CN107638805A - A kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol - Google Patents
A kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol Download PDFInfo
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- CN107638805A CN107638805A CN201711076072.4A CN201711076072A CN107638805A CN 107638805 A CN107638805 A CN 107638805A CN 201711076072 A CN201711076072 A CN 201711076072A CN 107638805 A CN107638805 A CN 107638805A
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- polyvinyl alcohol
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Abstract
The invention discloses a kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol, including previously prepared nascent state reverse osmosis membrane, then the polyvinyl alcohol crosslinked reaction solution containing graphene oxide is coated on nascent state reverse osmosis membrane, finally obtains the coating modified reverse osmosis membrane of graphene oxide/polyvinyl alcohol.Graphene oxide and serine are incorporated into polyethylene coating by the present invention, and it is modified, and can be improved polyethylene coating and are modified the problem of reverse osmosis membrane causes water flux decline and polyethylene coating easily to come off.
Description
Technical field
The present invention relates to a kind of preparation field of reverse osmosis membrane, more particularly to a kind of graphene oxide/polyvinyl alcohol coating
Modified reverse osmosis membrane preparation method.
Background technology
Reverse osmosis technology is under certain pressure effect, is acted on by means of the selective retention of reverse osmosis membrane by solution
The separation method that solute and solvent separate, it is widely used in sewage disposal and the purification of liquid and concentration, wherein most general
Time application be in water treatment technology, with reverse osmosis technology by the inorganic ions in raw water, bacterium, virus, organic matter and glue
The impurity such as body remove, to obtain the pure water of high quality.
But reverse osmosis membrane can also be polluted during purified water by the organic matter of some in water or inorganic matter, such as former
The impurity such as inorganic ions, bacterium, virus, organic matter and colloid in water can be attached on reverse osmosis membrane, cause the dirt of reverse osmosis membrane
Dye, the method in reverse osmosis membrane surface coating polyethylene alcohol coating is industrially usually used, so as to reach protection diaphragm and anti-soil
The effect of dye.However, this method of modifying bring maximum the drawbacks of be exactly that larger shadow is produced to the water flux of reverse osmosis membrane
Ring, substantially reduce the water flux of reverse osmosis membrane, and taken off as reverse osmosis membrane is readily soluble in water using polyethylene coating
Fall.
The content of the invention
It is an object of the invention to for above-mentioned the deficiencies in the prior art, there is provided a kind of graphene oxide/polyvinyl alcohol applies
The modified reverse osmosis membrane preparation method of layer, improve the decline of reverse osmosis membrane water flux, polyethylene coating is soluble in water and comes off
The problem of.
To solve the above problems, the technical solution used in the present invention is：
A kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol, comprises the following steps：
Step 1: the preparation of nascent state reverse osmosis membrane
The aqueous phase solution containing m-phenylene diamine (MPD), triethylamine and camphorsulfonic acid is prepared, the matter of m-phenylene diamine (MPD) in the aqueous phase solution
Amount concentration is 3-8%, and the mass concentration of triethylamine is 2-6%, and the mass concentration of camphorsulfonic acid is 5-10%；Preparation contains equal benzene three
The oil-phase solution of formyl chloride, the mass concentration 0.1-0.5% of pyromellitic trimethylsilyl chloride in the oil-phase solution；Polysulfones support membrane is pasted
In being immersed in the aqueous phase solution on stainless steel substrates, solvent is removed after taking-up, then be immersed in the oil-phase solution and carry out interface
Polymerisation, solvent is removed after taking-up, obtain nascent state reverse osmosis membrane；
Step 2: the preparation of the polyvinyl alcohol crosslinked reaction solution containing graphene oxide
Graphene oxide water solution and polyvinyl alcohol water solution are mixed, magnetic agitation 5-10min, ultrasonic disperse 30-
60min, crosslinking agent, serine and acid catalyst are then added, obtains the polyvinyl alcohol crosslinked reaction solution containing graphene oxide；
Step 3: the coating of nascent state reverse osmosis membrane
The polyvinyl alcohol crosslinked reaction solution containing graphene oxide is coated in the nascent state reverse osmosis membrane surface,
Reaction 5-20min in 60-120 DEG C of baking oven is put into, obtains the coating modified reverse osmosis membrane of graphene oxide/polyvinyl alcohol.
Further, the degree of polymerization of the polyvinyl alcohol is 1000-2000, and alcoholysis degree 99% is described to contain graphite oxide
The mass concentration of polyvinyl alcohol is 0.1-8% in the polyvinyl alcohol crosslinked reaction solution of alkene.
Further, in the polyvinyl alcohol crosslinked reaction solution containing graphene oxide, graphene oxide and polyethylene
The mass ratio of alcohol is 1: 20-50.
