CN101870598A - Nitrogenous and potassic super absorbent resin fertilizer and preparation method thereof - Google Patents
Nitrogenous and potassic super absorbent resin fertilizer and preparation method thereof Download PDFInfo
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- CN101870598A CN101870598A CN200910071920A CN200910071920A CN101870598A CN 101870598 A CN101870598 A CN 101870598A CN 200910071920 A CN200910071920 A CN 200910071920A CN 200910071920 A CN200910071920 A CN 200910071920A CN 101870598 A CN101870598 A CN 101870598A
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Abstract
The invention discloses a nitrogenous and potassic super absorbent resin fertilizer and a preparation method thereof. Based on ultrasonic treatment technology, the preparation method adopts a novel synthetizing process to prepare a biodegradable nitrogenous potassic absorbent resin fertilizer and is realized by the following steps: carrying out modification treatment on maize straws; carrying out ultrasonic treatment on the maize straws; and preparing nitrogenous and potassic absorbent resin. The modified maize straw powder is added with urea solution, then acrylate solution the neutralization degree of which is between 60 and 85 percent is prepared from the mixture by using KOH, and the acrylate solution is added into modified cellulose solution to make the super absorbent resin contain nitrogen and potassium elements. The raw material in the invention is from one of agricultural solid wastes, has low price and cannot cause any pollution to the environment. The prepared product has sustained release effect on nitrogen and potassium. The biodegradable nitrogenous and potassic absorbent resin can improve the moisture condition of the soil, can be degradated into an organic fertilizer, improves growing environment of crops and is suitable for agriculture popularization and utilization.
Description
Technical field
The present invention relates to a kind of high absorption water-resin that is used for agricultural fertilizer, be specifically related to super absorbent resin of a kind of nitrogenous and potassium element and preparation method thereof.
Background technology
Contain in the maize straw effective ingredients such as a large amount of sugars, robust fibre, protein and multiple in, trace element, belong to a kind of in the agricultural solid residue, also be a kind of renewable resources.But the maize straw Mierocrystalline cellulose is not gone up substantially and is utilized effectively at present, has both caused the resource significant wastage, again environment is polluted.From Sustainable utilization of resources, protection environment and biocompatible and Biodegradable characteristics, people have expressed very big expectation for the utilization of regeneration stalk cellulose.By the stalk cellulose recycling, development environment close friend's green product has become the hot fields in Green Chemistry, the chemical research.
The super absorbent resin raw material is starch mostly at present; or the Mierocrystalline cellulose that extracts in the balloonflower root cotton fiber; as Chinese patent; bulletin is: 101302270A; a kind of preparation method of nitrogenous High hydrophilous resin is to utilize the starch High hydrophilous resin that the grafted propylene nitrile makes under the condition of nitrogen protection, needs high temperature, nitrogen protection and mechanical stirring during gelatinization; polymerization time long production efficient is low, and cost is higher relatively.
With the carrier of super absorbent resin as fertilizer sources nutrient, adopt the method for chemosynthesis, with the method for fertilizer nutrient element and chemosynthesis, with fertilizer element chemical combination or be aggregated in the polymer molecule, make the moisture-retention sustained release fertilizer of chemosynthesis.Fertilizer and water-holding agent is compound integrated, make advanced subject and up-to-date direction that a kind of moisture-retention sustained release fertilizer with water retaining function and fertilizer nutrient slowly-releasing becomes fertilizer research, also be pressing for of agriculture production reality simultaneously.
Summary of the invention
The object of the present invention is to provide super absorbent resin fertilizer of a kind of nitrogenous and potassium and preparation method thereof; be a kind of nitrogenous element and potassium element; and degradable high water-absorbing resin fertilizer with slow releasing function; this preparation method is a raw material with corn stalk, Mono Chloro Acetic Acid, vinylformic acid, potassium hydroxide, Potassium Persulphate, ceric ammonium nitrate, urea etc.; simplify reactions steps, reduced the reaction requirement, need not nitrogen protection; shorten polymerization time greatly, improved production efficiency.
