agent containing active epoxy functional group, water according to 165: 1: 1 mixed solution of mass ratio, reaction temperature are 60 DEG C, react 12 hours.

Preferably, chelating agent described in S3 be iminodiacetic acid, two (carboxymethyl) ethylenediamines, carboxymethyl asparagic acid, One or more of five amine of tetraethyl alkene.

Preferably, the concentration of chelating agent solution is 0.1-0.3mol/L in S3, and adjusting pH value with alkaline solution is 9-11, instead Answering temperature is 60-80 DEG C, reaction time 9-12h, and the concentration of further chelating agent solution is 0.2mol/L, pH value 11, instead Answering temperature is 80 DEG C, reaction time 12h.

Preferably, the concentration of metal salt solution is 0.2mol/L in S4, and reaction temperature is 20-30 DEG C；

Preferably, metal salt solution is one of copper nitrate, zinc nitrate, manganese nitrate.

The three of technical solution of the present invention are that the polydimethylsiloxanes for providing above-mentioned metal ion surface modification are compound de- Application of the sulphur film in deep desulfurization of gasoline.

Compared with prior art, the present invention has the following technical effect that

There is empty d track in metal ion (majority is transition metal), it is easy to and the thiophene containing lone pair electrons is formed Complex promotes dissolution and diffusion of the thiophene in film, Cu is added during film preparation²⁺Y zeolite, Ni²⁺Y zeolite, Ag⁺Y Zeolite and Ag₂O particle etc. can make mixed substrate membrane containing nano-grade molecular sieve realize infiltration on the basis of not losing or losing selectivity less Flux greatly improves, but along with there is inorganic ion distribution uneven, agglomeration traits of inorganic matter during doping with And the organic and inorganic phase interface that is difficult to avoid that and lead to that cavity blemish occurs in use in permeable membrane and permeation flux is steady Qualitative bad technical problem.

The modified compound desulfurizing film of PDMS of surface metal ion of the present invention, avoids simple physical blending, metal ion It is sequestered in PDMS composite film surface by chemical grafting method, metal ion profile is uniform, is firmly combined, PDMS composite membrane table Face is smooth, does not cause to damage to film, solves agglomeration traits during doping of inorganic matter in the prior art and is difficult to keep away The problems such as film defect caused by the organic and inorganic phase interface exempted from.

The modified compound desulfurizing film of PDMS of surface metal ion of the present invention first contains work in the grafting of PDMS composite film surface The silane coupling agent of property epoxy-functional, then make epoxy ring-opening under alkaline condition, multiple tooth chelating agent is reacted to film surface, By the characteristic of chelating by metal ion-chelant to PDMS composite film surface, chelation can be to stablize the shape of cyclic compound Formula fixes metal, while leaving corresponding empty valence orbit to metal ion and receiving external lone pair electrons, reaches removing sulfide Purpose is chemically grafted chelating agent in film surface, and the desulfurization performance of PDMS film not only can be improved in fixing metal ions, The swelling resistance of PDMS film can be indirectly improved simultaneously,

The use of epoxy silane not only provided active site to grafting, but also combined PDMS composite film surface more closely, The swelling resistance of film is enhanced, the service life of film is improved；π complexing between metal ion and thiophene is significant to increase The strong infiltration evaporation desulfurization performance of PDMS film.

Specific embodiment

In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, With reference to embodiment The present invention is described in further detail.