CN101298040A - Mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbing agent and preparation thereof - Google Patents
Mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbing agent and preparation thereof Download PDFInfo
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Abstract
The invention pertains to the technical field of waste water processing, in particular to an adsorbent of thiol-group functionalized polyvinyl alcohol-gelatin compound cross-linking microspheres and a preparation method thereof. The adsorbent comprises that polyvinyl alcohol and gelatin are crossly clinked to form polymer microspheres, and then the keyed joint of a functional group, such as thiol-group is carried out. The adsorbent has adjustable composition and aperture, even size, large specific surface area, good high-concentration mercury ion adsorbing performance and trace amount of mercury ion adsorbing performance as well as good mechanical performance, and a damaged rate lower than 1.0 percent after being used for a plurality of times, thus being a new generation of mercury removing product with high performance and high efficiency and being able to be used in the waste water processing of heavy metal industry comprising mercury, lead, and cadmium, etc. with wider range of concentration. The method of the invention has simple technique, high production efficiency, high product quality and low cost, and is beneficial to mass production.
Description
Technical field
The invention belongs to technical field of waste water processing, be specifically related to a kind of mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent and preparation method thereof.
Background technology
The application of mercury in industrial circles such as papermaking, coating, cosmetics, anticorrisive agent, thermometer, Pressure gauge, fluorescent lamp and battery more and more widely, simultaneously, mercury also can bring a kind of serious environmental pollution problem.In all industrial heavy metal containing sewage dischargings, mercury is a kind of polluter to the ambient influnence maximum.According to estimates, the mercury pollution that global annual nature, artificial and ocean injection etc. increase newly is up to 5500 tons, so the processing of mercury-containing waste water, is directly connected to human physical and mental health.How to handle mercury efficiently, become the very important difficult problem that the mankind face.
The processing method of traditional mercury-containing waste water mainly contains chemical precipitation method, metallic reducing method, absorption method, ion-exchange, membrane separation process, microbial method etc.
Chemical precipitation method is to use the processing method of more general a kind of mercury-containing waste water, and this method has advantages such as technology is simple, easy to operate, economical and practical.Common precipitating reagent is lime, sulfide, bodied ferric sulfate, carbonate, and their mixture.Chemical precipitation method is easy to remove fast a large amount of mercury metal ions, but owing to be subjected to the influence of precipitating reagent and environmental condition, go out water concentration and often do not reach emission request, therefore also need further to handle, the sediment that produces must good treatment be disposed, otherwise can cause secondary pollution.
Ion-exchange is handled mercury-containing waste water, the degree of purification height, and non-secondary pollution, but this method is subjected to the influence of impurity in the waste water and the restriction of exchanger kind, output and cost.
Electrodialysis is a kind of of membrane separation technique, and it is under the DC electric field effect, is motive force with the potential difference, utilizes the selectivity of amberplex, electrolyte is separated from solution, thereby realize solution desalination, concentrate, the purpose of refining or purifying.Other membrane technology of handling mercury-containing waste water also has: hyperfiltration, liquid-film method, ultrafiltration etc.But film selectivity ratios when handling waste water is higher, different waste water must be studied the film that is complementary with it, and the composition of waste water also must be more stable, and the design of membrane module also is a difficult problem, embrane method is handled the investment of waste water also than higher, and these have all influenced the application of film.
Absorption method is to utilize porous solid matter, makes one or more materials in the water be attracted to the surface of solids and the method for removing.The adsorbent that can be used for handling mercury-containing waste water has: active carbon, weathered coal, sulfonated coal, blast-furnace cinder, zeolite, shitosan, diatomite, improvement fiber, activated alumina, eggshell etc.The mechanism of these sorbent treatment mercury-containing waste waters is not quite similar, and has plenty of physical absorption and accounts for leadingly, has plenty of chemisorbed and accounts for leadingly, and the adsorbent that has had both played suction-operated, played flocculation again.Absorption method has characteristics such as clearance height, equipment are simple relatively.The controlled condition of sorbent treatment mercury-containing waste water is many, contains chromium concn, pH value, adsorption time etc. as the composition of the addition of the granularity of adsorbent, adsorbent, waste water, waste water.Therefore, still need to develop new adsorbent material system and technology of preparing thereof efficient, with low cost and easy to use.
