CN107638805B - A kind of reverse osmosis membrane preparation method that graphene oxide/polyvinyl alcohol is coating modified - Google Patents
A kind of reverse osmosis membrane preparation method that graphene oxide/polyvinyl alcohol is coating modified Download PDFInfo
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Abstract
The invention discloses a kind of reverse osmosis membrane preparation methods that graphene oxide/polyvinyl alcohol is coating modified, 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 introduced into polyethylene coating by the present invention, are modified to it, and the problem of modified reverse osmosis membrane of polyethylene coating causes water flux decline and polyethylene coating to be easy to fall off can be improved.
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 coatings
Modified reverse osmosis membrane preparation method.
Background technique
Reverse osmosis technology is under certain pressure effect, and being acted on by means of the selective retention of reverse osmosis membrane will be in solution
The separation method that solute and solvent separate, it is widely used in sewage treatment and the purification of liquid and concentration, wherein most general
Time application be in water treatment technology, with reverse osmosis technology by inorganic ions, bacterium, virus, organic matter and the glue in raw water
The impurity such as body removal, to obtain the pure water of high quality.
But reverse osmosis membrane is during purified water, also can by water some organic matters or inorganic matter pollute, it is 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, industrially usually using the method in reverse osmosis membrane surface coating polyethylene alcohol coating, to reach protection diaphragm and anti-pollution
The effect of dye.However, the drawback of this method of modifying bring maximum is exactly to generate biggish shadow to the water flux of reverse osmosis membrane
It is loud, substantially reduce the water flux of reverse osmosis membrane, and take off as the use polyethylene coating of reverse osmosis membrane is readily soluble in water
It falls.
Summary of the invention
It is an object of the invention in view of the above shortcomings of the prior art, provide a kind of graphene oxide/polyvinyl alcohol painting
The modified reverse osmosis membrane preparation method of layer, improves that the decline of reverse osmosis membrane water flux, polyethylene coating is soluble easily in water and falls off
The problem of.
To solve the above problems, the technical solution used in the present invention is:
A kind of reverse osmosis membrane preparation method that graphene oxide/polyvinyl alcohol is coating modified, includes 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%；It prepares and 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
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 oxide
Graphene oxide water solution and polyvinyl alcohol water solution are mixed, magnetic agitation 5-10min, ultrasonic disperse 30-
Then 60min is added crosslinking agent, serine and acid catalyst, 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 nascent state reverse osmosis membrane surface,
It is put into 60-120 DEG C of baking oven and reacts 5-20min, obtain 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 be one of glutaraldehyde, butanedial, maleic anhydride, ethanedioic acid or a variety of, it is 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 be one of hydrochloric acid, sulfuric acid, nitric acid or a variety of, it is described contain graphene oxide
Polyvinyl alcohol crosslinked reaction solution in acid catalyst mass concentration be 0.05-0.5%.
Further, solvent is n-hexane in the oil-phase solution.
The beneficial effects of adopting the technical scheme are that
Graphene oxide and serine are introduced into polyethylene coating by the present invention, are modified to it, can be improved
The problem of modified reverse osmosis membrane of polyethylene coating causes water flux decline and polyethylene coating to be easy to fall off.
There is oxygen-containing functional group abundant on graphene oxide, can uniformly divide in hydrophilic poly-vinyl alcohol solution
It dissipates, and these oxygen-containing functional groups are able to participate in the cross-linking reaction of polyvinyl alcohol, applies graphene oxide in polyvinyl alcohol
It is consolidated and is existed in the form of chemical bonds in layer；The form that graphene oxide is stacked in polyethylene coating with two-dimentional synusia is equal
Even distribution, the graphene oxide that synusia stacks are similar to a rule through the nanochannel of polyvinyl alcohol protective layer, and oxygen
Carbon atom arrangement is regular in graphite alkene, has ultralow flowage friction power, so water flow can be worn with ultrafast flow rate
These nanochannels are crossed, 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 easily in water, and the functional groups such as amino, hydroxyl, carboxyl, molecule are contained on molecular structural formula
Amino in structure can react to form chemical bond with remaining acid chloride group, and carboxyl can be with remaining 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, thus
So that graphene oxide/polyvinyl alcohol coating is fixed on polyamide desalination layer surface in the form of chemical bond serine, increases
The binding force of graphene oxide/polyvinyl alcohol coating and reverse osmosis membrane keeps its not easy to fall off.