The technical problem to be solved in the present invention is realized by following scheme: the super absorbent resin fertilizer of a kind of nitrogenous and potassium of the present invention, after maize straw is ground into powder and ethanol and NaOH deionized water solution stirring reaction, add the reaction of Mono Chloro Acetic Acid and absolute ethyl alcohol and stirring, with reaction solution ethanolic soln washing and filtering, drying obtains the maize straw powder of modification; Add urea soln in the maize straw powder of modification it is fully dissolved, ultrasonication 4～7 minutes forms the modified fibre cellulose solution; With ceric ammonium nitrate and HNO
3Soluble in water, join in the modified fibre cellulose solution, being mixed with degree of neutralization with KOH is 60%～85% acrylate solution, get this solution and N,N methylene bis acrylamide and mix, this solution is joined in the modified fibre cellulose solution, ultrasonication 1～2 minute gets mixing solutions; In mixing solutions, add K
2S
2O
8The aqueous solution is dried to gel, promptly obtains nitrogenous, potassium super absorbent resin fertilizer of the present invention.
Concrete preparation method of the present invention may further comprise the steps:
1. the modification of maize straw: maize straw is ground into powder, cross 80～200 mesh sieve, get mass fraction and be 10～50 parts of corn stalk powders and 100～200 parts of ethanol, 20～100 parts of concentration and be 50% NaOH deionized water solution, behind stirring reaction 1～2h under 25～40 degree, add 15～70 parts of Mono Chloro Acetic Acids and 45 parts of dehydrated alcohols, stirring reaction 1～2h under 60～80 degree, with in the reaction solution and after-filtration, with concentration is 80%～90% ethanolic soln washing and filtering, and drying obtains the maize straw powder of modification;
2. the ultrasonication of maize straw: the maize straw powder of getting the modification of 2 parts of steps 1, adding concentration is that the urea soln of 10%-53.8% makes its dissolving, ultrasonication 4～7 minutes forms the modified fibre cellulose solution, with 0.1～0.2 part of ceric ammonium nitrate and 0.225～0.64 part of HNO
3Be dissolved in 5 parts the water, join in the modified fibre cellulose solution, being mixed with degree of neutralization with KOH is 60%～85% acrylate solution, get 15～40 parts of these solution and 0.045～0.255 part of N, the N-methylene-bisacrylamide mixes, this solution is joined in the modified fibre cellulose solution, and ultrasonication 1～2 minute gets mixing solutions;
3. the preparation of nitrogenous, potassium super absorbent resin fertilizer: in the mixing solutions that obtains of step 2, add 4 parts of concentration and be 2～5% K
2S
2O
8The aqueous solution reacted 30～60 minutes in the baking ovens at 60～100 degree, up to gel formation, after gel product takes out, dried to constant weight at 40～70 degree, promptly obtained the super absorbent resin fertilizer of nitrogenous and potassium of the present invention.
Characteristics of the present invention are:
The present invention prepares with maize straw that degradable is nitrogenous, potassium absorbent resin fertilizer is compared with traditional method, has simplified reactions steps, has reduced the reaction requirement, resin low cost, degradable and good water absorption.The present invention prepares nitrogenous, potassium with maize straw and has the degradable absorbent resin of slow releasing function.Step is simple, and mild condition is with low cost and realized rationally using of the resource conversion of agricultural wastes and urea, potash fertilizer.
The source of raw material is a kind of of agricultural solid residue among the present invention, and price is extremely cheap, and system finally reaches acid base equilibrium, can not cause any pollution to environment.Processing to maize straw is succinctly convenient, solid content height in the reaction system, and manufacture craft is simple.The ultrasonication technology is applied to the water-absorbing resin preparation, has shortened the reaction times greatly, handle the directly high temperature polymerization of back solution, preparation technology is simple, need not nitrogen protection; Prepared product water-retaining capacity is strong.Product has slow releasing function to nitrogen, potassium, prepares with maize straw that degradable is nitrogenous, the potassium absorbent resin can improve the moisture condition of soil, and can be biodegradable into fertilizer, improves crop growth environment, is suitable for the agricultural extension utilization.
