CN102633945A - Manufacturing method of compound type super absorbent resin - Google Patents
Manufacturing method of compound type super absorbent resin Download PDFInfo
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- CN102633945A CN102633945A CN2012101351082A CN201210135108A CN102633945A CN 102633945 A CN102633945 A CN 102633945A CN 2012101351082 A CN2012101351082 A CN 2012101351082A CN 201210135108 A CN201210135108 A CN 201210135108A CN 102633945 A CN102633945 A CN 102633945A
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Abstract
The invention relates to a manufacturing method of a compound type super absorbent resin. The manufacturing method provided by the invention comprises the following steps: pre-processing wheat straws, modifying sodium bentonite by cetyltrimethylammonium bromide, performing copolymerization on the pre-processed wheat straws, the modified bentonite, crylic acid and acrylamide to form the super absorbent resin; collecting a potassium peroxydisulfate solution, an eerie ammonium nitrate solution and a sodium sulfite solution as a compound initiator; and using N-N-methylene diacrylamide as a cross linker. The manufactured compound type super absorbent resin is low in cost and good in water absorbability and salt tolerance, and is applicable in a pH value ranging from 6-10, so that the manufacturing method provided by the invention can be widely applied in the industrial and agricultural production.
Description
Technical field
The present invention relates to a kind of preparation method of composite high water absorption resin, belong to chemistry and environmental technology field.
Background technology
Super absorbent resin can absorb and be equivalent to the water that the own wt hundred times arrives several thousand times, and the suction back can also keep very high water absorbent rate under limited pressure, is the strongest material of absorbent function in present all water-retaining agents.Absorbent resin makes it that application arranged in many aspects owing to its good water-absorbent and water-retentivity, such as gardening, and agricultural, health product.Just present domestic and international research present situation, existing High hydrophilous resin majority is to utilize a large amount of organic substance synthetic, cost is higher, and is difficult for by biological degradation, therefore demands developing the low and eco-friendly super absorbent resin of cost urgently.In recent years, when choosing the starting material of preparation absorbent resin, the wheat stalk of rich cellulose more and more comes into one's own.
Wheat stalk is a kind of reproducible resource, and not only aboundresources is with low cost, and content of cellulose can be up to about 40%.But annual have 95% above stalk resource to utilize approach to change into other forms to be dissipated serious waste of resources through different.The Crop in China stalk resource has a large capacity and a wide range, and present stage, its purposes was broadly divided into 4 aspects: as industrial raw material, be mainly used in industrial papermaking; Livestock feed; Fertilizer is made fertile also field; Fuel, the life in the countryside energy.Even so, resource is still reasonably developed for a long time, and major part is all burned, and this is the huge waste to natural resource, has caused the severe contamination of environment again.Utilize the Mierocrystalline cellulose of natural phant stalk to have the advantage of antimicrobial decomposition for the absorbent resin that skeleton prepares than the starch based resin, the salt resistance of resin also is improved, and also for effective utilization of stalk new method is provided.Simultaneously, other compositions in the stalk such as xylogen, semicellulose etc. all are the organic matters that help fertilizing soil.
The report that at present grafting prepares super absorbent resin about stalk cellulose mainly concentrates on the derivatived cellulose grafting and fastens, and the natural cellulose grafting to be super absorbent resin do not appear in the newspapers as yet.
Summary of the invention
Cause secondary pollution problems to prior art absorbent resin product prepn temperature is high, salt tolerance is poor, be difficult for degraded; The present invention provides a kind of method of utilizing wheat stalk Mierocrystalline cellulose, modified alta-mud graft acrylic acid and acrylic amide to prepare composite high water absorption resin, and present method normal temperature reacts down, secondary pollution is little, have the preparation method of water absorbing properties, biodegradable stalk base high water-absorption resin preferably.