Specific embodiment
Comparative example 1
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to be added in 1000ml deionized water, magnetic agitation
Aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made in 5min
Acid 5.9%), take pyromellitic trimethylsilyl chloride 3g be added 1000ml n-hexane in, stirring to dissolve, 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 water phase for 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 at 100 DEG C in an oven after the reaction was completed
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 be added in 1000ml deionized water, magnetic agitation
Aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made in 5min
Acid 5.9%), take pyromellitic trimethylsilyl chloride 3g be added 1000ml n-hexane in, stirring to dissolve, 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 is immersed in pyromellitic trimethylsilyl chloride-n-hexane oil of preparation and mixes
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 water, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution, adds glutaraldehyde 4g, levo-serine 2g and hydrochloric acid 1g, magnetic agitation
10min obtains 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
It on nascent state reverse osmosis membrane surface, is put into 100 DEG C of baking oven and reacts 10min, obtain the reverse osmosis of polyethylene coating modification
Film.
Embodiment 1
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to be added in 1000ml deionized water, magnetic agitation
Aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made in 5min
Acid 5.9%), take pyromellitic trimethylsilyl chloride 3g be added 1000ml n-hexane in, stirring to dissolve, 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 is immersed in pyromellitic trimethylsilyl chloride-n-hexane oil of preparation and mixes
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 water, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution；
Graphene oxide 0.8g is taken to be dissolved in 100ml deionized water, magnetic agitation 10min, ultrasonic disperse 2h are aoxidized
Graphene aqueous solution；
Graphene oxide water solution is mixed with polyvinyl alcohol water solution, magnetic agitation 10min, ultrasonic disperse 30min is 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, magnetic agitation 10min are added in the polyvinyl alcohol water solution of black alkene to be 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
Join reaction solution and be coated in nascent state reverse osmosis membrane surface, be put into 100 DEG C of baking oven and react 10min, obtain graphene oxide/
The modified reverse osmosis membrane of polyethylene coating.
Embodiment 2
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to be added in 1000ml deionized water, magnetic agitation
Aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made in 5min
Acid 5.9%), take pyromellitic trimethylsilyl chloride 3g be added 1000ml n-hexane in, stirring to dissolve, 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 is immersed in pyromellitic trimethylsilyl chloride-n-hexane oil of preparation and mixes
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 water, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution；
Graphene oxide 1.33g is taken to be dissolved in 100ml deionized water, 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 is 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, magnetic agitation 10min are added in the polyvinyl alcohol water solution of black alkene to be 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
Join reaction solution and be coated in nascent state reverse osmosis membrane surface, be put into 100 DEG C of baking oven and react 10min, obtain graphene oxide/
The modified reverse osmosis membrane of polyethylene coating.
Embodiment 3
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to be added in 1000ml deionized water, magnetic agitation
Aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made in 5min
Acid 5.9%), take pyromellitic trimethylsilyl chloride 3g be added 1000ml n-hexane in, stirring to dissolve, 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 is immersed in pyromellitic trimethylsilyl chloride-n-hexane oil of preparation and mixes
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 water, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution；
Graphene oxide 2g is taken to be dissolved in 100ml deionized water, magnetic agitation 10min, ultrasonic disperse 2h obtain oxidation stone
Black aqueous solution；
Graphene oxide water solution is mixed with polyvinyl alcohol water solution, magnetic agitation 10min, ultrasonic disperse 30min is 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, magnetic agitation 10min are added in the polyvinyl alcohol water solution of black alkene to be 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
Join reaction solution and be coated in nascent state reverse osmosis membrane surface, be put into 100 DEG C of baking oven and react 10min, obtain graphene oxide/
The modified reverse osmosis membrane of polyethylene coating.
