CN106565301A - Degradable mineral fertilizer water-retaining agent and preparation method thereof - Google Patents
Degradable mineral fertilizer water-retaining agent and preparation method thereof Download PDFInfo
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- CN106565301A CN106565301A CN201510891676.9A CN201510891676A CN106565301A CN 106565301 A CN106565301 A CN 106565301A CN 201510891676 A CN201510891676 A CN 201510891676A CN 106565301 A CN106565301 A CN 106565301A
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Abstract
The invention relates to a degradable mineral fertilizer water-retaining agent and a preparation method thereof, and is mainly applied to the agriculture and forestry field. The degradable mineral fertilizer water-retaining agent is prepared from Xinyang bentonite, activated mica, cassava starch, a water-soluble polymeric monomer, water, a free radical polymerization initiator, a cross-linking agent and other raw materials by means of mixing, heating polymerization, drying and crushing. Specifically, the adding weight of the Xinyang bentonite, activated mica and cassava starch respectively account for 20-100%, 20-100% and 20-60% of the water-soluble polymeric monomer. The degradable mineral fertilizer water-retaining agent provided by the invention is a fertilizer, also is a water-retaining agent, and can play the role of maintaining soil moisture, saving water resources, and supplying fertilizer stably and durably. The degradable mineral fertilizer water-retaining agent has the characteristics of simple preparation method and low cost, also has potassium endowment, water absorption and water retention multiple functions, and has biodegradability at the same time.
Description
Technical field
The invention belongs to agriculture and forestry technical field of fertilizers, be specifically related to a kind of degradable mineral fertilizer water retention agent and its
Preparation method.
Background technology
Slow release fertilizer be it is a kind of nutrient releasing speed is adjusted, new-type fertilizer with high content of technology, its nutrient releases
Put speed to regulate and control by physics, chemistry and animal nutrition, make supply and the crop pair of nutrient in fertilizer
The demand basic synchronization of nutrient, realizes dynamic equilibrium[1-2].The use of such new-type fertilizer, can reduce the loss of nutrient, improve fertilizer
Material utilization rate.
From the point of view of the present situation of production control slow release fertilizer in the world, oneself realizes that the control slow-release fertilizer kind of industrialized production is mainly
Polymer integument type npk fertilizer, its primary raw material are the chemical fertilizer of existing form.Its coated fertilizer, film-coating technique and fertilizer come
The present situation in source is mainly：
Nitrogen, phosphorus, potassium fertilizer raw material, weathered coal humic acids are carried out into peplos with cementing bonding material, coated fertilizer, is prepared
Envelope type slow release fertilizer, improves utilization rate of fertilizer 10～15%[3]。
Using the mixed polymers adhesive coating agent of waste plastic-starch, clay-polyester mixed polymer adhesive coating agent, sulfonation wood
The mixed polymers adhesive coating agent peplos of quality adhesive coating agent, humic acids, produce organic-inorganic compound slow release fertilizer[4].This
Bright application is improved on the coated fertilizer of slow-release fertilizer, introduces clay mineral, but main body fertilizer or chemical fertilizer, rather than
Difficulty utilizes mineral K.
Further technology development is to prepare agricultural Water-retaining slow-release fertilizer[5], will water-retaining agent and slow release fertilizer machinery it is mixed
Close.Potassium phosphorus element in slow release fertilizer derives from chemical fertilizer, rather than the mineral K that difficulty is utilized.
With granular urea as kernel fertilizer, with acrylic acid, potassium hydroxide, cross-linking agent and initiator as polymer raw, utilize
Chemical polymerization is in urea granules surface direct formation of film at surface manufacture cross linked polyacrylate potassium water-retaining agent peplos (wrapping up in) urea granules fertilizer
Water-keeping material is introduced slow-release fertilizer by the Technology and product of material[6], potassium therein derives from potassium hydroxide, nor difficult profit
Use mineral K.
Inventor in patent of invention CN 200910060543.1, using potassium breeze, ground phosphate rock, activation release enhancing agent, water-soluble
Property polymerized monomer such as acrylic acid, water, radical polymerization initiator and cross-linking agent raw material it is blended, heating polymerization, be dried, crush and
A kind of mineral fertilizer water retention agent is obtained, and has obtained invention patent mandate.Patent of invention major technique innovation be which by I
Slightly solubility potassium that state is present in a large number, Phosphate minerals are activated in water-retaining agent macromolecular material, obtain while having assigning fertilizer and protecting
The polymer composite of water function.But as its macromolecular scaffold is cross linked polyacrylate (sodium), it is difficult to give birth in soil
Thing is degraded.