Further, the crosslinking agent is the one or more in glutaraldehyde, butanedial, maleic anhydride, ethanedioic acid, described
Crosslinking agent quality concentration is 0.1-1.2% in polyvinyl alcohol crosslinked reaction solution containing graphene oxide.
Further, the serine is levo-serine, and the polyvinyl alcohol crosslinked reaction containing graphene oxide is molten
Serine mass concentration is 0.1-1% in liquid.
Further, the acid catalyst is the one or more in hydrochloric acid, sulfuric acid, nitric acid, described to contain graphene oxide
Polyvinyl alcohol crosslinked reaction solution in the mass concentration of acid catalyst be 0.05-0.5%.
Further, solvent is n-hexane in the oil-phase solution.
It is using beneficial effect caused by above-mentioned technical proposal：
Graphene oxide and serine are incorporated into polyethylene coating by the present invention, and it is modified, can be improved
Polyethylene coating, which is modified reverse osmosis membrane, causes water flux to decline the problem of easily being come off with polyethylene coating.
There is abundant oxygen-containing functional group on graphene oxide, can uniformly divide in hydrophilic poly-vinyl alcohol solution
Dissipate, and these oxygen-containing functional groups can be participated in the cross-linking reaction of polyvinyl alcohol, graphene oxide is applied in polyvinyl alcohol
Consolidated and existed in the form of chemical bonds in layer；Graphene oxide is equal in the form of two-dimentional synusia stacks in polyethylene coating
Even distribution, nanochannel of the graphene oxide that synusia stacks similar to a rule through polyvinyl alcohol protective layer, and oxygen
Carbon atom arrangement is regular in graphite alkene, has ultralow flowage friction power, so current can be worn with ultrafast flow rate
These nanochannels are crossed, so as to improve water flux.
The nascent state reverse osmosis membrane of preparation does not do any heat treatment, the unreacted acid chloride group function of reverse osmosis membrane surface residual
Group and amido functional group, and serine is soluble in water, and the functional groups such as amino, hydroxyl, carboxyl, its molecule are contained on molecular structural formula
Amino in structure can react to form chemical bond with remnants acid chloride group, and carboxyl can be with remnants amino and polyvinyl alcohol chain
On hydroxyl react to form chemical bond, hydroxyl can react to form chemical bond with the aldehyde radical or carboxyl of crosslinking agent, so as to
Graphene oxide/polyvinyl alcohol coating is fixed on polyamide desalination layer surface in the form of chemical bond by serine, increase
The adhesion of graphene oxide/polyvinyl alcohol coating and reverse osmosis membrane, do not allow it easy to fall off.
Embodiment
Comparative example 1
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to add in 1000ml deionized waters, magnetic agitation
5min, aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made
5.9%) acid, takes pyromellitic trimethylsilyl chloride 3g to add in 1000ml n-hexanes, stirring to dissolving, be made pyromellitic trimethylsilyl chloride-just oneself
Alkane oil-phase solution (pyromellitic trimethylsilyl chloride mass concentration 0.3% in oil-phase solution), it is molten to be immersed in the aqueous phase by polysulfones support membrane
In liquid, the immersion time is 25s, and solvent deionized water is removed after taking-up, then is immersed in pyromellitic trimethylsilyl chloride-n-hexane oil of preparation
Interface polymerization reaction is carried out in phase solution, the interface polymerization reaction time is 50s, is dried in an oven at 100 DEG C after the completion of reaction
It is dry to obtain reverse osmosis membrane.
Comparative example 2
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to add in 1000ml deionized waters, magnetic agitation
5min, aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made
5.9%) acid, takes pyromellitic trimethylsilyl chloride 3g to add in 1000ml n-hexanes, stirring to dissolving, be made pyromellitic trimethylsilyl chloride-just oneself
Alkane oil-phase solution (pyromellitic trimethylsilyl chloride mass concentration 0.3% in oil-phase solution), polysulfones support membrane is immersed in aqueous phase solution,
The immersion time is 25s, and solvent deionized water is removed after taking-up, then be immersed in preparation pyromellitic trimethylsilyl chloride-n-hexane oil phase it is molten
Interface polymerization reaction is carried out in liquid, the interface polymerization reaction time is 50s, removes solvent hexane after taking-up, it is anti-to obtain nascent state
Permeable membrane；
It is 1000 by the degree of polymerization, the polyvinyl alcohol 40g that alcoholysis degree is 99% is dissolved in 80 DEG C of 1000ml deionized waters, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution, adds glutaraldehyde 4g, levo-serine 2g and hydrochloric acid 1g, magnetic agitation
10min, obtain polyvinyl alcohol crosslinked reaction solution (polyvinyl alcohol mass concentration 3.8%, glutaraldehyde mass concentration in solution
0.38%, levo-serine mass concentration 0.19%, hydrochloric acid mass concentration 0.1%)；Polyvinyl alcohol crosslinked reaction solution is coated
On nascent state reverse osmosis membrane surface, reaction 10min in 100 DEG C of baking oven is put into, obtains the counter-infiltration of polyethylene coating modification
Film.