Technical scheme of the present invention is following:
A kind of preparation method of super absorbent resin comprises that step is following:
(1) pre-treatment of wheat stalk
With the wheat straw is raw material, cleans the back 70 ℃ of oven dry down, pulverizes, and crosses 100 mesh sieves;
Get undersized wheat straw, add the ammoniacal liquor of concentration 10～15wt%, soaked 48 hours, suction filtration, water cleans, oven dry; Wheat stalk after the WITH AMMONIA TREATMENT of learning from else's experience, adding concentration are that the salpeter solution of 1mol/L boils 45min, then with mixed solution suction filtration, distilled water flushing, oven dry; Accomplish the pre-treatment of wheat straw.
(2) preparation of modified alta-mud: get the 5g sodium bentonite and place 20mL zero(ppm) water; Regulating PH is 7～8; Add 40mL and be dissolved with the solution of 5.5m mol cetyl trimethylammonium bromide (CTAB), at 80 ℃ of reaction 2～3h down, behind the cool to room temperature with distilled water wash 2～4 times.70 ℃ of oven dry down, ground 100 mesh sieves, make modified alta-mud, kept dry.
(3) polyreaction prepares super absorbent resin
Getting pretreated wheat stalk and modified alta-mud mixes; Wheat stalk: modified alta-mud=(1～1.5): (0.08～0.15) mass ratio; Add potassium persulfate solution, cerous ammonium nitrate solution and sodium sulfite solution successively as composite initiator; In the composite initiator, the mass ratio of Potassium Persulphate, cerous ammonium nitrate and S-WAT is (12～16): (2～4): (4.5～6), stir 15min down at 50 ℃; Add vinylformic acid (AA) and two kinds of monomers of acrylic amide (AM) again, at 50 ℃ of following stirring reaction 1h; The N,N methylene bis acrylamide that adding accounts for two kinds of monomer mass summations 0.07%～0.12% continues stirring reaction 4h as linking agent down at 50 ℃; End product is taken out,, obtain super absorbent resin at 70 ℃ of following vacuum-drying 24h.
Wherein, two kinds of monomeric quality are than vinylformic acid: acrylic amide=2～3: mass ratio=5～6 of 1, two kind of monomer mass summation and wheat stalk: 1, and the composite initiator consumption is 1.0%～1.6% of vinylformic acid and two kinds of monomer mass summations of acrylic amide.
According to the present invention, in the above-mentioned steps (1), the ammoniacal liquor of 10～15wt%: stalk mass ratio=10～12: 1; The salpeter solution of 1mol/L: stalk mass ratio=11～13: 1.
According to the present invention, vinylformic acid is neutralized to the acrylic acid solution adding of degree of neutralization 70%～80% in the above-mentioned steps (3) with the KOH solution of 10mol/L.In the vinylformic acid with before be pure solution.Market can be purchased.
According to the present invention, the raw material monomer acrylic amide is the acrylic amine solution of massfraction 30～50% in the above-mentioned steps (3).Preferred acrylic amide is the acrylic amine solution of massfraction 40%.Market can be purchased.
Preferred according to the present invention; In the above-mentioned steps (3); In the said composite initiator, the mass ratio of Potassium Persulphate, cerous ammonium nitrate and S-WAT is 15: 3: 5, and the composite initiator consumption is 1.2%～1.5% of vinylformic acid (AA) and two kinds of monomer mass summations of acrylic amide (AM).Pure quality in vinylformic acid, acrylamide monomer.
According to the present invention, in the above-mentioned steps (3), said linking agent N,N methylene bis acrylamide consumption is 0.08%～0.1% of vinylformic acid (AA) and two kinds of monomer mass summations of acrylic amide (AM).Wherein the quality of linking agent N,N methylene bis acrylamide is in pure article.Said linking agent N,N methylene bis acrylamide is mixed with solution and adds, and the N,N methylene bis acrylamide strength of solution is 20mg/mL.
The super absorbent resin that the present invention prepares is stalk cellulose/wilkinite composite high water absorption resin, and the applicable pH value is between 6-10, and particularly suitable pH value of solution value is at 6-7.
The present invention with embodiment 1 as the most preferred technique scheme.
