CN102633945B - Manufacturing method of compound type super absorbent resin - Google Patents
Manufacturing method of compound type super absorbent resin Download PDFInfo
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- CN102633945B CN102633945B CN201210135108.2A CN201210135108A CN102633945B CN 102633945 B CN102633945 B CN 102633945B CN 201210135108 A CN201210135108 A CN 201210135108A CN 102633945 B CN102633945 B CN 102633945B
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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 own wt hundred times to the water of several thousand times, after water suction, can also keep very high water absorbent rate having under limits pressure, is the strongest material of absorbent function in current all water-retaining agents.Absorbent resin, due to its good water-absorbent and water-retentivity, makes it have in many aspects application, such as gardening, and agricultural, health product.With regard to current present Research both domestic and external, existing High hydrophilous resin majority is to utilize a large amount of organic substances synthetic, and cost is higher, and is difficult for being biodegradable, and therefore urgently develops the low and eco-friendly super absorbent resin of cost.In recent years, in the time choosing the starting material of preparing 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 40% left and right.But there is every year 95% above stalk resource to utilize approach to change into other forms to be dissipated by different, serious waste of resources.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, makes 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 again the severe contamination of environment.The Mierocrystalline cellulose that utilizes natural phant stalk has advantages of Resistance to microbes compared with starch based resin for the absorbent resin that skeleton prepares, and the salt resistance of resin is also improved, also for effective utilization of stalk provides new method.Meanwhile, other compositions in stalk as xylogen, hemicellulose etc. are all the organic matters that are conducive to fertilizing soil.
The report that at present super absorbent resin is prepared in grafting about stalk cellulose mainly concentrates on derivatived cellulose grafting and fastens, and natural cellulose grafting to be super absorbent resin there is not yet report.
Summary of the invention
High for prior art absorbent resin product preparation temperature, salt tolerance is poor, be difficult for degraded causes secondary pollution problems, the invention provides a kind of method of utilizing wheat stalk Mierocrystalline cellulose, modified alta-mud graft acrylic acid and acrylamide to prepare composite high water absorption resin, the preparation method who react under present method normal temperature, secondary pollution is little, there is good water absorbing properties, biodegradable straw base super absorbent resin.
Technical scheme of the present invention is as follows:
A preparation method for super absorbent resin, comprises that step is as follows:
(1) pre-treatment of wheat stalk
Take wheat straw as raw material, after cleaning, at 70 ℃, dry, pulverize, cross 100 mesh sieves;
Get the wheat straw under sieve, add the ammoniacal liquor of concentration 10～15wt%, soak 48 hours, suction filtration, water cleans, and dries; The wheat stalk of learning from else's experience after ammonia treatment, adding concentration is that the salpeter solution of 1mol/L boils 45min, then by mixed solution suction filtration, distilled water flushing, oven dry; Complete the pre-treatment of wheat straw.
(2) preparation of modified alta-mud: get 5g sodium bentonite and be placed in 20mL distilled water, regulating PH is 7～8, add 40mL to be dissolved with the solution of 5.5m mol cetyl trimethylammonium bromide (CTAB), at 80 ℃, react 2～3h, after cool to room temperature, use distilled water wash 2～4 times.At 70 ℃, dry, ground 100 mesh sieves, make modified alta-mud, kept dry.
(3) polyreaction is prepared 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 successively potassium persulfate solution, cerous ammonium nitrate solution and sodium sulfite solution as composite initiator, in composite initiator, the mass ratio of Potassium Persulphate, cerous ammonium nitrate and S-WAT is (12～16): (2～4): (4.5～6), at 50 ℃, stir 15min, add again vinylformic acid (AA) and two kinds of monomers of acrylamide (AM), stirring reaction 1h at 50 ℃; Add the N,N methylene bis acrylamide that accounts for two kinds of monomer mass summations 0.07%～0.12% as linking agent, at 50 ℃, continue stirring reaction 4h; End product is taken out, and at 70 ℃, vacuum-drying 24h, obtains super absorbent resin.
Wherein, the quality of two kinds of monomers is than vinylformic acid: acrylamide=2～3: mass ratio=5～6 of 1, two kind of monomer mass summation and wheat stalk: 1, and composite initiator consumption is 1.0%～1.6% of vinylformic acid and two kinds of monomer mass summations of acrylamide.
