CN103865002A - High-water absorption humic acid resin with water conserving, water retention and trace fertilizer sustained-release functions - Google Patents
High-water absorption humic acid resin with water conserving, water retention and trace fertilizer sustained-release functions Download PDFInfo
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- CN103865002A CN103865002A CN201410120234.XA CN201410120234A CN103865002A CN 103865002 A CN103865002 A CN 103865002A CN 201410120234 A CN201410120234 A CN 201410120234A CN 103865002 A CN103865002 A CN 103865002A
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Abstract
The invention discloses a preparation method and application of multifunctional high-water absorption humic acid resin with water conserving, water retention and trace fertilizer sustained-release functions. The preparation method comprises the following steps of chelating borax, zinc sulfate, manganese sulfate, ammonium molybdate, iron sulfate and the like by using a chelating agent, mixing the raw materials at the ratio of sodium (or potassium) humate solution to acrylic acid to cross-linking agent to trace fertilizer being (300-400):(80-100):(1-3):(6-10), adding an initiator, and performing reaction to prepare the high-water absorption humic acid resin. The resin has the water conserving, water retention and trace fertilizer sustained-release functions, and can be applied to the industries of agriculture, forestry, gardening and the like to fulfill the aim of increasing both production and income, and the growth and development requirements of crops can be well met.
Description
Technical field
The invention provides a kind of humic acids super absorbent resin with water conservation and moisture-holding and micro-fertilizer slow-release function, belong to agricultural production application field.
Background technology
In recent years, drought and water shortage phenomenon frequently occurs, and agriculture production has been formed to serious threat, and the efficient utilization and the grain security that realize water resources are national strategic demands.The super absorbent resin that research and development have water saving, water conservation and soil improvement function is important measures of agricultural production reply drought and water shortage phenomenon.
Traditional super absorbent resin can be divided into starch-series, cellulose-based and synthetic resins system.The research of humic acids super absorbent resin has in recent years caused people's great interest in recent years, is considered to the most rising a kind of super absorbent resin.Humic acids is a kind of organic macromolecule compound that occurring in nature extensively exists, and is the main component of soil ulmin in rich soil, in coal, marsh, pond, irrigation canals and ditches mud, exists in a large number.Because humic acids has good chemistry and biological activity, set it as raw material and prepare humic acids super absorbent resin, can bring into play the resistance that humic acids stimulating plant grew, increased crop, effect of improving plant nutrition, the preserve moisture and fertility ability that can improve again soil also can significantly reduce production costs simultaneously.But current research all concentrates on the pure organic humic acid super absorbent resin that complex functionality is single, multi-functional characteristic needs further to be developed.
Growing of crop be unable to do without moisture and fertilizer.The fertilizer that people have known is the chemical fertilizer of the macroelement such as nitrogenous, phosphorus, potassium, but the effect of micro-fertilizer (as boron, molybdenum, zinc, manganese, iron etc.) is also lacked to attention.In fact, although farm crop are very low to micro-fertile demand, while shortage, can grow cause to the normal growth of crop and have a strong impact on, the major reason that succession crop output can reduce be greatly exactly certain slightly fertilizer can not be supplemented in time.Trace element is the effective ingredient of plurality of enzymes, participates in carbon assimalation, carbohydrate transhipment, nitrogen metabolism and redox processes etc.Generally, according to soil and fertilizer deficiency extent and plant demand, using on the basis of nitrogen, phosphorus, potash fertilizer, it is the effective measure that obtain good quality and high output that timely and appropriate discovery enriches micro-fertilizer.Current, in agricultural production practice, because micro-fertile consumption is very few, micro-fertile series products is all generally to do Foliar Spraying to use, but because attention degree is inadequate, the production and selling situation of micro-fertilizer is very undesirable.
If the introduced plant required trace element of growing in humic acids super absorbent resin, the humic acid multifunctional super absorbent resin that obtained like this can both have the basic functions such as water saving, water conservation, there is again the new function of the micro-fertilizer of slowly-releasing, realize the sustained release of the required moisture of plant-growth and micro-fertilizer, humic acids super absorbent resin can be converted into again fertilizer and the improvement soil of Promoting plant growth after degraded simultaneously, has not yet to see research and the application report of this respect.
Summary of the invention
The object of the present invention is to provide a kind of humic acid multifunctional super absorbent resin with water conservation and moisture-holding and micro-fertilizer slow-release function.