For these reasons, absorption method is respond well for handling mercury-containing waste water.Key be prepare that displacement volume is big, preparation technology is simple, non-secondary pollution, environment compatibility is superior, the ratio of performance to price is high, be beneficial to the adsorbent of recovery, thereby provide control and control to contain new technology and new technology that high concentration or microscratch amount ion concentration of mercury pollute.
At present both at home and abroad also not about open source literature report and the patent application of the removal of mercury with mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent and preparation method thereof.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, provide that a kind of displacement volume is big, preparation technology simple, non-secondary pollution, be beneficial to adsorbing agent for removing mercury of recovery and preparation method thereof.
Adsorbing agent for removing mercury provided by the invention is a kind of mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere, and it is by gelatin and the polyvinyl alcohol crosslinked polymer microballoon that forms, more further functional groups such as sulfydryl and forming on the keyed jointing.And under the condition with glutaraldehyde as cross linker, utilize crosslinked between gelatin and the polyvinyl alcohol, and gelatin and polyvinyl alcohol self is crosslinked, overcome simple use gelatin, the defective of the aspects such as mechanical strength, service life, mass-transfer performance and ageing resistace when perhaps using polyvinyl alcohol merely as the adsorbent matrix.In addition, in keeping the polyvinyl alcohol-gelatine matrix outside peculiar functional group such as hydroxyl, amino and the amide groups etc., utilize simultaneously oh group on the polyvinyl alcohol-gelatine under alkali condition as initator, sulfydryl or polythiaether structure are incorporated in the polyvinyl alcohol-gelatine composite crosslinked microsphere matrix.Finally, by the suction-operated that utilizes the multi-functional group to be produced, and, produce extremely strong adsorption effect, thereby reach the purpose of purifying water body high concentration mercury ion or microscratch amount mercury ion to the mercury heavy metal ion.
The mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent that the present invention proposes, prepared by following method: adopting gelatin and polyvinyl alcohol earlier is primary raw material, glutaraldehyde water solution is a curing agent, prepares required spherical cross-linked polymer polymeric adsorbent; Be mixed solvent with water and non-aqueous volatile solvent again, do the function monomer, carry out further chemical crosslinking, make the mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent at last with the epithio chloropropane.
In the adsorbent, the content of sulfydryl is 0.1-9.0mmol/g.
The mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere preparation of adsorbent method that the present invention proposes is as follows:
(1) takes by weighing 5～15g gelatin and be dissolved in 50～250ml deionized water, be made into the aqueous solution of 1～10% (mass ratio).5～10g polyvinyl alcohol is dissolved in 50～200ml water, is made into the aqueous solution of 1～10% (mass ratio).Then with above-mentioned two kinds of solution by gelatin: the mass ratio of polyvinyl alcohol=1: 0.1～1 mixes and stirs evenly.Then regulate pH=1～4 of above-mentioned mixed water solution with hydrochloric acid.The nonionic surfactant (for example Tween-80, Si Ban-60) of solution weight 0.2% is dissolved in 80～160mL atoleine, under agitation add above-mentioned mixed aqueous solution (its volume be organic facies 1/5～1) then, stir about 0.2～1h, be warming up to 50～90 ℃ then, continue reaction 1～12 hour, reduce mixing speed, add 25% glutaraldehyde water solution (curing agent) of solution weight 2～10%, curing reaction is cessation reaction after 3～12 hours.After filtration, post processing such as washing, be prepared into the polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbing agent matrix, its particle diameter is 0.5 μ m～1.0mm.
(2) adopting 20～200mL water and 20～200mL non-aqueous volatile solvent is mixed solvent, wherein water: non-aqueous volatile solvent=1: 0.5～5 (volume ratio).Take by weighing the above-mentioned polyvinyl alcohol-gelatine composite crosslinked microsphere of 5～50g, water-non-aqueous volatile solvent solution soaked 6～72 hours, added 1～50mL epithio chloropropane, and wherein epithio chloropropane concentration remains on 5～15%.45～90 ℃ reaction is after 1～6 hour down, and the adding sodium hydroxide solution is regulated pH value to 10～14, continues reaction 6～36 hours again.Product is used 2mol/L HCl, 2mol/L HAc and 1mol/L NaOH solution washing successively.Be washed till neutrality with distilled water at last.Use absolute ethyl alcohol ultrasonic cleaning, filtration then, be dried to constant weight, make a kind of mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent at last.The content of sulfydryl is at 0.1～9.0mmol/g in the adsorbent.