The present invention is to be raw material with pretreated wheat stalk, vinylformic acid (AA), acrylic amide (AM) and modified alta-mud, is composite initiator with Potassium Persulphate, cerous ammonium nitrate and S-WAT, and N,N methylene bis acrylamide solution is that linking agent is prepared from.Modified alta-mud is to be raw material with the sodium bentonite, utilizes the synusia shape structure of smectite in the wilkinite and can in water or organic solvent, swelling be dispersed into colloid clay characteristic, inserts the organobentonite that organic insulating covering agent is processed through ion exchange technique.Organobentonite can form gel in all kinds of organic solvents, oils, liquid resin; Have good thickening, thixotropy, suspension stability, high-temperature stability, oilness, film-forming properties; Water tolerance and chemicalstability; In the preparation process, organobentonite can stably be dispersed in the aqueous solution of hydrophilic monomers such as vinylformic acid, can improve the intensity of composite high-water uptake property resin.
The stalk cellulose that the present invention prepares/wilkinite composite high water absorption resin is to be raw material with pretreated wheat stalk, vinylformic acid (AA), acrylic amide (AM) and modified alta-mud; With Potassium Persulphate, cerous ammonium nitrate and S-WAT is composite initiator; N,N methylene bis acrylamide solution is that linking agent is prepared from.The prepared composite high water absorption resin of the present invention comprehensively has water-absorbent, salt tolerance, erosion resistance and biodegradable preferably.Characteristics such as it is extensive that this process has raw material sources, pollution-free, economic, suitable, prepared absorbent resin cost is low, maximum water absorbent rate reaches 190-200g/g, inhale the salt solution multiplying power up to 25g/g about.Prepared absorbent resin product has the bigger pH value scope of application, helps industrial or agricultural and uses.
Description of drawings
Fig. 1 is prepared its water absorbent rate of absorbent resin of embodiment 1 and the relation of absorbent time.X-coordinate is meant absorbent time, and ordinate zou is a water absorbent rate measured under the corresponding absorbent time.
Fig. 2 be the prepared absorbent resin of embodiment 1 its inhale the relation of salt solution multiplying power and absorbent time.X-coordinate is meant to be inhaled the salt solution time, and ordinate zou is a suction salt solution multiplying power measured under the corresponding suction salt solution time.
That Fig. 3 shows is the result of experiment 3, is the graph of a relation of embodiment 1 its water absorbent rate of prepared super absorbent resin and pH value of solution.
Embodiment
Below in conjunction with specific embodiment and accompanying drawing the present invention is further specified, but be not limited thereto.The concentration of reagent is mass percent concentration among the embodiment.Among the embodiment, sodium bentonite is that Weifang development mining industry ltd produces; Acrylic amide is that massfraction is 40% solution, available from Binzhou Chemical Plant, Shandong Prov..
Embodiment 1: a kind of preparation method of super absorbent resin, and step is following:
(1) wheat straw pre-treatment: earth and the dust of removing the wheat stalk surface with water washing.70 ℃ of oven dry down,, sieve with 100 eye mesh screens then with its pulverizing; Take by weighing the wheat straw after the sieving of certain mass; With the ammoniacal liquor quality: stalk quality=ratio of 12: 1 adds the ammoniacal liquor of 12wt%, soaks 48 hours, and soaked wheat stalk suction filtration is also used the zero(ppm) water cleaning, drying; Get the wheat stalk after a certain amount of processing oven dry, with salpeter solution (1mol/L) quality: the salpeter solution that the ratio of stalk quality=12: 1 adds 1mol/L boils 45min, then to mixed solution suction filtration, distilled water flushing, oven dry; Subsequent use.
(2) preparation of modified alta-mud: get the 5g sodium bentonite and place 20mL zero(ppm) water, regulating pH is 7.5, adds the solution that 40mL is dissolved with 5.5m mol CTAB, at 80 ℃ of reaction 2h down, behind the cool to room temperature with distilled water wash 3 times.70 ℃ of oven dry down, ground 100 mesh sieves, make the organobentonite sample, put into moisture eliminator and preserve.