Object of the present invention is achieved through the following technical solutions:
(1) by weathered coal or brown coal or mud coal or the peat composed of rotten mosses or other low grade coal, after selected impurity elimination, be ground into 80-400 object powder;
(2) by above-mentioned powder: sodium hydroxide: sodium ethylene diamine tetracetate: the weight ratio of water=10～30:0.5～3:0.1～0.5:80～300 is mixed, stir, be heated to 70～90 DEG C of reaction 0.5-2 hour, after being down to room temperature, get supernatant liquor, the sodium humate solution that concentrated water content is 30～50%;
(3) by sodium humate solution: vinylformic acid: linking agent: after the weight ratio of micro-fertilizer=300～400:80～100:1～3:6～10 is fully mixed, 30～40 DEG C of stirring reactions 10～20 minutes, add the initiator of 5～15 weight parts, and be warming up to 70～90 DEG C reaction 0.5～1 hour, after cooling, filter, getting filter residue dry, pulverize and be finished product in 60～80 DEG C.
Vinylformic acid used need carry out part neutralization, and degree of neutralization is 50～80%, makes finished product pH value between 6.5-7.5;
Linking agent used can be N, one or more in N`-methylene-bisacrylamide, acrylamide, urea, formaldehyde;
Micro-fertilizer used is whole or several in borax, zinc sulfate, manganous sulfate, ammonium molybdate, ferrous sulfate, ratio can be allocated as required, and borax, zinc sulfate, manganous sulfate, ammonium molybdate, ferrous sulfate in advance one or more in sequestrant sodium ethylene diamine tetracetate, citric acid, oxalic acid carry out chelating pre-treatment;
Initiator used can be one or more in ammonium persulphate, Sodium Persulfate, Potassium Persulphate;
Sodium hydroxide in step (2) also available hydrogen potassium oxide replaces;
When use, can directly resin be embedded in to crop root, also can mix rear evenly spreading fertilizer over the fields in plantation ditch in the ratio of 1:10～20 and thin dry ground, earthing also waters permeablely, then plants.
The present invention has the following advantages:
1. the humic acid multifunctional super absorbent resin of preparation had both had water conservation and moisture-holding function, had again micro-fertilizer slow-release function, can better meet crop growth needs;
2. resin can be used as modifying agent and the water-holding agent of soil in agricultural, can improve seed percentage of germination, prevent that root is dry etc., can directly act on crop root, retaining and non-rot root;
3. the micro-fertilizer adding can need to be adjusted according to different soils environment and crop growth;
4. resin is applied to forestry, can be for breeding and afforestation, desert transformation etc.;
5. resin is applied in gardening field, can, as the water-holding agent of Nursery stock transplanting, improve the surviving rate of migration process plant.
Embodiment
Embodiment 1:
1) weathered coal is removed after the foreign material such as stone, iron wire, be ground into the powder of 200 order left and right with pulverizer;
2) get 10 kilograms, above-mentioned powder, add 1 kilogram, sodium hydroxide, 0.2 kilogram of sodium ethylene diamine tetracetate, 100 kilograms, water, stirs, and is heated to 90 DEG C of reactions 2 hours, and after cooling, the sodium humate solution of 30% left and right is got supernatant concentration and is become in centrifugation;
3) weight ratio of preparing micro-fertilizer is: sodium ethylene diamine tetracetate: Na
2b
4o
710H
2o:ZnSO
47H
2o:FeSO
47H
2o:MnSO
4h
2o:(NH
4)
2moO
4=15:7:2:3:2:0.5, adds in advance a small amount of water and stirs, can stable existence.
4) by sodium humate solution: vinylformic acid (degree of neutralization is 65%): N, N`-methylene-bisacrylamide: the raw material weight ratio of micro-fertilizer=300:100:2:6 fully mixes, 30 DEG C of stirring reactions 20 minutes, add 12 parts of Potassium Persulphates, and be warming up to 80 DEG C reaction 1 hour, cooling after filter, 70 DEG C dry, pulverize to obtain finished product.
Embodiment 2:
1) brown coal are removed after the foreign material such as stone, iron wire, be ground into the powder of 300 order left and right with pulverizer;
2) get 10 kilograms, above-mentioned powder, add 1.5 kilograms, sodium hydroxide, 0.4 kilogram of sodium ethylene diamine tetracetate, 150 kilograms, water, stirs, and is heated to 90 DEG C of reactions 2 hours, and after cooling, the sodium humate solution of 40% left and right is got supernatant concentration and is become in centrifugation;
3) weight ratio of preparing micro-fertilizer is: sodium ethylene diamine tetracetate: citric acid: Na
2b
4o
710H
2o:ZnSO
47H
2o:MnSO
4h
2o=10:6:8:2:1, adds in advance a small amount of water and stirs, can stable existence.