The method for preparing the mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent that the present invention proposes, adopt nonionic surfactant, can select tween series, sapn series, AEO series, APES series or alkylolamides polyoxy ethane ether series etc. for use.Non-aqueous volatile solvent adopts the organic solvent of low boiling, high polarity, as ethanol, oxolane, dioxane, acetonitrile or its mixture.
The mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent that the present invention proposes, it can not only guarantee that polymer absorbant has physics and mechanical properties such as enough mechanical strengths and dimensional stability, and it can significantly improve this polymeric material in the presence of the high concentration mercury ion to the absorption property of mercury ion and under little/trace amount mercury ion environment to effective absorbent properties of mercury ion.
The mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent that the present invention proposes, its preparation method is simple and easy to do, the combined coefficient height, mercaptan, thioether, amino and amide groups isoreactivity adsorption group quantity are many, prepared high molecular composite microsphere absorption property excellence, have wide range of applications, especially having wide application prospects aspect the heavy metal industrial effluent processing such as mercurous, plumbous, cadmium.
The invention has the advantages that: (1) it can significantly improve polyvinyl alcohol-gelatine complex microsphere adsorbent in the presence of the high concentration mercury ion to the absorption property of mercury ion and under little/trace amount mercury ion environment to effective absorbent properties of mercury ion.(2) this mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent, not only kept hydrophilic materials such as polyvinyl alcohol and gelatin to effective swelling of aqueous medium and contacting efficiency, but also guaranteed that by suitable cross-linking reaction this polyvinyl alcohol-gelatine material has physics and mechanical properties such as enough mechanical strengths and dimensional stability.(3) this crosslinked polymer microsphere adsorbing agent has composition and characteristics such as the aperture is controlled, all even microstructure porous of size, make this adsorbent surface have bigger serface, significantly increased the touch opportunity of itself and mercury ion, improved its absorbability and infiltration rate mercury ion.(4) last, preparation method of the present invention has that technology is easy, production efficiency is high, product quality is high and advantage such as with low cost, be the efficient removal of mercury product of high-performance of new generation, can be applicable to the mercurous widely process field that waits the heavy metal trade effluent of concentration range.
The loss late of the mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent that the present invention is prepared adopts following method to measure: with the mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent that makes among the present invention, accurately take by weighing 0.5g and put into 100mL distilled water, in 30 ℃ water bath with thermostatic control, stir 24h, filter, take out sample, naturally weigh after drying, according to the weight change counting loss rate before and after handling.Get its mean value by repeated experiments more than 3 times.
Mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbents adsorb mercury ion adsorption capacity and clearance that the present invention is prepared adopt static adsorptive method to detect, and step is as follows:
Under the room temperature, take by weighing the 0.5g sample and drop in the 100ml conical flask, this conical flask adds 25mL variable concentrations C more respectively
oUnder mercury ion solution (0.1g/L, 0.5g/L, 1g/L, 5g/L, 10g/L, 20g/L), reconciling pH value is 7, at room temperature stirring and adsorbing is 45 minutes, filtration is measured Hg in the dilution metering liquid with Italian DMA-80 mercury vapourmeter
2+Concentration C
1Calculate the adsorption capacity Q (mg/g) and the clearance q (%) of adsorbent respectively according to formula (1) and (2).