Prepared nitrogenous and potassium absorbent resin fertilizer can be used in the agriculture production, and its usage is the soil of granting plant root, but urea, potassium slowly discharge, reduce the amount of application and the number of times of urea, potassium.Can reduce the soil transpiration, reduce the loss and the seepage of moisture, make full use of moisture, when precipitation content is high, absorb redundant moisture, offer the necessary moisture of plant in the time of arid again, the balance of regulating the content of water in the soil.Through after certain usage period, can be degraded by microorganisms, turn fertilizer into for plant, be used to improve the crop planting environment, especially in the arid area, can not cause any pollution to environment.A large amount of depleted maize straws that this material makes full use of, with low cost, effect is obvious.
Result of use:
One, nitrogen, potassium are slowly discharged, reduce the amount of application and the number of times of nitrogen, potassium.Nitrogen discharges lentamente, the needs of crop whole growing have been satisfied to nitrogen, reduced the caused loss of leaching loss, volatilization and denitrification of urea, can be owing to excessive concentration works the mischief to crop yet, simultaneously owing to can make the base manure applied once, also save the labour, and solved the difficulty of manuring late under the dense planting situation.
Two, reduce the soil transpiration, reduce the loss and the seepage of moisture, make full use of moisture, when precipitation content is high, absorb redundant moisture, offer the necessary moisture of plant in the time of arid again, the balance of regulating the content of water in the soil;
Three, with KOH be neutralizing agent, eliminate the detrimentally affect of sodium ion; Raw material sources are wide, and are with low cost, promote in China easily.
Four, through after certain usage period, can be degraded by microorganisms, can not cause any pollution environment.A large amount of depleted maize straws that this material makes full use of, with low cost, effect is obvious.
Advance of the present invention show following some:
1. with the synthetic water-absorbing resin of straw.
2. nitrogen, potassium are slowly discharged, reduce the amount of application and the number of times of urea, potassium.
3. have degradation property, degraded product helps plant-growth;
4. raw material sources are wide, and are with low cost, promote in China easily.
Embodiment
Embodiment 1
1. the modification of maize straw: under the room temperature, maize straw is ground into powder, crosses 80～200 mesh sieve.Get mass fraction and be 10～50 parts of corn stalk powders and 100～200 parts of ethanol, 20～100 parts of concentration and be 50% NaOH deionized water solution, behind stirring reaction 1～2h under 25～40 degree, add 15～70 parts of Mono Chloro Acetic Acids and 45 parts of dehydrated alcohols, stirring reaction 1～2h under 60～80 degree.With in the reaction solution and after-filtration, be 80%～90% ethanolic soln washing and filtering with concentration, drying obtains the maize straw powder of modification.
2. the ultrasonication of maize straw: get the maize straw powder of the modification of 2 parts of steps 1, the urea soln that adds concentration and be 10%-53.8% fully dissolves it, and with ultrasonication 4～7 minutes, forms the modified fibre cellulose solution.Under the room temperature, 0.1～0.2 part of ceric ammonium nitrate and 0.225～0.64 part of HNO3 be dissolved in 5 parts the water, join in the modified fibre cellulose solution.Being mixed with degree of neutralization with KOH is 60%～85% acrylate solution, get 15～40 parts of these solution and 0.045～0.255 part of N, the N-methylene-bisacrylamide mixes, and this solution is joined in the modified fibre cellulose solution, continues to use ultrasonication 1～2 minute;
3. the preparation of nitrogenous, potassium High hydrophilous resin fertilizer: in the mixing solutions that obtains of step 2, add 4 parts of concentration and be 2～5% K
2S
2O
8The aqueous solution reacted 30～60 minutes in 60～100 degree baking ovens, up to gel formation.After gel product takes out, in 40～70 degree baking ovens, be dried to constant weight, promptly obtain nitrogenous, potassium High hydrophilous resin fertilizer of the present invention.