4) by sodium humate solution: vinylformic acid (degree of neutralization is 50%): N, N`-methylene-bisacrylamide: acrylamide: the raw material weight ratio of micro-fertilizer=300:90:2:1:6 fully mixes, 40 DEG C of stirring reactions 20 minutes, add 15 parts of ammonium persulphates, and be warming up to 90 DEG C reaction 0.5 hour, cooling after filter, 70 DEG C dry, pulverize to obtain finished product.
Embodiment 3:
1) peat composed of rotten mosses is removed after the foreign material such as stone, iron wire, be ground into the powder of 200 order left and right with pulverizer;
2) get 10 kilograms, above-mentioned powder, add 2 kilograms, potassium hydroxide, 0.5 kilogram of sodium ethylene diamine tetracetate, 200 kilograms, water, stirs, and is heated to 80 DEG C of reactions 1 hour, and after cooling, the potassium humate solution of 35% left and right is got supernatant concentration and is become in centrifugation;
3) weight ratio of preparing micro-fertilizer is: sodium ethylene diamine tetracetate: oxalic acid: Na
2b
4o
710H
2o:ZnSO
47H
2o:FeSO
47H
2o:MnSO
4h
2o=9:8:8:5:1:2, adds in advance a small amount of water and stirs, can stable existence;
4) by potassium humate solution: vinylformic acid (degree of neutralization is 77%): N, N`-methylene-bisacrylamide: the raw material weight ratio of micro-fertilizer=300:90:2:7 fully mixes, 35 DEG C of stirring reactions 10 minutes, add 15 parts of ammonium persulphates, and be warming up to 90 DEG C reaction 0.5 hour, cooling after filter, 70 DEG C dry, pulverize to obtain finished product.
A kind of application example of the humic acid multifunctional super absorbent resin with water conservation and moisture-holding and micro-fertilizer slow-release function:
1. homemade humic acid multifunctional super absorbent resin is mixed to rear evenly spreading fertilizer over the fields in plantation ditch in 1:20 ratio and thin dry ground, earthing also waters permeable, then plant garlic, under identical field management condition, than the soil volume increase 20.92% that does not use humic acid multifunctional super absorbent resin;
2. while homemade humic acid multifunctional super absorbent resin being applied to plantation soya bean, together with directly homemade humic acid multifunctional super absorbent resin being embedded in soya bean seed, 3g left and right trunk resin is buried at every strain seed place, earthing also waters permeable, under identical field management condition, than the soil volume increase 18.27% that does not use humic acid multifunctional super absorbent resin.
Claims (7)
1. a preparation method with the humic acids super absorbent resin of water conservation and moisture-holding and micro-fertilizer slow-release function, is characterized in that: comprise the steps:
(1) by weathered coal or brown coal or mud coal or the peat composed of rotten mosses or other low grade coal, after selected impurity elimination, be ground into 80-400 object powder;
(2) by above-mentioned powder: sodium hydroxide: sodium ethylene diamine tetracetate: the weight ratio of water=10～30:0.5～3:0.1～0.5:80～300 is mixed, stir, be heated to 70～90 DEG C of reaction 0.5-2 hour, after being down to room temperature, get supernatant liquor, the sodium humate solution that concentrated water content is 30～50%;
(3) by sodium humate solution: vinylformic acid: linking agent: after the weight ratio of micro-fertilizer=300～400:80～100:1～3:6～10 is fully mixed, 30～40 DEG C of stirring reactions 10～20 minutes, add the initiator of 5～15 weight parts, and be warming up to 70～90 DEG C reaction 0.5～1 hour, after cooling, filter, getting filter residue dry, pulverize and be finished product in 60～80 DEG C.
2. the preparation method of a kind of humic acids super absorbent resin with water conservation and moisture-holding and micro-fertilizer slow-release function as claimed in claim 1, it is characterized in that: vinylformic acid used need carry out part neutralization, degree of neutralization is 50～80%, makes finished product pH value between 6.5-7.5.
3. the preparation method of a kind of humic acids super absorbent resin with water conservation and moisture-holding and micro-fertilizer slow-release function as claimed in claim 1, it is characterized in that: linking agent used can be N, one or more in N`-methylene-bisacrylamide, acrylamide, urea, formaldehyde.
4. the preparation method of a kind of humic acids super absorbent resin with water conservation and moisture-holding and micro-fertilizer slow-release function as claimed in claim 1, it is characterized in that: micro-fertilizer used is whole or several in borax, zinc sulfate, manganous sulfate, ammonium molybdate, ferrous sulfate, ratio can be allocated as required, and borax, zinc sulfate, manganous sulfate, ammonium molybdate, ferrous sulfate in advance one or more in sequestrant sodium ethylene diamine tetracetate, citric acid, oxalic acid carry out chelating pre-treatment.
