CN107903111A - A kind of preparation method of the slow-release fertilizer of natural polymer subbase - Google Patents
A kind of preparation method of the slow-release fertilizer of natural polymer subbase Download PDFInfo
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- CN107903111A CN107903111A CN201711144922.XA CN201711144922A CN107903111A CN 107903111 A CN107903111 A CN 107903111A CN 201711144922 A CN201711144922 A CN 201711144922A CN 107903111 A CN107903111 A CN 107903111A
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- Prior art keywords
- slow
- fertilizer
- release
- high molecular
- natural polymer
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B15/00—Organic phosphatic fertilisers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/20—Liquid fertilisers
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Soil Sciences (AREA)
- Fertilizers (AREA)
Abstract
A kind of preparation method of the slow-release fertilizer of natural polymer subbase, belong to technical field of slow release fertilizer, can solve fertilizer prepared by existing sodium alginate does not have sustained release performance, improper fertilization, it may cause burn seedlings phenomenon, the present invention prepares high molecular slow-release liquid fertilizer, then is blended with high molecular slow-release liquid fertilizer and sodium alginate, instills boric acid and calcium chloride solution;Sodium ion in sodium alginate molecule is chlorinated the calcium ion substitution in calcium, generate calcium alginate not soluble in water, and the polyvinyl alcohol and acid reaction of reaction are not participated in high molecular slow-release liquid fertilizer, make surfaces cross-link, ultimately form the gel particle containing N P and K.The fertilizer of the present invention has sustained release performance.
Description
Technical field
The invention belongs to technical field of slow release fertilizer, and in particular to a kind of preparation method of the slow-release fertilizer of natural polymer subbase.
Background technology
Sodium alginate also known as sodium alginate, seaweed gel, algin, alginates.Alginic acid and its salt are by D-MANNOSE aldehyde
The long chain macromolecule compound that acid (referred to as M) and L- guluronic acids (referred to as G) are polymerized, molecular weight 106Left and right,
The structure of sodium alginate is as follows:
。
There is strongly hydrophilic group-COONa ,-COOH and-OH on the molecular backbone of sodium alginate, be it is a kind of poly- cloudy from
Sub- electrolyte, can exchange with acid cation, be complexed, chelate.And super absorbent resin is mainly by polymer chain
Hydrogen chain associative structure is formed between strongly hydrophilic group and hydrone and this mechanism that absorbs water generally has been accepted, therefore alginic acid
Sodium also has stronger water absorbing properties.In addition, alginic acid is rich in the nutrient and coordinate plant growth easily absorbed by crops
Active material, simultaneously because it is with good biological degradability and Environmental compatibility, sea is prepared by raw material of sodium alginate
Alginic acid base chemical fertilizer can play alginic acid and stimulate growth and development of plants, improves soil texture and improve the retain water and nutrients of soil
Ability;It can also suppress the growth of pathogenic bacteria in soil and breeding, to promoting plant growth, improvement fruit quality and other effects splendid;
Production cost can also be greatly lowered at the same time, therefore it belongs to environmental type material.
But the existing fertilizer prepared using sodium alginate, only simply urea or other materials are wrapped in
Wherein, without sustained release performance, improper fertilization, may cause burn seedlings phenomenon.
The content of the invention
The fertilizer that the present invention is prepared for existing sodium alginate does not have sustained release performance, and improper fertilization, may cause burn seedlings to show
As, there is provided a kind of preparation method of the slow-release fertilizer of natural polymer subbase.
The present invention adopts the following technical scheme that:
A kind of preparation method of the slow-release fertilizer of natural polymer subbase, includes the following steps:
The first step, prepares high molecular slow-release liquid fertilizer, weighs polyvinyl alcohol, adds flask, adds distilled water, stirred under the conditions of 90 DEG C
Mix to polyvinyl alcohol and dissolve;Add urea phosphate and p-methyl benzenesulfonic acid, under the conditions of 100-120 DEG C, react 100-150min;Again plus
Enter potassium hydroxide, under the conditions of 90-100 DEG C, react 80-100min, after reaction, obtain high molecular slow-release liquid fertilizer;
Second step, prepares 3% boric acid calcium chloride solution;
3rd step, high molecular slow-release liquid fertilizer and sodium alginate are uniformly mixed, obtain mixed solution;
The mixed solution that 3rd step obtains, is added dropwise to 3% boric acid calcium chloride solution of second step by the 4th step, soaks 30-
60min, obtains the slow-release fertilizer of natural polymer subbase.