According to the present invention, in 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, the acrylic acid solution that in above-mentioned steps (3), vinylformic acid is neutralized to degree of neutralization 70%～80% with the KOH solution of 10mol/L adds.In vinylformic acid and front pure solution.Market can be purchased.
According to the present invention, in above-mentioned steps (3), raw material monomer acrylamide is the acrylic amine solution of massfraction 30～50%.Preferably acrylamide is the acrylic amine solution of massfraction 40%.Market can be purchased.
Preferred according to the present invention, in above-mentioned steps (3), in described composite initiator, the mass ratio of Potassium Persulphate, cerous ammonium nitrate and S-WAT is 15: 3: 5, and composite initiator consumption is 1.2%～1.5% of vinylformic acid (AA) and two kinds of monomer mass summations of acrylamide (AM).In the sterling quality of vinylformic acid, acrylamide monomer.
According to the present invention, in above-mentioned steps (3), described 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 acrylamide (AM).Wherein the quality of linking agent N,N methylene bis acrylamide is in sterling.Described linking agent N,N methylene bis acrylamide is mixed with solution and adds, and 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 applicable pH value is between 6-10, and particularly suitable pH is at 6-7.
The present invention using embodiment 1 as most preferred technique scheme.
The present invention is take pretreated wheat stalk, vinylformic acid (AA), acrylamide (AM) and modified alta-mud as raw material, take Potassium Persulphate, cerous ammonium nitrate and S-WAT as composite initiator, N,N methylene bis acrylamide solution is that linking agent is prepared from.Modified alta-mud is take sodium bentonite as raw material, utilize montmorillonite in wilkinite lamellar structure and can be in water or organic solvent the swelling colloid clay characteristic that is dispersed into, insert by ion exchange technique the organobentonite that organic insulating covering agent is made.Organobentonite can form gel in all kinds of organic solvents, oils, liquid resin, there is good thickening property, thixotropy, suspension stability, high-temperature stability, oilness, film-forming properties, water tolerance and chemical stability, in preparation process, organobentonite can stably be dispersed in the aqueous solution of the hydrophilic monomers such as vinylformic acid, can improve the intensity of composite high-water uptake resin.
Stalk cellulose/wilkinite composite high water absorption resin that the present invention prepares is take pretreated wheat stalk, vinylformic acid (AA), acrylamide (AM) and modified alta-mud as raw material, take Potassium Persulphate, cerous ammonium nitrate and S-WAT as 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 good water-absorbent, salt tolerance, erosion resistance and biodegradable.The features such as it is extensive that this process has raw material sources, pollution-free, economic, applicable, prepared absorbent resin cost is low, and maximum water absorbent rate reaches 190-200g/g, inhales salt solution multiplying power up to 25g/g left and right.Prepared absorbent resin product has the larger pH value scope of application, is conducive to industrial or agricultural application.
Accompanying drawing explanation
Fig. 1 is the relation of its water absorbent rate of the prepared absorbent resin of embodiment 1 and absorbent time.X-coordinate refers to absorbent time, and ordinate zou is water absorbent rate measured under corresponding absorbent time.
Fig. 2 is its relation of inhaling salt solution multiplying power and absorbent time of the prepared absorbent resin of embodiment 1.X-coordinate refers to be inhaled the salt solution time, and ordinate zou is suction salt solution multiplying power measured under the corresponding suction salt solution time.
What Fig. 3 showed is the result of experiment 3, is the graph of a relation of its water absorbent rate of the prepared super absorbent resin of embodiment 1 and pH value of solution.
Embodiment
Below in conjunction with specific embodiment and accompanying drawing, the present invention will be further described, but be not limited to this.In embodiment, the concentration of reagent is mass percent concentration.In embodiment, sodium bentonite is that Weifang development mining industry company limited produces; Acrylamide is that massfraction is 40% solution, purchased from Binzhou Chemical Plant, Shandong Prov..