The preparation method is identical with embodiment 1, the maize straw powder of described modification, and using urea concentration is that 20% solution fully dissolves it.
The preparation method is identical with embodiment 1, the maize straw powder of described modification, and using urea concentration is that 30% solution fully dissolves it.
The preparation method is identical with embodiment 1, the maize straw powder of described modification, and using urea concentration is that 40% solution fully dissolves it.
The preparation method is identical with embodiment 1, the maize straw powder of described modification, and using urea concentration is that 58% solution fully dissolves it.
Claims (2)
1. the super absorbent resin fertilizer of a nitrogenous and potassium, it is characterized in that: after maize straw is ground into powder and ethanol and NaOH deionized water solution stirring reaction, add the reaction of Mono Chloro Acetic Acid and absolute ethyl alcohol and stirring, with reaction solution ethanolic soln washing and filtering, drying obtains the maize straw powder of modification; Add urea soln in the maize straw powder of modification it is fully dissolved, ultrasonication 4～7 minutes forms the modified fibre cellulose solution; With ceric ammonium nitrate and HNO
3Soluble in water, join in the modified fibre cellulose solution, being mixed with degree of neutralization with KOH is 60%～85% acrylate solution, get this solution and N,N methylene bis acrylamide and mix, this solution is joined in the modified fibre cellulose solution, ultrasonication 1～2 minute gets mixing solutions; In mixing solutions, add K
2S
2O
8The aqueous solution is dried to gel, promptly obtains nitrogenous, potassium super absorbent resin fertilizer of the present invention.
2. the preparation method of the super absorbent resin fertilizer of and potassium nitrogenous as 1 one kinds of rights is characterized in that: may further comprise the steps:
(1). the modification of maize straw: maize straw is ground into powder, cross 80～200 mesh sieve, get mass fraction and be 10～50 parts of corn stalk powders and 100～200 parts of ethanol, 20～100 parts of concentration and be 50% NaOH deionized water solution, behind stirring reaction 1～2h under 25～40 degree, add 15～70 parts of Mono Chloro Acetic Acids and 45 parts of dehydrated alcohols, stirring reaction 1～2h under 60～80 degree, with in the reaction solution and after-filtration, with concentration is 80%～90% ethanolic soln washing and filtering, and drying obtains the maize straw powder of modification;
(2). the ultrasonication of maize straw: the maize straw powder of getting the modification of 2 parts of steps 1, adding concentration is that the urea soln of 10%-53.8% makes its dissolving, ultrasonication 4～7 minutes forms the modified fibre cellulose solution, with 0.1～0.2 part of ceric ammonium nitrate and 0.225～0.64 part of HNO
3Be dissolved in 5 parts the water, join in the modified fibre cellulose solution, being mixed with degree of neutralization with KOH is 60%～85% acrylate solution, get 15～40 parts of these solution and 0.045～0.255 part of N, the N-methylene-bisacrylamide mixes, this solution is joined in the modified fibre cellulose solution, and ultrasonication 1～2 minute gets mixing solutions;
(3). the preparation of nitrogenous, potassium super absorbent resin fertilizer: in the mixing solutions that obtains of step 2, add 4 parts of concentration and be 2～5% K
2S
2O
8The aqueous solution reacted 30～60 minutes in 60～100 degree baking ovens, up to gel formation, after gel product takes out, dried to constant weight, promptly at 40～70 degree.