Therefore, mineral fertilizer water retention agent also further carries out the necessity of basic structure innovation, makes both in distress
Dissolubility potassium mineral assign fertilizer and water conservation basic function, and be capable of geobiont degraded environment friendly.
List of references：
[1] He Xusheng, Li Suxia, Li Xuhui etc. the progress [J] of controlled availability fertilizers. plant nutrient and fertilizer journal,
1998,4(2):97～106,
[2]Hall W.L.New methology for slow-release fertilizers[J].Book of
abstracts,218th,ACS National meeting[C].New Orleans,1999.]
[3] CN 200510051250.9, double-control composite slow-release fertilizer and preparation method thereof；CN
200510104226.7, a kind of coated slow releasing fertilizer and preparation method thereof；CN 200410024201.1, a kind of slow-release fertilizer and
Its preparation method.
[4] CN 200410078164.2, method for producing organic and inorganic compound slow release fertilizer.
[5] CN 03153942.4, a kind of Water-retaining slow-release fertilizer.
[6] CN 200410078165.7, a kind of production method of water preserving type film coated urea fertilizer.
The content of the invention
It is an object of the invention to provide a kind of degradable mineral fertilizer water retention agent and preparation method thereof, the letter of the method technique
Single, low cost, made product have potash fertilizer and water conservation dual-use function.
To achieve these goals, the technical scheme is that：Degradable mineral fertilizer water retention agent, it is characterised in that it
Mixed by Xinyang bentonite, activation Muscovitum, tapioca, water-soluble polymeric monomer, water, radical polymerization initiator and cross-linking agent Jing
Close, heating glycerol polymerization, drying, crushing and be obtained；Wherein, Xinyang bentonite, activation Muscovitum, the addition weight point of tapioca
Not Wei water-soluble polymeric monomer 20%～100%, 20%～100%, 20%～60%, the addition of radical polymerization initiator
Weight for water-soluble polymeric monomer 0.01%～1.0%, the addition weight of cross-linking agent is the 0.01% of water-soluble polymeric monomer
～2.0%, water-soluble polymeric monomer formation weight concentration soluble in water is molten for the water-soluble polymeric monomer of 10wt%～35wt%
Liquid.
The preparation method of above-mentioned degradable mineral fertilizer water retention agent, it is characterised in that it comprises the steps：
1) Xinyang bentonite in powder is broken to into mean diameter≤45 μm；
2) Muscovitum that the weight content of potassium oxide is not less than 5.0% is crushed, crosses 80 mesh sub-sieves；Then by 100 parts of powder
Muscovitum after broken and 20 parts of Sodium Chloride mixing, are placed in ceramic crucible, 800 DEG C of reacting by heating 2 hours, and activation Muscovitum is obtained；
3) by the water-soluble polymeric list for forming weight concentration for 10wt%～35wt% water-soluble polymeric monomer soluble in water
Liquid solution, will enter in radical polymerization initiator and cross-linking agent in water-soluble polymeric monomer solution, obtains dissolved with radical polymerization
Close the water-soluble polymeric monomer solution of initiator and cross-linking agent；Xinyang bentonite, activation Muscovitum and tapioca are added to molten
In having the water-soluble polymeric monomer solution of radical polymerization initiator and cross-linking agent, mixing dispersion obtains mixed material；
4) graft polymerization product is obtained after heat the mixed material after dispersion 1～5 hour in 40～90 DEG C in the reactor；
5) polymerizate is less than 20wt% in 100～120 DEG C of dryings to water content, is crushed to 0.1～5.0mm (with machinery
Method), obtain granular degradable mineral fertilizer water retention agent.
The present invention is described in detail below：
1st, Xinyang bentonite
Bentonite is the nonmetallic minerals with montmorillonite as main mineral constituent, and smectite structure is by two silica four sides
Body presss from both sides the 2 of one layer of alumina octahedral composition：1 type crystal structure, as the layer structure that montmorillonite structure cell is formed has some sun
Ion, such as Cu, Mg, Na, K etc., and these cationes are very unstable with the effect of montmorillonite structure cell, easily handed over by other cationes
Change, therefore there is preferable ion exchangeable, there are confinement capabilities to nutritional labelings such as potassium ions.