(3) with in the KOH solution of 7mL, 10mol/L and 6mL vinylformic acid (AA), fully mixing and obtaining degree of neutralization is 80% acrylic acid solution;
(4) get modified alta-mud 0.12g in pretreated wheat stalk 1.00g of step (1) and the step (2) in three mouthfuls of round-bottomed flasks.Add composite initiator: the 4.5ml potassium persulfate solution, the cerous ammonium nitrate solution of 0.9ml and 1.5mL sodium sulfite solution, the concentration of potassium persulfate solution, cerous ammonium nitrate solution, sodium sulfite solution is 20mg/mL, at 50 ℃ of following stirring reaction 15min; The process neutral acrylic acid solution 9.30ml of adding step (3) and massfraction are 40% acrylamide soln 3.35ml, at 50 ℃ of following stirring reaction 1h; Add 0.3ml N,N methylene bis acrylamide solution (20mg/mL), at 50 ℃ of following stirring reaction 4h.
Final product is taken out at 70 ℃ of following vacuum-drying 24h, obtain super absorbent resin.Through detecting, the maximum water absorbent rate of gained stalk base high water-absorption resin reaches 196.7g/g, and is as shown in Figure 1; The maximum salt solution multiplying power of inhaling reaches 24.2g/g, and is as shown in Figure 2.
Embodiment 2: of embodiment 1, different is the consumption of wheat stalk:
Get pretreated wheat stalk of 1.20g and 0.12g modified alta-mud in three mouthfuls of round-bottomed flasks, all the other are operated with embodiment 1.The maximum water absorbent rate of gained composite high water absorption resin can reach 168.8g/g, inhales the salt solution multiplying power and reaches 22.2g/g.
Embodiment 3: of embodiment 1, different is the bentonite consumption:
Get pretreated wheat stalk of 1.00 grams and 0.09g modified alta-mud in three mouthfuls of round-bottomed flasks, all the other are operated with embodiment 1.The maximum water absorbent rate of gained composite high water absorption resin can reach 188.5g/g, inhales in the salt solution multiplying power and reaches 23.7g/g.
Embodiment 4: of embodiment 1, different is the consumption that has changed initiator:
Get pretreated wheat stalk of 1.00g and 0.12g modified alta-mud in three mouthfuls of round-bottomed flasks; The cerous ammonium nitrate solution (20mg/mL) that adds 3.6ml potassium persulfate solution (20mg/mL) and 0.72ml; 1.2ml sodium sulfite solution (20mg/mL), at 50 ℃ of following stirring reaction 15min; Add 9.30ml again through neutral acrylic acid solution, 3.35ml acrylamide soln (massfraction is 40%), at 50 ℃ of following stirring reaction 1h.
In there-necked flask, add 0.3mLN, N-methylene-bisacrylamide solution (20mg/mL) is at 50 ℃ of following stirring reaction 4h; Final product is taken out at 70 ℃ of following vacuum-drying 24h, obtain super absorbent resin, maximum water absorbent rate can reach 160.5g/g, and the maximum salt solution multiplying power of inhaling reaches 19.5g/g.
Embodiment 5: of embodiment 1, different is that the vinylformic acid degree of neutralization is different, specific as follows:
Get pretreated wheat stalk of 1.00 grams and 0.12g modified alta-mud in three mouthfuls of round-bottomed flasks; Add 4.5ml potassium persulfate solution (20mg/mL) and the cerous ammonium nitrate solution (20mg/mL) of 0.9ml and the sodium sulfite solution (20mg/mL) of 1.5ml, at 50 ℃ of following stirring reaction 15min; In there-necked flask, add 8.7ml through neutral acrylic acid solution (degree of neutralization 70%), 3.35ml acrylamide soln (massfraction is 40%), at 50 ℃ of following stirring reaction 1h; All the other operations are with embodiment 1.The maximum water absorbent rate of gained composite high water absorption resin can reach 164.8g/g, and the maximum salt solution multiplying power of inhaling can reach 19.8g/g.