Embodiment 1
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to add in 1000ml deionized waters, magnetic agitation
5min, aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made
5.9%) acid, takes pyromellitic trimethylsilyl chloride 3g to add in 1000ml n-hexanes, stirring to dissolving, be made pyromellitic trimethylsilyl chloride-just oneself
Alkane oil-phase solution (pyromellitic trimethylsilyl chloride mass concentration 0.3% in oil-phase solution), polysulfones support membrane is immersed in aqueous phase solution,
The immersion time is 25s, and solvent deionized water is removed after taking-up, then be immersed in preparation pyromellitic trimethylsilyl chloride-n-hexane oil phase it is molten
Interface polymerization reaction is carried out in liquid, the interface polymerization reaction time is 50s, removes solvent hexane after taking-up, it is anti-to obtain nascent state
Permeable membrane；
It is 1000 by the degree of polymerization, the polyvinyl alcohol 40g that alcoholysis degree is 99% is dissolved in 80 DEG C of 900ml deionized waters, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution；
Take graphene oxide 0.8g to be dissolved in 100ml deionized waters, magnetic agitation 10min, ultrasonic disperse 2h, aoxidized
Graphene aqueous solution；
Graphene oxide water solution is mixed with polyvinyl alcohol water solution, magnetic agitation 10min, ultrasonic disperse 30min, obtained
To the polyvinyl alcohol water solution containing graphene oxide (mass ratio of graphene oxide and polyvinyl alcohol is 1: 50)；To oxygen-containing fossil
Glutaraldehyde 4g, levo-serine 2g and hydrochloric acid 1g are added in the polyvinyl alcohol water solution of black alkene, magnetic agitation 10min, is contained
Polyvinyl alcohol crosslinked reaction solution (polyvinyl alcohol mass concentration 3.8%, the glutaraldehyde mass concentration in solution of graphene oxide
0.38%, levo-serine mass concentration 0.19%, hydrochloric acid mass concentration 0.1%), the polyvinyl alcohol containing graphene oxide is handed over
Connection reaction solution be coated in nascent state reverse osmosis membrane surface, is put into 100 DEG C of baking oven and reacts 10min, obtain graphene oxide/
The reverse osmosis membrane that polyethylene coating is modified.
Embodiment 2
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to add in 1000ml deionized waters, magnetic agitation
5min, aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made
5.9%) acid, takes pyromellitic trimethylsilyl chloride 3g to add in 1000ml n-hexanes, stirring to dissolving, be made pyromellitic trimethylsilyl chloride-just oneself
Alkane oil-phase solution (pyromellitic trimethylsilyl chloride mass concentration 0.3% in oil-phase solution), polysulfones support membrane is immersed in aqueous phase solution,
The immersion time is 25s, and solvent deionized water is removed after taking-up, then be immersed in preparation pyromellitic trimethylsilyl chloride-n-hexane oil phase it is molten
Interface polymerization reaction is carried out in liquid, the interface polymerization reaction time is 50s, removes solvent hexane after taking-up, it is anti-to obtain nascent state
Permeable membrane；
It is 1000 by the degree of polymerization, the polyvinyl alcohol 40g that alcoholysis degree is 99% is dissolved in 80 DEG C of 900ml deionized waters, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution；
Take graphene oxide 1.33g to be dissolved in 100ml deionized waters, magnetic agitation 10min, ultrasonic disperse 2h, obtain oxygen
Graphite aqueous solution；
Graphene oxide water solution is mixed with polyvinyl alcohol water solution, magnetic agitation 10min, ultrasonic disperse 30min, obtained
To the polyvinyl alcohol water solution containing graphene oxide (mass ratio of graphene oxide and polyvinyl alcohol is 1: 30)；To oxygen-containing fossil
Glutaraldehyde 4g, levo-serine 2g and hydrochloric acid 1g are added in the polyvinyl alcohol water solution of black alkene, magnetic agitation 10min, is contained
Polyvinyl alcohol crosslinked reaction solution (polyvinyl alcohol mass concentration 3.8%, the glutaraldehyde mass concentration in solution of graphene oxide
0.38%, levo-serine mass concentration 0.19%, hydrochloric acid mass concentration 0.1%), the polyvinyl alcohol containing graphene oxide is handed over
Connection reaction solution be coated in nascent state reverse osmosis membrane surface, is put into 100 DEG C of baking oven and reacts 10min, obtain graphene oxide/
The reverse osmosis membrane that polyethylene coating is modified.