Q＝(C
o-C
1)*25/0.5 (1)
q＝(C
o-C
1)*100％/C
o (2)
The specific embodiment
The present invention will be further described below in conjunction with embodiment:
Embodiment 1
Take by weighing the 9.6g gelatin and be dissolved in the 118.4ml deionized water, be made into the aqueous solution of 7.5% (mass ratio).The 9g polyvinyl alcohol is dissolved in the 171ml water, is made into the aqueous solution of 5% (mass ratio).Then with above-mentioned two kinds of solution by gelatin: the mass ratio of polyvinyl alcohol=1: 0.6 mixes and stirs evenly.Then regulate the pH=4 of above-mentioned mixed water solution with 5% hydrochloric acid.The Tween-80 of solution weight 0.2% is dissolved in the 100mL atoleine, under agitation add above-mentioned mixed aqueous solution (its volume be organic facies 1/2) then, be warming up to 70 ℃ behind the stir about 0.5h, continue reaction 2 hours, reduce mixing speed, 25% glutaraldehyde water solution that adds solution weight 5% is cured and reacts cessation reaction after 4 hours.After filtration, post processing such as washing, prepare polyvinyl alcohol-gelatine composite crosslinked microsphere.By projection electron microscope (TEM) test shows, this polyvinyl alcohol-gelatine composite crosslinked microsphere material has the micropore of size homogeneous, and the aperture is about 50 μ m.
Adopting 100mL water and 100mL dioxane is mixed solvent, wherein water: dioxane=1: 1 (volume ratio).Take by weighing the above-mentioned polyvinyl alcohol-gelatine composite crosslinked microsphere of 20g, water-non-aqueous volatile solvent solution soaked 12 hours, added 20mL epithio chloropropane, and wherein epithio chloropropane concentration remains on below 10%.75 ℃ are reacted after 2 hours down, add 2% sodium hydroxide solution and regulate pH value to 11, continue reaction 14 hours again.Product is used 2mol/L HCl, 2mol/L HAc and 1mol/LNaOH solution washing successively.Be washed till neutrality with distilled water at last.Using absolute ethyl alcohol ultrasonic cleaning, filtration then, be dried to constant weight, make a kind of mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent at last, is 4.1mmol/g by the content that returns sulfydryl in the argentometric titration mensuration adsorbent.
Through the loss late test, the loss late of this mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent is 0.8%.Detect through static adsorptive method, this adsorbent is the mercuric nitrate absorption 45 minutes of 0.1g/L to the 25mL initial concentration, records its remaining ion concentration of mercury and is respectively 3.18mg/L, and its adsorption capacity is respectively the 4.84mgHg/g adsorbent, and clearance is respectively 96.8%.Detect through static adsorptive method, this adsorbent is the mercuric nitrate absorption 45 minutes of 20g/L to the 25mL initial concentration, records its remaining ion concentration of mercury and is respectively 260.9mg/L, and its adsorption capacity is respectively the 987.0mgHg/g adsorbent, and clearance is respectively 98.7%.
Embodiment 2
Identical with embodiment 1, but the consumption of epithio chloropropane becomes 30mL by 20mL, is 6.05mmol/g by the content that returns sulfydryl in the argentometric titration mensuration adsorbent.Through the loss late test, the loss late of this mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent is 0.8%.Detect through static adsorptive method, this adsorbent is the mercuric nitrate absorption 45 minutes of 0.1g/L to the 25mL initial concentration, records its remaining ion concentration of mercury and is respectively 1.79mg/L, and its adsorption capacity is respectively the 4.91mgHg/g adsorbent, and clearance is respectively 98.2%.Detect through static adsorptive method, this adsorbent is the mercuric nitrate absorption 45 minutes of 20g/L to the 25mL initial concentration, records its remaining ion concentration of mercury and is respectively 225.4mg/L, and its adsorption capacity is respectively the 988.7mgHg/g adsorbent, and clearance is respectively 98.9%.
Embodiment 3
Identical with embodiment 1, but the consumption of epithio chloropropane becomes 10mL by 20mL, is 1.88mmol/g by the content that returns sulfydryl in the argentometric titration mensuration adsorbent.Through the loss late test, the loss late of this mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent is 0.9%.Detect through static adsorptive method, this adsorbent is the mercuric nitrate absorption 45 minutes of 0.1g/L to the 25mL initial concentration, records its remaining ion concentration of mercury and is respectively 7.68mg/L, and its adsorption capacity is respectively the 4.62mgHg/g adsorbent, and clearance is respectively 92.3%.Detect through static adsorptive method, this adsorbent is the mercuric nitrate absorption 45 minutes of 20g/L to the 25mL initial concentration, records its remaining ion concentration of mercury and is respectively 485.2mg/L, and its adsorption capacity is respectively the 975.7mgHg/g adsorbent, and clearance is respectively 97.6%.