In the first step, the mass ratio of polyvinyl alcohol, urea phosphate and potassium hydroxide is 1:21.35:1.25;
In the first step, p-methyl benzenesulfonic acid accounts for urea phosphate mass ratio as 1.5%.
In 3rd step, the mass ratio of sodium alginate and high molecular slow-release liquid fertilizer is 1:40~45.
In 4th step, the volume ratio of mixed solution and 3% boric acid calcium chloride solution is 1:20.
Reaction principle of the present invention is as follows:
1. under the action of initiator p-methyl benzenesulfonic acid, esterification, the product and hydrogen of production occur for urea phosphate and polyvinyl alcohol
Potassium oxide reacts, and obtains final product, is the mixture of polyvinyl alcohol urea phosphate ester and urea phosphate, interacts between hydroxyl
Crosslinked network structure is easily formed, urea phosphate is wrapped in the network system of polyvinyl alcohol urea phosphate ester, and formation uniformly contains
The organic and hydrosol of inorganic nutrients.
2. being blended with high molecular slow-release liquid fertilizer and sodium alginate, boric acid and calcium chloride solution are instilled;In sodium alginate molecule
Sodium ion be chlorinated calcium ion substitution in calcium, generate calcium alginate not soluble in water, and do not join in high molecular slow-release liquid fertilizer
Add the polyvinyl alcohol and acid reaction of reaction, make surfaces cross-link, ultimately form the gel particle containing N P and K.
The structure of product to illustrate the invention, does examination of infrared spectrum to the present invention, finds out from infrared spectrogram, poly- second
In 3500 ~ 3200cm in enol molecule-1There is absworption peak in vicinity, illustrates for the blunt peak of associate hydrogen bond, vinyl (- CH2-CH2-)
Strong absworption peak appear in 3100 ~ 2850cm-1Between;And in 1107cm-1There is the suction of alkyl phosphate P-O-C structures in place
Receive peak;In 2988.29 cm-1Place has an absworption peak to be absorbed for the stretching vibration of C-H on sodium alginate macromolecular hexatomic ring, and extra large
The absorption of mosanom fiber here is weaker, its reason is sodium alginate macromolecular and Ca2+Form " egg-box " structure, limit
The stretching vibration of C-H on hexatomic ring is made so that dipole moment change is smaller, therefore absworption peak is weaker.Similarly, 3424.3 cm-1Place is big
The stretching vibration of O-H is also limited on molecule hexatomic ring, and the position of O-H stretching vibration peaks is moved to lower wave number, is seen at the same time
Observe O-H stretching vibration peaks in calcium alginate fibre to broaden, illustrate that the hydroxyl of simply part participates in coordination, other hydroxyls are mutually formed
Close, formed and absorbed in higher wave number, and with lower wave number overlap of peaks and so that peak shape broadens.It can be seen from the above that macromolecule slow release fertilizer
In contain polyvinyl alcohol urea phosphate, sodium alginate, show that the structure of polyvinyl alcohol urea phosphate is not sent out after adding sodium alginate
Changing, in addition, sodium alginate is coated on top layer with being partially converted into calcium alginate after calcium chloride reaction, seaweed is still contained in inside
Sour sodium.
Beneficial effects of the present invention are as follows:
1. sodium alginate is rich in the nutrient easily absorbed by crops and the active material of coordinate plant growth, simultaneously because
, with good biological degradability and Environmental compatibility, sea can be played by preparing seaweed acidic group chemical fertilizer as raw material using sodium alginate for it
Alginic acid stimulates growth and development of plants, improves soil texture, and can improve the retain water and nutrients ability of soil;It can also suppress in soil
Growth of pathogenic bacteria and breeding, to promoting plant growth, improvement fruit quality and other effects splendid;Production can also be greatly lowered at the same time
Cost, therefore it belongs to environmental type material.