Embodiment 6: of embodiment 1, different is that dosage of crosslinking agent is different:
Add 0.60mLN, N-methylene-bisacrylamide solution (20mg/mL) is at 50 ℃ of following stirring reaction 4h.All the other operations are with embodiment 1.The maximum water absorbent rate of gained super absorbent resin can reach 172.1g/g, and the maximum salt solution multiplying power of inhaling can reach 20.8g/g.
Comparative Examples: embodiment 1 is said, and different is not add modified alta-mud.
Get the wheat straw after sieving, with the ammoniacal liquor quality: stalk quality=ratio of 12: 1 adds the ammoniacal liquor of 12wt%, soaks 48 hours, and soaked wheat stalk suction filtration is also used the zero(ppm) water cleaning, drying; Get the wheat stalk after a certain amount of processing oven dry, with the salpeter solution quality: the salpeter solution that the ratio of stalk quality=12: 1 adds 1mol/L boils 45min, then to mixed solution suction filtration, distilled water flushing, oven dry;
Get pretreated wheat stalk 1.00g in three mouthfuls of round-bottomed flasks.Add composite initiator: the 4.5ml potassium persulfate solution, the cerous ammonium nitrate solution of 0.9ml and 1.5mL sodium sulfite solution, the concentration of potassium persulfate solution, cerous ammonium nitrate solution, sodium sulfite solution is 20mg/mL, at 50 ℃ of following stirring reaction 15min; The acrylic acid solution 9.30ml of adding degree of neutralization 80% and massfraction are 40% acrylamide soln 3.35ml, at 50 ℃ of following stirring reaction 1h; Add 0.3ml N,N methylene bis acrylamide solution (20mg/mL), at 50 ℃ of following stirring reaction 4h; End product is taken out at 70 ℃ of following vacuum-drying 24h, obtain absorbent resin.Through detecting, the maximum water absorbent rate of gained absorbent resin is 134.5g/g, and maximum suction salt solution multiplying power is 19.6g/g.
The soaking effect experiment of stalk cellulose of the present invention/wilkinite composite high water absorption resin
Experiment 1: at room temperature, take by weighing the prepared dry good super absorbent resin of 0.1g embodiment 1, put into the beaker that 250mL zero(ppm) water is housed, respectively at 20min with electronic balance; 40min, 60min, 80min, 90min; 100min, 110min, 120min, 140min; 160min measures the quality after its suction during 180min, and calculate its water absorbent rate.
Experiment 2: at room temperature, take by weighing the prepared dry good super absorbent resin of 0.1g embodiment 1, put into the 250mL massfraction and be the beaker of 0.9% NaCl solution with electronic balance; Respectively at 20min, 40min, 60min; 80min, 90min, 100min; 110min, the quality after measuring it during 120min and inhaling salt solution, and calculate it and inhale the salt solution multiplying power.
Experiment 3: in room temperature, the beaker of 250mL zero(ppm) water is regulated the pH value and in the 2-10 scope, is changed, and takes by weighing 0.1g embodiment 1 prepared dry good super absorbent resin with electronic balance and adds wherein, surveys its water absorbent rate.
Detection method:
The calculation formula of water absorbent rate is following:
Q(％)＝(M
1-M
2)/M
2
Wherein, M
1(g) and M
2(g) be respectively the quality of the super absorbent resin of embodiment 1 when initial constantly at t.
The influence of soak time:
That Fig. 1 shows is the result of experiment 1, is the graph of a relation of embodiment 1 its water absorbent rate of prepared super absorbent resin and absorbent time; That Fig. 2 shows is the result of experiment 2, is the graph of a relation of its suction salt solution multiplying power of embodiment 1 prepared super absorbent resin and absorbent time;
As shown in Figure 1, along with the increase of time, the absorption multiplying power of this super absorbent resin in zero(ppm) water becomes increase trend, tends to balance later at 120min.As can be seen from Figure 2, resin water absorbent rate rate of rise when just beginning to soak is very fast, then slowly slows down, and tends to balance gradually later at 80min.Maximum water absorbent rate can reach 196.7g/g, and maximum absorption salt ratio can reach 24.2g/g.