Embodiment 1: a kind of preparation method of super absorbent resin, step is as follows:
(1) wheat straw pre-treatment: wash earth and the dust of removing wheat stalk surface with water.At 70 ℃, dry, then pulverized, sieve with 100 eye mesh screens, take the wheat straw after the sieving of certain mass, with ammoniacal liquor quality: stalk quality=12: 1 ratio adds the ammoniacal liquor of 12wt%, soak 48 hours, by soaked wheat stalk suction filtration and use distilled water cleaning, drying; Get the wheat stalk after a certain amount of processing is dried, with salpeter solution (1mol/L) quality: stalk quality=12: the salpeter solution that 1 ratio adds 1mol/L boils 45min, then to mixed solution suction filtration, distilled water flushing, oven dry; For subsequent use.
(2) preparation of modified alta-mud: get 5g sodium bentonite and be placed in 20mL distilled water, regulating pH is 7.5, adds 40mL to be dissolved with the solution of 5.5m mol CTAB, reacts 2h at 80 ℃, uses distilled water wash 3 times after cool to room temperature.At 70 ℃, dry, ground 100 mesh sieves, make organobentonite sample, put into moisture eliminator and preserve.
(3), with in the KOH solution of 7mL, 10mol/L and 6mL vinylformic acid (AA), being fully uniformly mixed and obtaining degree of neutralization is 80% acrylic acid solution;
(4) get modified alta-mud 0.12g in the pretreated wheat stalk 1.00g of step (1) and step (2) in three mouthfuls of round-bottomed flasks.Add composite initiator: 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, stirring reaction 15min at 50 ℃; Add the acrylic acid solution 9.30ml through neutralization of step (3) and the acrylamide soln 3.35ml that massfraction is 40%, stirring reaction 1h at 50 ℃; Add 0.3ml N,N methylene bis acrylamide solution (20mg/mL), stirring reaction 4h at 50 ℃.
Final product is taken out to vacuum-drying 24h at 70 ℃, obtain super absorbent resin.After testing, the maximum water absorbent rate of gained straw base super absorbent resin reaches 196.7g/g, as shown in Figure 1; The maximum salt solution multiplying power of inhaling reaches 24.2g/g, as shown in Figure 2.
Embodiment 2: as described in Example 1, difference is the consumption of wheat stalk:
Get the pretreated wheat stalk of 1.20g and 0.12g modified alta-mud in three mouthfuls of round-bottomed flasks, all the other operate with embodiment 1.The maximum water absorbent rate of gained composite high water absorption resin can reach 168.8g/g, inhales salt solution multiplying power and reaches 22.2g/g.
Embodiment 3: as described in Example 1, difference is bentonite consumption:
Get 1.00 grams of pretreated wheat stalks and 0.09g modified alta-mud in three mouthfuls of round-bottomed flasks, all the other operate with embodiment 1.The maximum water absorbent rate of gained composite high water absorption resin can reach 188.5g/g, inhales in salt solution multiplying power and reaches 23.7g/g.
Embodiment 4: as described in Example 1, difference is the consumption that has changed initiator:
Get the pretreated wheat stalk of 1.00g and 0.12g modified alta-mud in three mouthfuls of round-bottomed flasks, add the cerous ammonium nitrate solution (20mg/mL) of 3.6ml potassium persulfate solution (20mg/mL) and 0.72ml, the sodium sulfite solution (20mg/mL) of 1.2ml, stirring reaction 15min at 50 ℃; Add again acrylic acid solution, the 3.35ml acrylamide soln (massfraction be 40%) of 9.30ml through neutralization, stirring reaction 1h at 50 ℃.
In there-necked flask, add 0.3mLN, N-methylene-bisacrylamide solution (20mg/mL), stirring reaction 4h at 50 ℃; Final product is taken out to vacuum-drying 24h at 70 ℃, 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: as described in Example 1, difference is vinylformic acid degree of neutralization difference, specific as follows:
Get 1.00 grams of pretreated wheat stalks and 0.12g modified alta-mud in three mouthfuls of round-bottomed flasks, add the cerous ammonium nitrate solution (20mg/mL) of 4.5ml potassium persulfate solution (20mg/mL) and 0.9ml and the sodium sulfite solution (20mg/mL) of 1.5ml, stirring reaction 15min at 50 ℃; In there-necked flask, add acrylic acid solution (degree of neutralization 70%), the 3.35ml acrylamide soln (massfraction be 40%) of 8.7ml through neutralization, stirring reaction 1h at 50 ℃; All the other operate 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: as described in Example 1, difference is dosage of crosslinking agent difference:
Add 0.60mLN, N-methylene-bisacrylamide solution (20mg/mL), stirring reaction 4h at 50 ℃.All the other operate 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.