The produced bentonite of District, Xinyang Area, Henan Province bentonite ore, potassium content are high, consisting of：
Wherein potassium-bearing mineral such as hydromica content is high, up to 3.3%, K2O content reaches 1.80%.From the bentonite conduct
One of degradable mineral fertilizer water retention agent key component, can increase soil potassium content to a certain extent.
The bentonitic addition weight in Xinyang is the 20～100% of water-soluble polymeric monomer.
2nd, activate Muscovitum
Muscovitum mineral resources are widely present in China, and reserves enrich very much, aluminosilicate nonmetallic mineral of the category containing potassium, tool
There is layer structure.The chemical formula of Muscovitum is KAl2(AlSi3O10)(OH)2, wherein SiO245.2%th, Al2O338.5%th, K2O
11.8%th, H2O 4.5%, additionally, containing a small amount of Na, Ca, Mg, Ti, Cr, Mn, Fe and F etc..Potassium content is higher.
Potassium major part in Muscovitum is all insoluble potassium, it is only minimal amount of can be remaining in natural conditions in air slaking
Most of potassium needs various chemical methodes to be discharged.The method for carrying potassium, is roughly divided into two kinds：A kind of is wet method, is exactly with strong
Acid is being acidified white mica so as to discharge potassium ion；Also one kind is exactly dry method, usually using high-temperature calcination, adopts and helps
, in the state of high-temperature fusion, there is ion exchange, extract potassium ion in flux.Two methods can obtain higher potassium
Release rate, so there is wide exploitation prospect using Muscovitum manufacture potash fertilizer.
The present invention adopts calcination method.First mixed with the mica powder after crushing as cosolvent with Sodium Chloride, forged at high temperature
Burn, now potassium element has been activated, obtain activating Muscovitum dry powder.
The addition weight of activation Muscovitum is the 20～100% of water-soluble polymeric monomer.
3rd, tapioca
Starch is a kind of high glycan, is mainly formed by connecting by α-D glycosidic bonds by the surplus base of glucose, and chemical constitution is
(C6H10O5) n, n is the degree of polymerization.Native starch all contains amylose and amylopectin, the amylopectin contained in tapioca
80 are up to the ratio of amylose：20, it is easy to which graft copolymerization, and aboundresources occur, with good biology drop
Solution performance.
The addition weight of tapioca for water-soluble polymeric monomer 20～60%.
4th, water-soluble polymeric monomer
Described water-soluble polymeric monomer is containing carboxyl or sulfonic polymerized monomer.Typical water-soluble ionic-type polymerization
Monomer is：Acrylic or methacrylic acid and its alkali metal salts or ammonium salt, 2- acrylamide-2-methylpro panesulfonic acids or pi-allyl
Sulfonic acid and its alkali metal salts or ammonium salt；It can also be starch-grafted above-mentioned polymerized monomer.
Water-soluble polymeric monomer weight concentration in aqueous solution be 10wt% to 40wt%, preferred 20wt%～
30wt%, water-soluble polymeric monomer can partly or wholly use the form that alkali metal or ammonium compoundss are neutralized to use.
5th, radical polymerization initiator
The radical polymerization initiator for being adapted to this Type of Collective is persulfate, such as：Potassium peroxydisulfate, sodium peroxydisulfate or persulfuric acid
Ammonium, these water soluble starters can be used in mixed way, and when being used in mixed way, be any proportioning.Persulfate can also and reproducibility
Material such as ferrous ion, sodium sulfite, sodium sulfite etc. are used with synthesis redox system.With the use of when each composition match somebody with somebody
Than being determined by the quantitative relation of chemical equation.
0.01wt%～1.0wt% of the consumption of radical polymerization initiator for water-soluble polymeric monomer weight, preferably
0.05wt%～0.3wt%.
6th, cross-linking agent
Cross-linking agent used in the present invention is that per molecule at least contains two polymerisable unsaturated groups.Typical cross-linking agent
Have：Bisacrylamide such as N, N '-methylene-bisacrylamide.
0.01wt%～2.0wt% of the consumption of cross-linking agent for water-soluble polymeric monomer weight, preferred 0.05wt%～
1wt%.