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| CN200910071920A CN101870598A (en) | 2009-04-25 | 2009-04-25 | Nitrogenous and potassic super absorbent resin fertilizer and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060959A (en) * | 2010-12-03 | 2011-05-18 | 中国科学院长春应用化学研究所 | Method for preparing polyacrylic acid water-retaining agent |
| CN103113511A (en) * | 2013-03-14 | 2013-05-22 | 安徽省煤炭科学研究院 | Preparation method of high molecular material coolant |
| 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 |
| CN103896691A (en) * | 2012-12-27 | 2014-07-02 | 青岛鑫垚保水高新材料有限公司 | Preparation method of super absorbent polymer (compound) water retention fertilizer |
| CN105175197A (en) * | 2015-07-15 | 2015-12-23 | 中北大学 | Water-retaining high-molecular slow-release nitrogen-potassium fertilizer and preparation method thereof |
| CN105585380A (en) * | 2015-12-23 | 2016-05-18 | 成都新柯力化工科技有限公司 | Compound fertilizer synergist modified by oxidized graphene and preparation method of compound fertilizer synergist |
| CN106187432A (en) * | 2016-07-01 | 2016-12-07 | 河南工业大学 | A kind of preparation method of Water-retaining slow-release fertilizer |
| CN106748141A (en) * | 2016-12-22 | 2017-05-31 | 安徽康坶国际化肥股份有限公司 | A kind of good fertilizer of nutrition equilibrium nutrient releasing speed |
| CN107417393A (en) * | 2017-07-31 | 2017-12-01 | 中北大学 | A kind of preparation of cellulose base multiple nutrient macromolecule slow-release or control-release fertilizer |
| CN111592411A (en) * | 2020-04-20 | 2020-08-28 | 山东省轻工农副原料研究所 | Compound fertilizer for improving stress resistance of Chinese yam and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060959B (en) * | 2010-12-03 | 2012-07-04 | 中国科学院长春应用化学研究所 | Method for preparing polyacrylic acid water-retaining agent |
| CN102060959A (en) * | 2010-12-03 | 2011-05-18 | 中国科学院长春应用化学研究所 | Method for preparing polyacrylic acid water-retaining agent |
| CN103896691A (en) * | 2012-12-27 | 2014-07-02 | 青岛鑫垚保水高新材料有限公司 | Preparation method of super absorbent polymer (compound) water retention fertilizer |
| CN103113511A (en) * | 2013-03-14 | 2013-05-22 | 安徽省煤炭科学研究院 | Preparation method of high molecular material coolant |
| 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 |
| CN105175197B (en) * | 2015-07-15 | 2019-08-23 | 中北大学 | A kind of water-retaining type high molecular slow-release nitrogen potash fertilizer and preparation method thereof |
| CN105175197A (en) * | 2015-07-15 | 2015-12-23 | 中北大学 | Water-retaining high-molecular slow-release nitrogen-potassium fertilizer and preparation method thereof |
| CN105585380A (en) * | 2015-12-23 | 2016-05-18 | 成都新柯力化工科技有限公司 | Compound fertilizer synergist modified by oxidized graphene and preparation method of compound fertilizer synergist |
| CN106187432A (en) * | 2016-07-01 | 2016-12-07 | 河南工业大学 | A kind of preparation method of Water-retaining slow-release fertilizer |
| CN106748141A (en) * | 2016-12-22 | 2017-05-31 | 安徽康坶国际化肥股份有限公司 | A kind of good fertilizer of nutrition equilibrium nutrient releasing speed |
| CN107417393A (en) * | 2017-07-31 | 2017-12-01 | 中北大学 | A kind of preparation of cellulose base multiple nutrient macromolecule slow-release or control-release fertilizer |
| CN107417393B (en) * | 2017-07-31 | 2020-12-11 | 中北大学 | Preparation of cellulose-based multi-nutrient-element polymer sustained and controlled release fertilizer |
| CN111592411A (en) * | 2020-04-20 | 2020-08-28 | 山东省轻工农副原料研究所 | Compound fertilizer for improving stress resistance of Chinese yam and preparation method thereof |
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Application publication date: 20101027 |