5. the preparation method of a kind of humic acids super absorbent resin with water conservation and moisture-holding and micro-fertilizer slow-release function as claimed in claim 1, is characterized in that: initiator used can be one or more in ammonium persulphate, Sodium Persulfate, Potassium Persulphate.
6. the preparation method of a kind of humic acids super absorbent resin with water conservation and moisture-holding and micro-fertilizer slow-release function as claimed in claim 1, is characterized in that: the sodium hydroxide in step (2) also available hydrogen potassium oxide replaces.
7. a humic acids super absorbent resin with water conservation and moisture-holding and micro-fertilizer slow-release function, is characterized in that: it is to obtain by the arbitrary preparation method described in claim 1-7.
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|---|---|---|---|---|
| CN104311371A (en) * | 2014-10-20 | 2015-01-28 | 柳州市天姿园艺有限公司 | Preparation method of slow release urea |
| CN104355794A (en) * | 2014-10-20 | 2015-02-18 | 柳州市天姿园艺有限公司 | Slow release urea |
| CN104496656A (en) * | 2014-12-04 | 2015-04-08 | 西北农林科技大学 | Water-retention and slow-release calcium fertilizer and preparation method thereof |
| CN105176536A (en) * | 2015-09-15 | 2015-12-23 | 江苏锦宇环境工程有限公司 | Preparation method of weathered coal humic acid water retention agent |
| CN105294278A (en) * | 2015-11-19 | 2016-02-03 | 福建农林大学 | Sugarcane charcoal-based water and fertilizer double-controlled composite slow-release carrier and preparation method thereof |
| CN105732900A (en) * | 2016-04-14 | 2016-07-06 | 安徽农业大学 | Super absorbent resin containing boron and preparing method thereof |
| CN105859966A (en) * | 2016-04-14 | 2016-08-17 | 安徽农业大学 | High water-absorbing resin containing zinc element and a preparation method thereof |
| CN105859967A (en) * | 2016-04-14 | 2016-08-17 | 安徽农业大学 | High water-absorbing resin containing iron ions and preparation method thereof |
| CN106380352A (en) * | 2016-08-30 | 2017-02-08 | 陕西省蒲城绿桥农化有限责任公司 | Method for preparing humic acid chelated copper |
| CN107337562A (en) * | 2017-06-27 | 2017-11-10 | 安徽省瑞森生物科技有限责任公司 | A kind of method for activating lignite humic acid and preparing water-holding slow-release humic acid biological fertilizer |
| CN108623748A (en) * | 2018-05-24 | 2018-10-09 | 中国农业大学 | A kind of load boron fibre element super absorbent resin and preparation method thereof |
| EP3305746A4 (en) * | 2016-07-01 | 2018-10-31 | Qingdao Xinyaodi Agricultural Technology Joint-Stock Co., Ltd. | Organic-inorganic polymeric water-retaining fertilizer and preparation method therefor |
| CN109020737A (en) * | 2018-10-22 | 2018-12-18 | 艾生豪 | Organic multicomponent microelement fertilizer preparation method with water retention |
| CN109293453A (en) * | 2018-12-10 | 2019-02-01 | 井冈山大学 | A kind of citrus Special-purpose fruit tree biological organic fertilizer and preparation method thereof |
| CN109400347A (en) * | 2018-11-09 | 2019-03-01 | 中国农业科学院农业资源与农业区划研究所 | It is a kind of suitable for winter wheat or the phosphorus ammonium Humic acid synergistic support preparation method of spring maize base manure |
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| EP3305746A4 (en) * | 2016-07-01 | 2018-10-31 | Qingdao Xinyaodi Agricultural Technology Joint-Stock Co., Ltd. | Organic-inorganic polymeric water-retaining fertilizer and preparation method therefor |
| US10544065B2 (en) | 2016-07-01 | 2020-01-28 | Qingdao Xinyaodi Agricultural Technology Joint-Stock Co., Ltd. | Organic-inorganic polymeric water-retaining fertilizer and preparation method of the same |
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| CN108623748B (en) * | 2018-05-24 | 2020-06-12 | 中国农业大学 | Boron-loaded cellulose super absorbent resin and preparation method thereof |
| CN109020737A (en) * | 2018-10-22 | 2018-12-18 | 艾生豪 | Organic multicomponent microelement fertilizer preparation method with water retention |
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