First, liquid absorbency rate assay method
In the present invention, adopt and determine and calculate the liquid absorbency rate for inhaling distilled water, tap water and normal saline with the following method：
Weigh 0.5～1.0g dryings and the pelletized product after pulverization process is placed in 500～1000ml beakers, add
1000ml distilled water or 500ml tap waters weigh 0.5～1.0g dryings and the pelletized product after pulverization process is placed in 150ml
100ml 0.9%NaCl solution is added in beaker, after standing 24 hours, unnecessary water is filtered off with 30 mesh mesh screens, is weighed up gel
Quality, is calculated as follows water absorbent rate：
Liquid absorbency rate=(gel quality-dry glue quality)/dry glue quality.
2nd, Potassium release quantity measuring method
The present invention is collected containing potassium solution using post elution method, detects potassium sustained release performance with atomic absorption spectrography (AAS).
The invention has the beneficial effects as follows：By raw material through chemical reaction such as Xinyang bentonite, activation Muscovitum, tapiocas
(the compound process route of first mixing dispersion repolymerization), is embedded in by water-soluble polymeric monomer, radical polymerization initiator
In the hydrogel being collectively forming with cross-linking agent；Thus obtain that the cost of raw material is lower, the mono- ﹑ liquid absorbency rates of preparation technology Jian are high, solidifying
Glue intensity is higher, salt resistant character preferably, it is gentle to the activation condition of slightly solubility mineral K (can be to slightly solubility mineral K, low cost
Using), the sustainable degradable mineral fertilizer water retention agent for providing the element such as potassium needed according to plant.
Degradable mineral fertilizer water retention agent obtained in of the invention, the cost of raw material decline 20～60% than sodium polyacrylate.
The scope of liquid absorbency rate that experiment measures this series of products is：Inhale distilled water multiplying power be 100～500g/g, inhale tap water times
Rate be 60～350g/g, inhale normal saline multiplying power be 20～55g/g, 3～6 months degradables more than 50% in soil, institute
Continuous total volume containing potassium oxide is more than 60%.
The degradable mineral fertilizer water retention agent of the present invention is both fertilizer, is water-retaining agent again, holding can be played in agriculture and forestry
Soil moisture, saving water resource, steady persistently fertilizer supplier.Main production raw material reserves of the present invention extremely enrich, and have work
Skill flow process is short, reduced investment, the advantages of be easy to large-scale production.
Specific embodiment
For a better understanding of the present invention, present disclosure is further elucidated with reference to embodiment, but the present invention
Content is not limited solely to the following examples.
Embodiment 1：
In weight concentration is 10%, 300 grams of acrylic acid solutions that its degree of neutralization is 100% is made with sodium hydroxide, stirring
Lower addition 15g tapiocas, N, 0.003 gram of N '-methylene-bisacrylamide, 0.003 gram of potassium peroxydisulfate, dissolving, then by machinery
24 grams of Xinyang bentonite crushed, 24 grams of Muscovitum of activation are added thereto, stirring or ultrasonic disperse 10 minutes.It is mixed after by dispersion
The compound material agitating heating after 5 hours at 40 DEG C in the reactor, then rise 30 DEG C of high-temperature and react 5 hours, obtain polymerizate；It is poly-
Closing product and 20% being less than in 120 DEG C of dryings to water content, make which be crushed to 0.1～2.0mm with the method for machinery, finally giving can
Degraded mineral fertilizer water retention agent (pelletized product).
Embodiment 2：
In weight concentration is 300 grams of acrylic acid solutions that 30%, degree of neutralization is 80%, stirring is lower to add 25g para arrowroots
Powder, N, 0.09 gram of N '-methylene-bisacrylamide, 0.09 gram of potassium peroxydisulfate, dissolving, then Xinyang swelling that mechanical activation comminution is crossed
90 grams of soil, 90 grams of Muscovitum of activation are added thereto, stirring or ultrasonic disperse 10 minutes.By the mixed material after dispersion in the reactor
After 90 DEG C of heating 1 hour, then the reaction 1 hour of 10 DEG C of high-temperature is risen, obtain polymerizate；Polymerizate is in 100 DEG C of dryings to containing
The water yield is less than 20%, makes which be crushed to 0.1～2.0mm with the method for machinery, finally gives degradable mineral fertilizer water retention agent (grain
Shape product).