The influence of pH:
That Fig. 3 shows is the result of experiment 3, is the graph of a relation of embodiment 1 its water absorbent rate of prepared super absorbent resin and pH value of solution.
The water-intake rate of this super absorbent resin has different variations under different pH value situation.In pH＜6 o'clock water absorbent rate reduce in addition this resin dissolves in solution, when the pH value is between the 6-7, water absorbent rate just in time, in pH＞7 o'clock, water absorbent rate reduces slightly.This this super absorbent resin of explanation to the susceptibility of acid greater than alkali.Because when pH value of solution hour, a large amount of H in the solution
+Existence, hinder resin network expansion, and influence water absorbing properties because of causing because of electrostatic repulsion between the particle.
It can also be seen that by Fig. 3 this sintetics has the bigger pH value scope of application, is beneficial to agricultural use in addition.
Claims (7)
1. the preparation method of a super absorbent resin comprises that step is following:
(1) pre-treatment of wheat stalk
With the wheat straw is raw material, cleans the back 70 ℃ of oven dry down, pulverizes, and crosses 100 mesh sieves;
Get undersized wheat straw, add the ammoniacal liquor of concentration 10～15wt%, soaked 48 hours, suction filtration, water cleans, oven dry; Wheat stalk after the WITH AMMONIA TREATMENT of learning from else's experience, adding concentration are that the salpeter solution of 1mol/L boils 45min, then with mixed solution suction filtration, distilled water flushing, oven dry; Accomplish the pre-treatment of wheat straw;
(2) preparation of modified alta-mud: get the 5g sodium bentonite and place 20mL zero(ppm) water; Regulating PH is 7～8; Add 40mL and be dissolved with the solution of 5.5mmol cetyl trimethylammonium bromide, at 80 ℃ of reaction 2～3h down, behind the cool to room temperature with distilled water wash 2～4 times; 70 ℃ of oven dry down, ground 100 mesh sieves, make modified alta-mud, kept dry;
(3) polyreaction prepares super absorbent resin
Getting pretreated wheat stalk and modified alta-mud mixes; Wheat stalk: modified alta-mud=(1～1.5): (0.08～0.15) mass ratio adds potassium persulfate solution, cerous ammonium nitrate solution and sodium sulfite solution successively as composite initiator, in the composite initiator; The mass ratio of Potassium Persulphate, cerous ammonium nitrate and S-WAT is (12～16): (2～4): (4.5～6); Stir 15min down at 50 ℃, add two kinds of monomers of vinylformic acid and acrylic amide again, at 50 ℃ of following stirring reaction 1h; The N,N methylene bis acrylamide that adding accounts for two kinds of monomer mass summations 0.07%～0.12% continues stirring reaction 4h as linking agent down at 50 ℃; End product is taken out,, promptly get at 70 ℃ of following vacuum-drying 24h;
Wherein, two kinds of monomeric quality are than vinylformic acid: acrylic amide=2～3: mass ratio=5～6 of 1, two kind of monomer mass summation and wheat stalk: 1, and the composite initiator consumption is 1.0～1.6% of vinylformic acid and two kinds of monomer mass summations of acrylic amide.
2. the preparation method of super absorbent resin as claimed in claim 1 is characterized in that in the step (1) ammoniacal liquor of 10～15wt%: stalk mass ratio=10～12: 1; The salpeter solution of 1mol/L: stalk mass ratio=11～13: 1.
3. the preparation method of super absorbent resin as claimed in claim 1 is characterized in that the middle vinylformic acid of step (3) is neutralized to the acrylic acid solution adding of degree of neutralization 70%～80% with the KOH solution of 10mol/L.
4. the preparation method of super absorbent resin as claimed in claim 1 is characterized in that the raw material monomer acrylic amide is the acrylic amine solution of massfraction 30～50% in the step (3).