Embodiment 3
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to add in 1000ml deionized waters, magnetic agitation
5min, aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made
5.9%) acid, takes pyromellitic trimethylsilyl chloride 3g to add in 1000ml n-hexanes, stirring to dissolving, be made pyromellitic trimethylsilyl chloride-just oneself
Alkane oil-phase solution (pyromellitic trimethylsilyl chloride mass concentration 0.3% in oil-phase solution), polysulfones support membrane is immersed in aqueous phase solution,
The immersion time is 25s, and solvent deionized water is removed after taking-up, then be immersed in preparation pyromellitic trimethylsilyl chloride-n-hexane oil phase it is molten
Interface polymerization reaction is carried out in liquid, the interface polymerization reaction time is 50s, removes solvent hexane after taking-up, it is anti-to obtain nascent state
Permeable membrane；
It is 1000 by the degree of polymerization, the polyvinyl alcohol 40g that alcoholysis degree is 99% is dissolved in 80 DEG C of 900ml deionized waters, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution；
Take graphene oxide 2g to be dissolved in 100ml deionized waters, magnetic agitation 10min, ultrasonic disperse 2h, obtain aoxidizing stone
Black aqueous solution；
Graphene oxide water solution is mixed with polyvinyl alcohol water solution, magnetic agitation 10min, ultrasonic disperse 30min, obtained
To the polyvinyl alcohol water solution containing graphene oxide (mass ratio of graphene oxide and polyvinyl alcohol is 1: 20)；To oxygen-containing fossil
Glutaraldehyde 4g, levo-serine 2g and hydrochloric acid 1g are added in the polyvinyl alcohol water solution of black alkene, magnetic agitation 10min, is contained
Polyvinyl alcohol crosslinked reaction solution (polyvinyl alcohol mass concentration 3.8%, the glutaraldehyde mass concentration in solution of graphene oxide
0.38%, levo-serine mass concentration 0.19%, hydrochloric acid mass concentration 0.1%), the polyvinyl alcohol containing graphene oxide is handed over
Connection reaction solution be coated in nascent state reverse osmosis membrane surface, is put into 100 DEG C of baking oven and reacts 10min, obtain graphene oxide/
The reverse osmosis membrane that polyethylene coating is modified.
Embodiment 4
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to add in 1000ml deionized waters, magnetic agitation
5min, aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made
5.9%) acid, takes pyromellitic trimethylsilyl chloride 3g to add in 1000ml n-hexanes, stirring to dissolving, be made pyromellitic trimethylsilyl chloride-just oneself
Alkane oil-phase solution (pyromellitic trimethylsilyl chloride mass concentration 0.3% in oil-phase solution), polysulfones support membrane is immersed in aqueous phase solution,
The immersion time is 25s, and solvent deionized water is removed after taking-up, then be immersed in preparation pyromellitic trimethylsilyl chloride-n-hexane oil phase it is molten
Interface polymerization reaction is carried out in liquid, the interface polymerization reaction time is 50s, removes solvent hexane after taking-up, it is anti-to obtain nascent state
Permeable membrane；
It is 1000 by the degree of polymerization, the polyvinyl alcohol 40g that alcoholysis degree is 99% is dissolved in 80 DEG C of 900ml deionized waters, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution；
Take graphene oxide 4g to be dissolved in 100ml deionized waters, magnetic agitation 10min, ultrasonic disperse 2h, obtain aoxidizing stone
Black aqueous solution；
Graphene oxide water solution is mixed with polyvinyl alcohol water solution, magnetic agitation 10min, ultrasonic disperse 30min, obtained
To the polyvinyl alcohol water solution containing graphene oxide (mass ratio of graphene oxide and polyvinyl alcohol is 1: 10)；To oxygen-containing fossil
Glutaraldehyde 4g, levo-serine 2g and hydrochloric acid 1g are added in the polyvinyl alcohol water solution of black alkene, magnetic agitation 10min, is contained
Polyvinyl alcohol crosslinked reaction solution (polyvinyl alcohol mass concentration 3.8%, the glutaraldehyde mass concentration in solution of graphene oxide
0.38%, levo-serine mass concentration 0.19%, hydrochloric acid mass concentration 0.1%), the polyvinyl alcohol containing graphene oxide is handed over
Connection reaction solution be coated in nascent state reverse osmosis membrane surface, is put into 100 DEG C of baking oven and reacts 10min, obtain graphene oxide/
The reverse osmosis membrane that polyethylene coating is modified.