Embodiment 4
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to be added in 1000ml deionized water, magnetic agitation
Aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made in 5min
Acid 5.9%), take pyromellitic trimethylsilyl chloride 3g be added 1000ml n-hexane in, stirring to dissolve, 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 is immersed in pyromellitic trimethylsilyl chloride-n-hexane oil of preparation and mixes
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 water, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution；
Graphene oxide 4g is taken to be dissolved in 100ml deionized water, magnetic agitation 10min, ultrasonic disperse 2h obtain oxidation stone
Black aqueous solution；
Graphene oxide water solution is mixed with polyvinyl alcohol water solution, magnetic agitation 10min, ultrasonic disperse 30min is 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, magnetic agitation 10min are added in the polyvinyl alcohol water solution of black alkene to be 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
Join reaction solution and be coated in nascent state reverse osmosis membrane surface, be put into 100 DEG C of baking oven and react 10min, obtain graphene oxide/
The modified reverse osmosis membrane of polyethylene coating.
Embodiment 5
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to be added in 1000ml deionized water, magnetic agitation
Aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made in 5min
Acid 5.9%), take pyromellitic trimethylsilyl chloride 3g be added 1000ml n-hexane in, stirring to dissolve, 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 is immersed in pyromellitic trimethylsilyl chloride-n-hexane oil of preparation and mixes
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 water, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution；
Graphene oxide 0.8g is taken to be dissolved in 100ml deionized water, magnetic agitation 10min, ultrasonic disperse 2h are aoxidized
Graphene aqueous solution；
Graphene oxide water solution is mixed with polyvinyl alcohol water solution, magnetic agitation 10min, ultrasonic disperse 30min is 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, magnetic agitation 10min are added in the polyvinyl alcohol water solution of black alkene to be 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
Join reaction solution and be coated in nascent state reverse osmosis membrane surface, be put into 100 DEG C of baking oven and react 10min, obtain graphene oxide/
The modified reverse osmosis membrane of polyethylene coating.
Embodiment 6
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to be added in 1000ml deionized water, magnetic agitation
Aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made in 5min
Acid 5.9%), take pyromellitic trimethylsilyl chloride 3g be added 1000ml n-hexane in, stirring to dissolve, 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 is immersed in pyromellitic trimethylsilyl chloride-n-hexane oil of preparation and mixes
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 water, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution；
Graphene oxide 1.33g is taken to be dissolved in 100ml deionized water, 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 is 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, magnetic agitation 10min are added in the polyvinyl alcohol water solution of black alkene to be 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
Join reaction solution and be coated in nascent state reverse osmosis membrane surface, be put into 100 DEG C of baking oven and react 10min, obtain graphene oxide/
The modified reverse osmosis membrane of polyethylene coating.
Embodiment 7
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to be added in 1000ml deionized water, magnetic agitation
Aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made in 5min
Acid 5.9%), take pyromellitic trimethylsilyl chloride 3g be added 1000ml n-hexane in, stirring to dissolve, 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 is immersed in pyromellitic trimethylsilyl chloride-n-hexane oil of preparation and mixes
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 water, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution；
Graphene oxide 2g is taken to be dissolved in 100ml deionized water, magnetic agitation 10min, ultrasonic disperse 2h obtain oxidation stone
Black aqueous solution；
Graphene oxide water solution is mixed with polyvinyl alcohol water solution, magnetic agitation 10min, ultrasonic disperse 30min is 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, magnetic agitation 10min are added in the polyvinyl alcohol water solution of black alkene to be 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
Join reaction solution and be coated in nascent state reverse osmosis membrane surface, be put into 100 DEG C of baking oven and react 10min, obtain graphene oxide/
The modified reverse osmosis membrane of polyethylene coating.