Embodiment 4
Identical with embodiment 1, but gelatin: and the mass ratio of polyvinyl alcohol became 1: 0.8 by 1: 0.6.Through the loss late test, the loss late of this mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent is 0.6%.Detect through static adsorptive method, this adsorbent is the mercuric nitrate absorption 45 minutes of 0.1g/L to the 25mL initial concentration, records its remaining ion concentration of mercury and is respectively 9.46mg/L, and its adsorption capacity is respectively the 4.77mgHg/g adsorbent, and clearance is respectively 95.4%.Detect through static adsorptive method, this adsorbent is the mercuric nitrate absorption 45 minutes of 20g/L to the 25mL initial concentration, records its remaining ion concentration of mercury and is respectively 316.4mg/L, and its adsorption capacity is respectively the 984.2mgHg/g adsorbent, and clearance is respectively 98.4%.
Embodiment 5
Identical with embodiment 1, but gelatin: and the mass ratio of polyvinyl alcohol became 1: 1.0 by 1: 0.6.Through the loss late test, the loss late of this mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent is 0.4%.Detect through static adsorptive method, this adsorbent is the mercuric nitrate absorption 45 minutes of 0.1g/L to the 25mL initial concentration, records its remaining ion concentration of mercury and is respectively 11.58mg/L, and its adsorption capacity is respectively the 4.42mgHg/g adsorbent, and clearance is respectively 88.4%.Detect through static adsorptive method, this adsorbent is the mercuric nitrate absorption 45 minutes of 20g/L to the 25mL initial concentration, records its remaining ion concentration of mercury and is respectively 605.9mg/L, and its adsorption capacity is respectively the 969.7mgHg/g adsorbent, and clearance is respectively 97.0%.
Embodiment 6
Identical with embodiment 1, but the consumption of atoleine becomes 150mL by 100mL.This polyvinyl alcohol-gelatine composite crosslinked microsphere material has the micropore of size homogeneous, and the aperture is about 16 μ m.Through the loss late test, the loss late of this mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent is 0.6%.Detect through static adsorptive method, this adsorbent is the mercuric nitrate absorption 45 minutes of 0.1g/L to the 25mL initial concentration, records its remaining ion concentration of mercury and is respectively 1.98mg/L, and its adsorption capacity is respectively the 4.90mgHg/g adsorbent, and clearance is respectively 98.0%.Detect through static adsorptive method, this adsorbent is the mercuric nitrate absorption 45 minutes of 20g/L to the 25mL initial concentration, records its remaining ion concentration of mercury and is respectively 213.6mg/L, and its adsorption capacity is respectively the 989.3mgHg/g adsorbent, and clearance is respectively 98.9%.
Embodiment 7
Identical with embodiment 1, but the consumption of Tween-80 becomes 0.4% by solution weight 0.2%.This polyvinyl alcohol-gelatine composite crosslinked microsphere material has the micropore of size homogeneous, and the aperture is about 22 μ m.Through the loss late test, the loss late of this mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent is 0.7%.Detect through static adsorptive method, this adsorbent is the mercuric nitrate absorption 45 minutes of 0.1g/L to the 25mL initial concentration, records its remaining ion concentration of mercury and is respectively 1.58mg/L, and its adsorption capacity is respectively the 4.92mgHg/g adsorbent, and clearance is respectively 98.4%.Detect through static adsorptive method, this adsorbent is the mercuric nitrate absorption 45 minutes of 20g/L to the 25mL initial concentration, records its remaining ion concentration of mercury and is respectively 206.5mg/L, and its adsorption capacity is respectively the 989.7mgHg/g adsorbent, and clearance is respectively 99.0%.