Embodiment 5
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to add in 1000ml deionized waters, magnetic agitation
5min, aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made
5.9%) acid, takes pyromellitic trimethylsilyl chloride 3g to add in 1000ml n-hexanes, stirring to dissolving, be made pyromellitic trimethylsilyl chloride-just oneself
Alkane oil-phase solution (pyromellitic trimethylsilyl chloride mass concentration 0.3% in oil-phase solution), polysulfones support membrane is immersed in aqueous phase solution,
The immersion time is 25s, and solvent deionized water is removed after taking-up, then be immersed in preparation pyromellitic trimethylsilyl chloride-n-hexane oil phase it is molten
Interface polymerization reaction is carried out in liquid, the interface polymerization reaction time is 50s, removes solvent hexane after taking-up, it is anti-to obtain nascent state
Permeable membrane；
It is 2000 by the degree of polymerization, the polyvinyl alcohol 40g that alcoholysis degree is 99% is dissolved in 80 DEG C of 900ml deionized waters, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution；
Take graphene oxide 0.8g to be dissolved in 100ml deionized waters, magnetic agitation 10min, ultrasonic disperse 2h, aoxidized
Graphene aqueous solution；
Graphene oxide water solution is mixed with polyvinyl alcohol water solution, magnetic agitation 10min, ultrasonic disperse 30min, obtained
To the polyvinyl alcohol water solution containing graphene oxide (mass ratio of graphene oxide and polyvinyl alcohol is 1: 50)；To oxygen-containing fossil
Glutaraldehyde 4g, levo-serine 2g and hydrochloric acid 1g are added in the polyvinyl alcohol water solution of black alkene, magnetic agitation 10min, is contained
Polyvinyl alcohol crosslinked reaction solution (polyvinyl alcohol mass concentration 3.8%, the glutaraldehyde mass concentration in solution of graphene oxide
0.38%, levo-serine mass concentration 0.19%, hydrochloric acid mass concentration 0.1%), the polyvinyl alcohol containing graphene oxide is handed over
Connection reaction solution be coated in nascent state reverse osmosis membrane surface, is put into 100 DEG C of baking oven and reacts 10min, obtain graphene oxide/
The reverse osmosis membrane that polyethylene coating is modified.
Embodiment 6
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to add in 1000ml deionized waters, magnetic agitation
5min, aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made
5.9%) acid, takes pyromellitic trimethylsilyl chloride 3g to add in 1000ml n-hexanes, stirring to dissolving, be made pyromellitic trimethylsilyl chloride-just oneself
Alkane oil-phase solution (pyromellitic trimethylsilyl chloride mass concentration 0.3% in oil-phase solution), polysulfones support membrane is immersed in aqueous phase solution,
The immersion time is 25s, and solvent deionized water is removed after taking-up, then be immersed in preparation pyromellitic trimethylsilyl chloride-n-hexane oil phase it is molten
Interface polymerization reaction is carried out in liquid, the interface polymerization reaction time is 50s, removes solvent hexane after taking-up, it is anti-to obtain nascent state
Permeable membrane；
It is 2000 by the degree of polymerization, the polyvinyl alcohol 40g that alcoholysis degree is 99% is dissolved in 80 DEG C of 900ml deionized waters, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution；
Take graphene oxide 1.33g to be dissolved in 100ml deionized waters, magnetic agitation 10min, ultrasonic disperse 2h, obtain oxygen
Graphite aqueous solution；
Graphene oxide water solution is mixed with polyvinyl alcohol water solution, magnetic agitation 10min, ultrasonic disperse 30min, obtained
To the polyvinyl alcohol water solution containing graphene oxide (mass ratio of graphene oxide and polyvinyl alcohol is 1: 30)；To oxygen-containing fossil
Glutaraldehyde 4g, levo-serine 2g and hydrochloric acid 1g are added in the polyvinyl alcohol water solution of black alkene, magnetic agitation 10min, is contained
Polyvinyl alcohol crosslinked reaction solution (polyvinyl alcohol mass concentration 3.8%, the glutaraldehyde mass concentration in solution of graphene oxide
0.38%, levo-serine mass concentration 0.19%, hydrochloric acid mass concentration 0.1%), the polyvinyl alcohol containing graphene oxide is handed over
Connection reaction solution be coated in nascent state reverse osmosis membrane surface, is put into 100 DEG C of baking oven and reacts 10min, obtain graphene oxide/
The reverse osmosis membrane that polyethylene coating is modified.