Described in comparative example: embodiment 1, difference is not add modified alta-mud.
Get the wheat straw after sieving, with ammoniacal liquor quality: stalk quality=12: 1 ratio adds the ammoniacal liquor of 12wt%, soak 48 hours, by soaked wheat stalk suction filtration and use distilled water cleaning, drying; Get the wheat stalk after a certain amount of processing is dried, with salpeter solution quality: stalk quality=12: the salpeter solution that 1 ratio 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: 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, stirring reaction 15min at 50 ℃; Add the acrylic acid solution 9.30ml of degree of neutralization 80% and the acrylamide soln 3.35ml that massfraction is 40%, stirring reaction 1h at 50 ℃; Add 0.3ml N,N methylene bis acrylamide solution (20mg/mL), stirring reaction 4h at 50 ℃; End product is taken out to vacuum-drying 24h at 70 ℃, obtain absorbent resin.After testing, 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/wilkinite composite high water absorption resin of the present invention
Experiment 1: at room temperature, take the prepared dried super absorbent resin of 0.1g embodiment 1 with electronic balance, put into the beaker that 250mL distilled water is housed, respectively at 20min, 40min, 60min, 80min, 90min, 100min, 110min, 120min, 140min, 160min, when 180min, measure the quality after its water suction, and calculate its water absorbent rate.
Experiment 2: at room temperature, take the prepared dried super absorbent resin of 0.1g embodiment 1 with electronic balance, put into 250mL massfraction and be the beaker of 0.9% NaCl solution, respectively at 20min, 40min, 60min, 80min, 90min, 100min, 110min, measures it and inhales the quality after salt solution when 120min, and calculates it and inhale salt solution multiplying power.
Experiment 3: in room temperature, the beaker of 250mL distilled water, regulates pH value to change within the scope of 2-10, takes the prepared dried super absorbent resin of 0.1g embodiment 1 with electronic balance and adds wherein, surveys its water absorbent rate.
Detection method:
The calculation formula of water absorbent rate is as follows:
Q(％)＝(M
1-M
2)/M
2
Wherein, M
1and M (g)
2(g) be respectively in t moment and the quality of the super absorbent resin of embodiment 1 when initial.
The impact of soak time:
What Fig. 1 showed is the result of experiment 1, is the graph of a relation of its water absorbent rate of the prepared super absorbent resin of embodiment 1 and absorbent time; What Fig. 2 showed is the result of experiment 2, is the graph of a relation of its suction salt solution multiplying power of the prepared super absorbent resin of embodiment 1 and absorbent time;
As shown in Figure 1, along with the increase of time, the absorbency of this super absorbent resin in distilled water becomes increase trend, after 120min, tends to balance.As can be seen from Figure 2, resin water absorbent rate rate of rise in the time just starting to soak is very fast, then slowly slows down, and after 80min, tends to balance gradually.Maximum water absorbent rate can reach 196.7g/g, and maximum absorption salt ratio can reach 24.2g/g.
The impact of pH:
What Fig. 3 showed is the result of experiment 3, is the graph of a relation of its water absorbent rate of the prepared super absorbent resin of embodiment 1 and pH value of solution.
The water-intake rate of this super absorbent resin has different variations in different pH value situations.In the time of pH < 6, even this resin dissolves is in solution in water absorbent rate reduction, and in the time that pH value is between 6-7, just in time, in the time of pH > 7, water absorbent rate reduces water absorbent rate slightly.This illustrates that this super absorbent resin is greater than alkali to sour susceptibility.Because when pH value of solution hour, a large amount of H in solution
+existence, hinder the resin network expansion because causing because of electrostatic repulsion between particle, and affect water absorbing properties.
In addition it can also be seen that by Fig. 3 this sintetics has the larger pH value scope of application, is beneficial to agricultural use.