5. the preparation method of super absorbent resin as claimed in claim 1; It is characterized in that in the step (3); In the said composite initiator; The mass ratio of Potassium Persulphate, cerous ammonium nitrate and S-WAT is 15: 3: 5, and the composite initiator consumption is 1.2%～1.5% of vinylformic acid and two kinds of monomer mass summations of acrylic amide; Pure quality in vinylformic acid, acrylamide monomer.
6. the preparation method of super absorbent resin as claimed in claim 1 is characterized in that in the step (3), and said linking agent N,N methylene bis acrylamide consumption is 0.08～0.1% of vinylformic acid and two kinds of monomer mass summations of acrylic amide.
7. the preparation method of super absorbent resin as claimed in claim 1 is characterized in that in the step (3), and said linking agent N,N methylene bis acrylamide is mixed with solution and adds, and the N,N methylene bis acrylamide strength of solution is 20mg/mL.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838714A (en) * | 2012-10-15 | 2012-12-26 | 成都理工大学 | Preparation method of straw composite super absorbent resin |
| CN103804056A (en) * | 2014-02-27 | 2014-05-21 | 盐城工学院 | Method for preparing straw based super absorbent resin fertilizer at normal temperature |
| CN104492390A (en) * | 2014-12-19 | 2015-04-08 | 宾远华 | Corn starch-based absorbent material and preparation method thereof |
| CN104761681A (en) * | 2015-04-23 | 2015-07-08 | 山东大学 | Preparation method for enteromorpha-based hydrogel |
| CN106673865A (en) * | 2017-02-21 | 2017-05-17 | 安徽帝元现代农业投资发展有限公司 | Zinc glutamate chelate enhanced biomass-charcoal-based slow-release fertilizer and preparation method thereof |
| CN107417858A (en) * | 2017-07-21 | 2017-12-01 | 南京理工大学 | A kind of preparation method of the composite high-water-absorptivresin resin comprising diatomite and cellulose |
| CN107502367A (en) * | 2017-09-05 | 2017-12-22 | 霍邱金木鱼农业科技有限公司 | A kind of heavy metal adsorption type soil conditioner and preparation method thereof |
| CN108912282A (en) * | 2018-06-07 | 2018-11-30 | 南京林业大学 | A kind of production method of multiple elements design graft modification high hydroscopic resin |
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| CN114920874A (en) * | 2022-06-21 | 2022-08-19 | 中国恩菲工程技术有限公司 | Organic bentonite modified oil-absorbing resin and preparation method thereof |
| CN116283027A (en) * | 2023-02-03 | 2023-06-23 | 北京市政建设集团有限责任公司 | Engineering soil water reducing agent with high water content, preparation method and application thereof |
| CN116855258A (en) * | 2023-07-10 | 2023-10-10 | 贵州省土壤肥料研究所(贵州省生态农业工程技术研究中心)(贵州省农业资源与环境研究所) | Salt-resistant agricultural water-retaining agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101234800A (en) * | 2008-02-19 | 2008-08-06 | 武汉理工大学 | Composite material for treating azo dyes waste water and preparing method thereof |
| CN101974193A (en) * | 2010-11-17 | 2011-02-16 | 武汉工程大学 | Method for preparing low-leaching-rate water-swellable rubbers |
-
2012
- 2012-05-03 CN CN201210135108.2A patent/CN102633945B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101234800A (en) * | 2008-02-19 | 2008-08-06 | 武汉理工大学 | Composite material for treating azo dyes waste water and preparing method thereof |
| CN101974193A (en) * | 2010-11-17 | 2011-02-16 | 武汉工程大学 | Method for preparing low-leaching-rate water-swellable rubbers |
Non-Patent Citations (2)
| Title |
|---|
| ZUOHAO MA等: "Synthesis and characterization of a novel super-absorbent based on wheat straw", 《BIORESOURCE TECHNOLOGY》 * |
| 徐玉文等: "膨润土/丙烯酸/丙烯酰胺三元共聚物的合成与吸水性能研究", 《矿物学报》 * |
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