Embodiment 7
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to add in 1000ml deionized waters, magnetic agitation
5min, aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made
5.9%) acid, takes pyromellitic trimethylsilyl chloride 3g to add in 1000ml n-hexanes, stirring to dissolving, be made pyromellitic trimethylsilyl chloride-just oneself
Alkane oil-phase solution (pyromellitic trimethylsilyl chloride mass concentration 0.3% in oil-phase solution), polysulfones support membrane is immersed in aqueous phase solution,
The immersion time is 25s, and solvent deionized water is removed after taking-up, then be immersed in preparation pyromellitic trimethylsilyl chloride-n-hexane oil phase it is molten
Interface polymerization reaction is carried out in liquid, the interface polymerization reaction time is 50s, removes solvent hexane after taking-up, it is anti-to obtain nascent state
Permeable membrane；
It is 2000 by the degree of polymerization, the polyvinyl alcohol 40g that alcoholysis degree is 99% is dissolved in 80 DEG C of 900ml deionized waters, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution；
Take graphene oxide 2g to be dissolved in 100ml deionized waters, magnetic agitation 10min, ultrasonic disperse 2h, obtain aoxidizing stone
Black aqueous solution；
Graphene oxide water solution is mixed with polyvinyl alcohol water solution, magnetic agitation 10min, ultrasonic disperse 30min, obtained
To the polyvinyl alcohol water solution containing graphene oxide (mass ratio of graphene oxide and polyvinyl alcohol is 1: 20)；To oxygen-containing fossil
Glutaraldehyde 4g, levo-serine 2g and hydrochloric acid 1g are added in the polyvinyl alcohol water solution of black alkene, magnetic agitation 10min, is contained
Polyvinyl alcohol crosslinked reaction solution (polyvinyl alcohol mass concentration 3.8%, the glutaraldehyde mass concentration in solution of graphene oxide
0.38%, levo-serine mass concentration 0.19%, hydrochloric acid mass concentration 0.1%), the polyvinyl alcohol containing graphene oxide is handed over
Connection reaction solution be coated in nascent state reverse osmosis membrane surface, is put into 100 DEG C of baking oven and reacts 10min, obtain graphene oxide/
The reverse osmosis membrane that polyethylene coating is modified.
Embodiment 8
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to add in 1000ml deionized waters, magnetic agitation
5min, aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made
5.9%) acid, takes pyromellitic trimethylsilyl chloride 3g to add in 1000ml n-hexanes, stirring to dissolving, be made pyromellitic trimethylsilyl chloride-just oneself
Alkane oil-phase solution (pyromellitic trimethylsilyl chloride mass concentration 0.3% in oil-phase solution), polysulfones support membrane is immersed in aqueous phase solution,
The immersion time is 25s, and solvent deionized water is removed after taking-up, then be immersed in preparation pyromellitic trimethylsilyl chloride-n-hexane oil phase it is molten
Interface polymerization reaction is carried out in liquid, the interface polymerization reaction time is 50s, removes solvent hexane after taking-up, it is anti-to obtain nascent state
Permeable membrane；
It is 2000 by the degree of polymerization, the polyvinyl alcohol 40g that alcoholysis degree is 99% is dissolved in 80 DEG C of 900ml deionized waters, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution；
Take graphene oxide 4g to be dissolved in 100ml deionized waters, magnetic agitation 10min, ultrasonic disperse 2h, obtain aoxidizing stone
Black aqueous solution；
Graphene oxide water solution is mixed with polyvinyl alcohol water solution, magnetic agitation 10min, ultrasonic disperse 30min, obtained
To the polyvinyl alcohol water solution containing graphene oxide (mass ratio of graphene oxide and polyvinyl alcohol is 1: 10)；To oxygen-containing fossil
Glutaraldehyde 4g, levo-serine 2g and hydrochloric acid 1g are added in the polyvinyl alcohol water solution of black alkene, magnetic agitation 10min, is contained
Polyvinyl alcohol crosslinked reaction solution (polyvinyl alcohol mass concentration 3.8%, the glutaraldehyde mass concentration in solution of graphene oxide
0.38%, levo-serine mass concentration 0.19%, hydrochloric acid mass concentration 0.1%), the polyvinyl alcohol containing graphene oxide is handed over
Connection reaction solution be coated in nascent state reverse osmosis membrane surface, is put into 100 DEG C of baking oven and reacts 10min, obtain graphene oxide/
The reverse osmosis membrane that polyethylene coating is modified.
Comparative example 1-2 and embodiment the 1-8 reverse osmosis membrane prepared are placed in water, at 25 DEG C, 150psi pressure,
Under the test condition of the aqueous solution of 2000ppm sodium chloride, control sample and coating oxidation stone are being measured after film stable operation 30min
The water flux and salt rejection rate of the reverse osmosis membrane of black alkene/polyethylene coating, test result are shown in Table 1.