Claims (5)
1. a preparation method for composite high water absorption resin, comprises that step is as follows:
(1) pre-treatment of wheat stalk
Take wheat straw as raw material, after cleaning, at 70 ℃, dry, pulverize, cross 100 mesh sieves;
Get the wheat straw under sieve, add the ammoniacal liquor of concentration 10～15wt%, soak 48 hours, suction filtration, water cleans, and dries; The wheat stalk of learning from else's experience after ammonia treatment, adding concentration is that the salpeter solution of 1mol/L boils 45min, then by mixed solution suction filtration, distilled water flushing, oven dry; Complete the pre-treatment of wheat straw;
The ammoniacal liquor of described 10～15wt%: stalk mass ratio=10～12:1; The salpeter solution of 1mol/L: stalk mass ratio=11～13:1;
(2) preparation of modified alta-mud: get 5g sodium bentonite and be placed in 20mL distilled water, regulating pH is 7～8, add 40mL to be dissolved with the solution of 5.5m mol cetyl trimethylammonium bromide, at 80 ℃, react 2～3h, after cool to room temperature, use distilled water wash 2～4 times; At 70 ℃, dry, ground 100 mesh sieves, make modified alta-mud, kept dry;
(3) polyreaction is prepared 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 successively potassium persulfate solution, ceric ammonium nitrate solution and sodium sulfite solution as composite initiator, in composite initiator, the mass ratio of Potassium Persulphate, ceric ammonium nitrate and S-WAT is (12～16): (2～4): (4.5～6), at 50 ℃, stir 15min, add again two kinds of monomers of vinylformic acid and acrylamide, stirring reaction 1h at 50 ℃; Add the N that accounts for two kinds of monomer mass summations 0.07% ~ 0.12%, N '-methylene-bisacrylamide, as linking agent, continues stirring reaction 4h at 50 ℃; End product is taken out, and at 70 ℃, vacuum-drying 24h, to obtain final product;
Wherein, the quality of two kinds of monomers is than vinylformic acid: acrylamide=2～3:1, the mass ratio=5～6:1 of two kinds of monomer mass summations and wheat stalk, and composite initiator consumption is 1.0～1.6% of vinylformic acid and two kinds of monomer mass summations of acrylamide;
The acrylic acid solution that vinylformic acid is neutralized to degree of neutralization 70% ~ 80% with the KOH solution of 10mol/L adds.
2. the preparation method of composite high water absorption resin as claimed in claim 1, is characterized in that in step (3), raw material monomer acrylamide is the acrylamide soln of massfraction 30～50%.
3. the preparation method of composite high water absorption resin as claimed in claim 1, it is characterized in that in step (3), in described composite initiator, the mass ratio of Potassium Persulphate, ceric ammonium nitrate and S-WAT is 15:3:5, and composite initiator consumption is 1.2%～1.5% of vinylformic acid and two kinds of monomer mass summations of acrylamide; In the sterling quality of vinylformic acid, acrylamide monomer.
4. the preparation method of composite high water absorption resin as claimed in claim 1, is characterized in that in step (3), described linking agent N, and N '-methylene-bisacrylamide consumption is 0.08 ~ 0.1% of vinylformic acid and two kinds of monomer mass summations of acrylamide.
5. the preparation method of composite high water absorption resin as claimed in claim 1, is characterized in that in step (3), described linking agent N, and N '-methylene-bisacrylamide is mixed with solution and adds, N, N '-methylene-bisacrylamide strength of solution is 20mg/mL.
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| CN102838714B (en) * | 2012-10-15 | 2015-06-17 | 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 |
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| 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 |
| CN109970917A (en) * | 2019-04-04 | 2019-07-05 | 黑龙江大学 | A kind of super absorbent resin and preparation method thereof containing montmorillonite |
| CN112500530B (en) * | 2020-10-30 | 2022-05-31 | 广西大学 | Calcium carbonate/bagasse cellulose-based super absorbent resin and preparation method thereof |
| CN113683730A (en) * | 2021-08-27 | 2021-11-23 | 西华大学 | Corn straw cellulose-based water-absorbent resin composite material and preparation method thereof |
| 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 |
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