Embodiment 8
M-phenylene diamine (MPD) 70g, triethylamine 40g and camphorsulfonic acid 70g is taken to be added in 1000ml deionized water, magnetic agitation
Aqueous phase solution (m-phenylene diamine (MPD) mass concentration 5.9%, triethylamine mass concentration 3.4%, camphor sulphur in aqueous phase solution is made in 5min
Acid 5.9%), take pyromellitic trimethylsilyl chloride 3g be added 1000ml n-hexane in, stirring to dissolve, 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 is immersed in pyromellitic trimethylsilyl chloride-n-hexane oil of preparation and mixes
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 water, machine
Tool stirs 15min, obtains polyvinyl alcohol water solution；
Graphene oxide 4g is taken to be dissolved in 100ml deionized water, magnetic agitation 10min, ultrasonic disperse 2h obtain oxidation stone
Black aqueous solution；
Graphene oxide water solution is mixed with polyvinyl alcohol water solution, magnetic agitation 10min, ultrasonic disperse 30min is 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, magnetic agitation 10min are added in the polyvinyl alcohol water solution of black alkene to be 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
Join reaction solution and be coated in nascent state reverse osmosis membrane surface, be put into 100 DEG C of baking oven and react 10min, obtain graphene oxide/
The modified reverse osmosis membrane of polyethylene coating.
Reverse osmosis membrane prepared by comparative example 1-2 and embodiment 1-8 is placed in water, at 25 DEG C, 150psi pressure,
Under the test condition of the aqueous solution of 2000ppm sodium chloride, comparative 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 number | 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 not 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 added 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 is gradually increased, oxygen
The water flux of the modified reverse osmosis membrane of graphite alkene/polyethylene coating is also gradually increased, however when graphene oxide and is gathered
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 instead
It has dropped, this is primarily due to the increase with graphene oxide content, and the dispersion in poly-vinyl alcohol solution becomes more
It is difficult, it is easier to reunite.And the content of graphene oxide influences not 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
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify to technical solution documented by previous embodiment or equivalent replacement of some of the technical features；And
These are modified or replaceed, the spirit and scope for technical solution of the embodiment of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (5)
1. a kind of reverse osmosis membrane preparation method that graphene oxide/polyvinyl alcohol is coating modified, it is characterised in that: including walking as follows
It is rapid:
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 quality of m-phenylene diamine (MPD) is dense in the aqueous phase solution
Degree is 3-8%, and the mass concentration of triethylamine is 2-6%, and the mass concentration of camphorsulfonic acid is 5-10%；It prepares and contains equal three formyl of benzene
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
It is immersed in the aqueous phase solution 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 oxide
Graphene 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 is 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 nascent state reverse osmosis membrane surface, is put into
5-20min is reacted in 60-120 DEG C of baking oven, obtains the coating modified reverse osmosis membrane of graphene oxide/polyvinyl alcohol；
The degree of polymerization of the polyvinyl alcohol is 1000-2000, alcoholysis degree 99%, the polyvinyl alcohol friendship containing graphene oxide
The mass concentration for joining polyvinyl alcohol in reaction solution is 0.1-8%；
In the polyvinyl alcohol crosslinked reaction solution containing graphene oxide, the mass ratio of graphene oxide and polyvinyl alcohol is 1:
20-50。
2. a kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol according to claim 1,
Be characterized in that: the crosslinking agent is one of glutaraldehyde, butanedial, maleic anhydride, ethanedioic acid or a variety of, the oxygen-containing fossil
Crosslinking agent quality concentration is 0.1-1.2% in the polyvinyl alcohol crosslinked reaction solution of black alkene.
3. a kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol according to claim 1,
Be characterized in that: the serine is levo-serine, silk ammonia in the polyvinyl alcohol crosslinked reaction solution containing graphene oxide
Sour mass concentration is 0.1-1%.
4. a kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol according to claim 1,
Be characterized in that: the acid catalyst is one of hydrochloric acid, sulfuric acid, nitric acid or a variety of, the polyethylene containing graphene oxide
The mass concentration of acid catalyst is 0.05-0.5% in alcohol and cross linking reaction solution.
5. a kind of coating modified reverse osmosis membrane preparation method of graphene oxide/polyvinyl alcohol according to claim 1,
Be characterized in that: solvent is n-hexane in the oil-phase solution.
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| 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 |
| EP3841062A4 (en) * | 2018-08-24 | 2022-06-01 | Shanghai Tetrels Material Technology Co., Ltd. | Devices and methods for water-filtration membranes |
| 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 |
| 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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