Table 1
| Reverse osmosis membrane is numbered | Water flux/GFD | Salt rejection rate/% |
| Comparative example 1 | 23.57 | 98.22 |
| Comparative example 2 | 18.73 | 98.30 |
| Embodiment 1 | 20.59 | 98.34 |
| Embodiment 2 | 21.06 | 98.51 |
| Embodiment 3 | 22.34 | 98.21 |
| Embodiment 4 | 16.78 | 98.04 |
| Embodiment 5 | 19.33 | 98.53 |
| Embodiment 6 | 20.97 | 98.69 |
| Embodiment 7 | 21.45 | 98.36 |
| Embodiment 8 | 15.31 | 98.16 |
Comparative example 1 is the reverse osmosis membrane of no polyethylene coating, and comparative example 2 is that coating polyethylene applies on reverse osmosis membrane
Layer, and embodiment 1-8 is the graphene oxide that different quality is with the addition of in polyethylene coating, it is from table 1 it can be found that poly-
In vinyl alcohol coating the content of graphene oxide has important influence to the water flux of reverse osmosis membrane, either the degree of polymerization 1000
The polyvinyl alcohol of polyvinyl alcohol or the degree of polymerization 2000, as the mass ratio of graphene oxide and polyvinyl alcohol gradually increases, oxygen
The water flux for the reverse osmosis membrane that graphite alkene/polyethylene coating is modified also gradually increases, but when graphene oxide is with gathering
When the mass ratio of vinyl alcohol is more than 1: 20, the water flux of the coating modified reverse osmosis membrane of graphene oxide/polyvinyl alcohol is on the contrary
It has dropped, this is primarily due to the increase of graphene oxide content, and its scattered in poly-vinyl alcohol solution becomes more
It is difficult, it is easier to reunite.And the content of graphene oxide influences not on the salt rejection rate of reverse osmosis membrane in polyethylene coating
Greatly, salt rejection rate is still maintained at higher level.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention is described in detail with reference to the foregoing embodiments, it will be understood by those within the art that：It still may be used
To be modified to the technical scheme described in previous embodiment, or equivalent substitution is carried out to which part technical characteristic；And
These modifications are replaced, and the essence of appropriate technical solution is departed from the spirit and model of technical scheme of the embodiment of the present invention
Enclose.
Claims (7)
- A kind of 1. coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol, it is characterised in that：Including following step Suddenly：Step 1: the preparation of nascent state reverse osmosis membraneThe aqueous phase solution containing m-phenylene diamine (MPD), triethylamine and camphorsulfonic acid is prepared, the quality of m-phenylene diamine (MPD) is dense in the aqueous phase solution Spend for 3-8%, the mass concentration of triethylamine is 2-6%, and the mass concentration of camphorsulfonic acid is 5-10%；Preparation contains the equal formyl of benzene three The oil-phase solution of chlorine, the mass concentration 0.1-0.5% of pyromellitic trimethylsilyl chloride in the oil-phase solution；Polysulfones support membrane is affixed on not The aqueous phase solution is immersed on rust steel disc, solvent is removed after taking-up, then be immersed in the oil-phase solution and carry out interfacial polymerization Reaction, removes solvent after taking-up, obtains nascent state reverse osmosis membrane；Step 2: the preparation of the polyvinyl alcohol crosslinked reaction solution containing graphene oxideGraphene oxide water solution and polyvinyl alcohol water solution are mixed, magnetic agitation 5-10min, ultrasonic disperse 30-60min, Then crosslinking agent, serine and acid catalyst are added, obtains the polyvinyl alcohol crosslinked reaction solution containing graphene oxide；Step 3: the coating of nascent state reverse osmosis membraneThe polyvinyl alcohol crosslinked reaction solution containing graphene oxide is coated in the nascent state reverse osmosis membrane surface, is put into Reaction 5-20min, obtains the coating modified reverse osmosis membrane of graphene oxide/polyvinyl alcohol in 60-120 DEG C of baking oven.
- 2. a kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol according to claim 1, its It is characterised by：The degree of polymerization of the polyvinyl alcohol is 1000-2000, alcoholysis degree 99%, the poly- second containing graphene oxide The mass concentration of polyvinyl alcohol is 0.1-8% in enol cross-linking reaction solution.
- 3. a kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol according to claim 2, its It is characterised by：In the polyvinyl alcohol crosslinked reaction solution containing graphene oxide, the quality of graphene oxide and polyvinyl alcohol Than for 1: 20-50.
- 4. a kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol according to claim 1, its It is characterised by：The crosslinking agent is glutaraldehyde, the one or more in butanedial, maleic anhydride, ethanedioic acid, the oxygen-containing fossil Crosslinking agent quality concentration is 0.1-1.2% in the polyvinyl alcohol crosslinked reaction solution of black alkene.
- 5. a kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol according to claim 1, its It is characterised by：The serine is levo-serine, silk ammonia in the polyvinyl alcohol crosslinked reaction solution containing graphene oxide Sour mass concentration is 0.1-1%.
- 6. a kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol according to claim 1, its It is characterised by：The acid catalyst is hydrochloric acid, the one or more in sulfuric acid, nitric acid, the polyethylene containing graphene oxide The mass concentration of acid catalyst is 0.05-0.5% in alcohol and cross linking reaction solution.