Embodiment 8
Identical with embodiment 1, but Tween-80 becomes Arlacel-20, and consumption becomes 0.4% by solution weight 0.2%.This polyvinyl alcohol-gelatine composite crosslinked microsphere material has the micropore of size homogeneous, and the aperture is about 38 μ m.Through the loss late test, the loss late of this mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent is 0.8%.Detect through static adsorptive method, this adsorbent is the mercuric nitrate absorption 45 minutes of 0.1g/L to the 25mL initial concentration, records its remaining ion concentration of mercury and is respectively 2.87mg/L, and its adsorption capacity is respectively the 4.86mgHg/g adsorbent, and clearance is respectively 97.1%.Detect through static adsorptive method, this adsorbent is the mercuric nitrate absorption 45 minutes of 20g/L to the 25mL initial concentration, records its remaining ion concentration of mercury and is respectively 226.7mg/L, and its adsorption capacity is respectively the 988.7mgHg/g adsorbent, and clearance is respectively 98.9%.
By the above as seen, a kind of mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent of the present invention's preparation, It can be up to 99.0% to the adsorption rate of mercury ion in the presence of the high concentration mercury ion, under little/trace amount mercury ion environment to mercury from The absorptivity of son also can be up to 98.4%. The mechanics satisfactory mechanical property of this adsorbent, its breakage rate can be lower than after repeatedly using Below 1.0%. This invention has that preparation technology is simple and convenient, production efficiency is high, product quality is high and the advantage such as with low cost, Be high-performance high-efficient mercury removing product of new generation, can be applicable to the widely mercurous processing that waits the heavy metal trade effluent of concentration range The field.
Claims (4)
1, a kind of mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent, it is characterized in that following method prepares: with gelatin and polyvinyl alcohol is primary raw material, and glutaraldehyde water solution is a curing agent, prepares required spherical cross-linked polymer polymeric adsorbent; Be mixed solvent with water and non-aqueous volatile solvent again, do the function monomer with the epithio chloropropane, carry out further chemical crosslinking, make the mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent at last, the content of sulfydryl is 0.1-9.0mmol/g in the adsorbent.
2, as right 1 described mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere preparation of adsorbent method, it is characterized in that concrete steps are as follows:
(1) takes by weighing 5～15g gelatin and be dissolved in 50～250ml deionized water, be made into mass ratio and be 1～10% the aqueous solution, 5～10g polyvinyl alcohol is dissolved in 50～200ml water, be made into mass ratio and be 1～10% the aqueous solution; Then with above-mentioned two kinds of solution by gelatin: the mass ratio of polyvinyl alcohol=1: 0.1～1 mixes and stirs evenly; Then regulate pH=1～4 of above-mentioned mixed water solution with hydrochloric acid; The nonionic surfactant of solution weight 0.2% is dissolved in 80～160mL atoleine, under agitation add above-mentioned mixed aqueous solution then, stir 0.2～1h, be warming up to 50～90 ℃ then, continue reaction 1～12 hour, reduce mixing speed, add 25% glutaraldehyde water solution of solution weight 2～10%, curing reaction is cessation reaction after 3～12 hours; After filtration, the washing, be prepared into the polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbing agent matrix, its particle diameter is 0.5 μ m～1.0mm;
(2) adopting 20～200mL water and 20～200mL non-aqueous volatile solvent is mixed solvent, and wherein water and non-aqueous volatile solvent volume ratio are 1: 0.5～1: 5; Take by weighing the above-mentioned polyvinyl alcohol-gelatine composite crosslinked microsphere of 5～50g, water-non-aqueous volatile solvent solution soaked 6～72 hours, added 1～50mL epithio chloropropane, and wherein epithio chloropropane concentration remains on 5～15%; 45～90 ℃ were reacted 1～6 hour down, added sodium hydroxide solution and regulated pH value to 10～14, continued reaction 6～36 hours again; Product is used 2mol/L HCl, 2mol/L HAc and 1mol/L NaOH solution washing successively; Be washed till neutrality with distilled water at last; Use absolute ethyl alcohol ultrasonic cleaning, filtration then, be dried to constant weight, make a kind of mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbent at last.
3, mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere preparation of adsorbent method according to claim 2 is characterized in that described nonionic surfactant is tween series, sapn series, AEO series, APES series or alkylolamides polyoxy ethane ether series.
4, a kind of mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere preparation of adsorbent method according to claim 2 is characterized in that described non-aqueous volatile solvent is ethanol, oxolane, dioxane or acetonitrile, or wherein several mixtures.
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2008
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