Embodiment 3：
In weight concentration is 300 grams of acrylic acid solutions that 25%, degree of neutralization is 70%, stirring is lower to add 15g para arrowroots
Powder, N, 1.5 grams of N '-methylene-bisacrylamide, 0.75 gram of potassium peroxydisulfate, dissolving, then Xinyang bentonite that mechanical activation comminution is crossed
15 grams, 15 grams of Muscovitum of activation be added thereto, stirring or ultrasonic disperse 10 minutes.By the mixed material after dispersion in the reactor in
After 70 DEG C are heated 3 hours, then the reaction 2 hours of 20 DEG C of high-temperature is risen, obtain polymerizate；Polymerizate is in 110 DEG C of dryings to aqueous
Amount is made which be crushed to 0.1～2.0mm with the method for machinery, finally gives degradable mineral fertilizer water retention agent (granular less than 20%
Product).
Embodiment 4：
In weight concentration is 300 grams of acrylic acid solutions that 20%, degree of neutralization is 70%, stirring is lower to add 20g para arrowroots
Powder, N, 0.06 gram of N '-methylene-bisacrylamide, 0.2 gram of potassium peroxydisulfate, dissolving, then Xinyang bentonite that mechanical activation comminution is crossed
45 grams, 45 grams of Muscovitum of activation be added thereto, stirring or ultrasonic disperse 10 minutes.By the mixed material after dispersion in the reactor in
After 90 DEG C are heated 1 hour, then the reaction 1 hour of 10 DEG C of high-temperature is risen, obtain polymerizate；Polymerizate is in 130 DEG C of dryings to aqueous
Amount is made which be crushed to 0.1～2.0mm with the method for machinery, finally gives degradable mineral fertilizer water retention agent (granular less than 20%
Product).
Each raw material cited by the present invention can realize the present invention, and the bound value and its interval value of each raw material can
Realize the present invention, embodiment numerous to list herein；The bound value of present invention process parameter (such as temperature, time etc.) and
Its interval value can realize the present invention, embodiment numerous to list herein.
Generated degradable mineral fertilizer water retention agent, its pH value are invented above：Accumulation Potassium release rate is big within 6.5-7.5,10 days
In 60%, repeat water suction number of times and be more than 5 times, water absorbent rate is more than 200.
Although the present invention has been described in detail, and provides some instantiations, to this area knack
Personnel say, as long as it is obvious that can do various change or amendment without departing from the spirit and scope of the present invention.
Claims (10)
1. a kind of degradable mineral fertilizer water retention agent, it is characterised in that：Described degradable mineral fertilizer water retention agent is swollen by Xinyang
Profit soil, activation Muscovitum, tapioca, water-soluble polymeric monomer, water, radical polymerization initiator and cross-linking agent are blended, heating
It is polymerized, is dried and crushes and be obtained；Wherein, described Xinyang bentonite, activation Muscovitum, the addition weight of tapioca are respectively
20%～100%, 20%～100%, the 20%～60% of water-soluble polymeric monomer, the addition weight of radical polymerization initiator
For the 0.01%～1.0% of water-soluble polymeric monomer, the addition weight of cross-linking agent for water-soluble polymeric monomer 0.01%～
2.0%, water-soluble polymeric monomer is soluble in water to form the water-soluble polymeric monomer solution that weight concentration is 10%～35%.
2. a kind of degradable mineral fertilizer water retention agent according to claim 1, it is characterised in that：The weight of potassium oxide is contained
Amount is not less than 5.0% Muscovitum and crushes, and crosses 80 mesh sub-sieves；Then the Muscovitum and 20 parts of Sodium Chloride mixing after crush 100 parts,
It is placed in ceramic crucible, 800 DEG C of reacting by heating 2 hours, activation Muscovitum is obtained.
3. a kind of degradable mineral fertilizer water retention agent according to claim 1, it is characterised in that：Described Xinyang bentonite
Addition weight for water-soluble polymeric monomer 30%～60%.
4. a kind of degradable mineral fertilizer water retention agent according to claim 1, it is characterised in that：Described activation Muscovitum
Addition weight for water-soluble polymeric monomer 30%～60%.
5. a kind of degradable mineral fertilizer water retention agent according to claim 1, it is characterised in that：Described water-soluble polymeric
Monomer is polymerized monomer containing carboxyl or monomer containing sulfonic polymeric.
6. a kind of degradable mineral fertilizer water retention agent according to claim 5, it is characterised in that：Described water-soluble polymeric
Monomer is acrylic acid or its alkali metal salts or ammonium salt, methacrylic acid or its alkali metal salts or ammonium salt, 2- acrylamido -2- first
Base propane sulfonic acid or its alkali metal salts or ammonium salt, allyl sulphonic acid or its alkali metal salts or ammonium salt or be starch-grafted above-mentioned poly-
Close monomer.