- 7. a kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol according to claim 1, its It is characterised by：Solvent is n-hexane in the oil-phase solution.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108176260A (en) * | 2018-01-05 | 2018-06-19 | 天津工业大学 | A kind of preparation method of the hydrophilic seperation film of pressure response type |
| CN110038446A (en) * | 2019-05-31 | 2019-07-23 | 自然资源部天津海水淡化与综合利用研究所 | A kind of antipollution aromatic polyamide composite reverse osmosis membrane and preparation method thereof |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974238A (en) * | 2012-11-02 | 2013-03-20 | 东华大学 | Film surface hydrophilicity modifying method through PVA grafting by utilizing biological preparation |
| CN104437111A (en) * | 2014-12-16 | 2015-03-25 | 彭博 | Anti-pollution polyamide composite membrane and preparation method thereof |
| CN104437110A (en) * | 2014-12-15 | 2015-03-25 | 彭博 | High-flux polyamide composite film |
| CN104607068A (en) * | 2015-01-20 | 2015-05-13 | 苏州信望膜技术有限公司 | Bio-adhesion-resistant porous separation membrane as well as preparation method and application thereof |
| CN105073235A (en) * | 2013-04-12 | 2015-11-18 | 通用电气公司 | Membranes comprising graphene |
| WO2017044845A1 (en) * | 2015-09-10 | 2017-03-16 | Nitto Denko Corporation | Selectively permeable graphene oxide/ polyvinyl alcohol membrane for dehydration |
| CN106861465A (en) * | 2017-03-31 | 2017-06-20 | 深圳市国创新能源研究院 | A kind of antipollution combined oxidation Graphene NF membrane and preparation method thereof |
| JP2017136546A (en) * | 2016-02-03 | 2017-08-10 | 次世代型膜モジュール技術研究組合 | Carbon dioxide separation membrane and production method of the same |
-
2017
- 2017-11-03 CN CN201711076072.4A patent/CN107638805B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974238A (en) * | 2012-11-02 | 2013-03-20 | 东华大学 | Film surface hydrophilicity modifying method through PVA grafting by utilizing biological preparation |
| CN105073235A (en) * | 2013-04-12 | 2015-11-18 | 通用电气公司 | Membranes comprising graphene |
| CN104437110A (en) * | 2014-12-15 | 2015-03-25 | 彭博 | High-flux polyamide composite film |
| CN104437111A (en) * | 2014-12-16 | 2015-03-25 | 彭博 | Anti-pollution polyamide composite membrane and preparation method thereof |
| CN104607068A (en) * | 2015-01-20 | 2015-05-13 | 苏州信望膜技术有限公司 | Bio-adhesion-resistant porous separation membrane as well as preparation method and application thereof |
| WO2017044845A1 (en) * | 2015-09-10 | 2017-03-16 | Nitto Denko Corporation | Selectively permeable graphene oxide/ polyvinyl alcohol membrane for dehydration |
| JP2017136546A (en) * | 2016-02-03 | 2017-08-10 | 次世代型膜モジュール技術研究組合 | Carbon dioxide separation membrane and production method of the same |
| CN106861465A (en) * | 2017-03-31 | 2017-06-20 | 深圳市国创新能源研究院 | A kind of antipollution combined oxidation Graphene NF membrane and preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108176260A (en) * | 2018-01-05 | 2018-06-19 | 天津工业大学 | A kind of preparation method of the hydrophilic seperation film of pressure response type |
| CN112638823A (en) * | 2018-08-24 | 2021-04-09 | 上海特瑞思材料科技有限公司 | Water filtration membrane device and method of making |
| CN112638823B (en) * | 2018-08-24 | 2023-11-28 | 上海特瑞思材料科技有限公司 | Water filtration membrane device and preparation method |
| CN110882632A (en) * | 2018-09-10 | 2020-03-17 | 新奥科技发展有限公司 | Reverse osmosis membrane and preparation method thereof |
| CN110882632B (en) * | 2018-09-10 | 2022-03-11 | 新奥科技发展有限公司 | Reverse osmosis membrane and preparation method thereof |
| CN110038446A (en) * | 2019-05-31 | 2019-07-23 | 自然资源部天津海水淡化与综合利用研究所 | A kind of antipollution aromatic polyamide composite reverse osmosis membrane and preparation method thereof |
| CN110302683A (en) * | 2019-07-09 | 2019-10-08 | 浙江海纳环保科技有限公司 | The preparation method of new anti-pollution reverse osmosis membrane based on molecular channel structural adjustment |
| CN112705055A (en) * | 2019-10-25 | 2021-04-27 | 中国海洋大学 | High-flux nano composite film and preparation method thereof |
| CN111718638A (en) * | 2020-07-16 | 2020-09-29 | 王康 | Functionalized graphene-water-based epoxy resin anticorrosive material and preparation method thereof |
| CN112844077A (en) * | 2020-12-26 | 2021-05-28 | 宁波日新恒力科技有限公司 | Reverse osmosis membrane with PE microporous membrane as base material and preparation method thereof |
| CN114082307A (en) * | 2021-12-08 | 2022-02-25 | 湖南澳维环保科技有限公司 | Anti-oxidation reverse osmosis membrane and preparation method thereof |
| CN114082307B (en) * | 2021-12-08 | 2024-04-26 | 湖南澳维科技股份有限公司 | Antioxidant reverse osmosis membrane and preparation method thereof |
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