7. a kind of degradable mineral fertilizer water retention agent according to claim 1, it is characterised in that：Described radical polymerization
Initiator is persulfate；The addition weight of radical polymerization initiator for water-soluble polymeric monomer 0.05%～0.3%.
8. a kind of degradable mineral fertilizer water retention agent according to claim 7, it is characterised in that：Described radical polymerization
Mixture of the initiator for one kind or any proportioning in potassium peroxydisulfate, sodium peroxydisulfate and Ammonium persulfate..
9. a kind of degradable mineral fertilizer water retention agent according to claim 1, it is characterised in that：Described cross-linking agent per point
Son at least contains two polymerisable unsaturated groups；The addition weight of cross-linking agent for water-soluble polymeric monomer 0.05%～
1.0%.
10. the preparation method of the degradable mineral fertilizer water retention agent described in a kind of any one of claim 1～9 claim, its
It is characterised by, described preparation method specifically includes following steps：
1) Xinyang bentonite in powder is broken to into mean diameter≤45 μm；
2) Muscovitum that the weight content of potassium oxide is not less than 5.0% is crushed, crosses 80 mesh sub-sieves；Then after crush 100 parts
Muscovitum and the mixing of 20 parts of Sodium Chloride, be placed in ceramic crucible, 800 DEG C of reacting by heating 2 hours are obtained activation Muscovitum；
3) the water-soluble polymeric monomer solution that weight concentration is 10%～35% is formed by water-soluble polymeric monomer soluble in water, will
Enter in radical polymerization initiator and cross-linking agent in water-soluble polymeric monomer solution, obtain dissolved with radical polymerization initiator and
The water-soluble polymeric monomer solution of cross-linking agent；Xinyang bentonite, activation Muscovitum and tapioca are added to dissolved with radical polymerization
Close in the water-soluble polymeric monomer solution of initiator and cross-linking agent, mixing dispersion obtains mixed material；
4) polymerizate is obtained after heat the mixed material after dispersion 1～5 hour in 40～90 DEG C in the reactor；
5) polymerizate is less than 20wt% in 100～120 DEG C of dryings to water content, is crushed to 0.1～5.0mm, obtains degradable ore deposit
Thing fertilizer water-retaining agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107177358A (en) * | 2017-05-26 | 2017-09-19 | 全椒县香妃农业专业合作社 | A kind of plantation water-loss reducer of soil and preparation method thereof |
| CN107182508A (en) * | 2017-06-12 | 2017-09-22 | 重庆市林业科学研究院 | A kind of Three Gorges Reservoir revegetation and restoration methods |
| CN108947702A (en) * | 2018-09-19 | 2018-12-07 | 河北工程大学 | A kind of selenium-rich type water-retaining agent and preparation method thereof with anion response characteristic |
| CN111285740A (en) * | 2020-03-26 | 2020-06-16 | 张蕾 | Special fertilizer for overcoming soil continuous cropping obstacle |
| CN113861993A (en) * | 2021-09-29 | 2021-12-31 | 浙江墨泉生态建设有限公司 | Composite agriculture and forestry water-retaining agent and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107177358A (en) * | 2017-05-26 | 2017-09-19 | 全椒县香妃农业专业合作社 | A kind of plantation water-loss reducer of soil and preparation method thereof |
| CN107182508A (en) * | 2017-06-12 | 2017-09-22 | 重庆市林业科学研究院 | A kind of Three Gorges Reservoir revegetation and restoration methods |
| CN108947702A (en) * | 2018-09-19 | 2018-12-07 | 河北工程大学 | A kind of selenium-rich type water-retaining agent and preparation method thereof with anion response characteristic |
| CN108947702B (en) * | 2018-09-19 | 2021-06-08 | 河北工程大学 | Selenium-rich water-retaining agent with anion response characteristic and preparation method thereof |
| CN111285740A (en) * | 2020-03-26 | 2020-06-16 | 张蕾 | Special fertilizer for overcoming soil continuous cropping obstacle |
| CN111285740B (en) * | 2020-03-26 | 2021-11-23 | 沈阳华清源农业发展有限公司 | Special fertilizer for overcoming soil continuous cropping obstacle |
| CN113861993A (en) * | 2021-09-29 | 2021-12-31 | 浙江墨泉生态建设有限公司 | Composite agriculture and forestry water-retaining agent and preparation method and application thereof |
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