2. the present invention is by chemical reaction, in a product, at the same time containing element needed for tri- plant growth of N, P, K,
Disposable fertilizer only need to be applied, you can meet nutritional ingredient needed for plant growth.
3. nutrient of the present invention is the purpose that sustained release is realized by the effect of material in soil, not using difficult degradation
Material, environment will not be polluted.
Brief description of the drawings
Fig. 1 is the preparation principle of high molecular slow-release liquid fertilizer of the present invention, wherein:1- urea phosphates;2- polyvinyl alcohol urea phosphate esters;
Fig. 2 is the preparation principle of the slow-release fertilizer of the natural based high molecular of the present invention;
Fig. 3 is infrared spectrogram of the present invention, wherein:3- polyvinyl alcohol urea phosphates;The slow-release fertilizer of 4- natural polymer subbases;
Fig. 4 is that the nutritional ingredient of the present invention in the soil discharges test chart.
Embodiment
Embodiment 1, is in mass ratio 1:21.35:1.25 ratio weighs polyvinyl alcohol, urea phosphate and potassium hydroxide, right
Toluenesulfonic acid accounts for urea phosphate mass ratio as 1.5%.
The first step, prepares high molecular slow-release liquid fertilizer, weighs polyvinyl alcohol, adds flask, adds distilled water, 90 DEG C of conditions
Lower stirring to polyvinyl alcohol dissolves;Add urea phosphate and p-methyl benzenesulfonic acid, under the conditions of 100-120 DEG C, react 100-150min;
Potassium hydroxide is added, under the conditions of 90-100 DEG C, 80-100min is reacted, after reaction, obtains high molecular slow-release liquid fertilizer;
Second step, prepares 3% boric acid calcium chloride solution;
3rd step, high molecular slow-release liquid fertilizer and sodium alginate are uniformly mixed, obtain mixed solution;
The mixed solution that 3rd step obtains, is added dropwise to 3% boric acid calcium chloride solution of second step by the 4th step, immersion
30min, obtains the slow-release fertilizer of natural polymer subbase.
In 3rd step, the mass ratio of sodium alginate and high molecular slow-release liquid fertilizer is 1:40~45.
In 4th step, the volume ratio of mixed solution and 3% boric acid calcium chloride solution is 1:20.
Nutritional ingredient is as follows in test gained fertilizer:N:7.9%、P(P2O5):20.5%、K(K2O):2.2%.
Embodiment 2, is in mass ratio 1:21.35:1.25 ratio weighs polyvinyl alcohol, urea phosphate and potassium hydroxide, right
Toluenesulfonic acid accounts for urea phosphate mass ratio as 1.5%.
The first step, prepares high molecular slow-release liquid fertilizer, weighs polyvinyl alcohol, adds flask, adds distilled water, 90 DEG C of conditions
Lower stirring to polyvinyl alcohol dissolves;Add urea phosphate and p-methyl benzenesulfonic acid, under the conditions of 100-120 DEG C, react 100-150min;
Potassium hydroxide is added, under the conditions of 90-100 DEG C, 80-100min is reacted, after reaction, obtains high molecular slow-release liquid fertilizer;
Second step, prepares 3% boric acid calcium chloride solution;
3rd step, high molecular slow-release liquid fertilizer and sodium alginate are uniformly mixed, obtain mixed solution;
The mixed solution that 3rd step obtains, is added dropwise to 3% boric acid calcium chloride solution of second step by the 4th step, immersion
40min, obtains the slow-release fertilizer of natural polymer subbase.
In 3rd step, the mass ratio of sodium alginate and high molecular slow-release liquid fertilizer is 1:40~45.
In 4th step, the volume ratio of mixed solution and 3% boric acid calcium chloride solution is 1:20.
Nutritional ingredient is as follows in test gained fertilizer:N:7.5%、P(P2O5):20.2%、K(K2O):2.1%.
Embodiment 3, is in mass ratio 1:21.35:1.25 ratio weighs polyvinyl alcohol, urea phosphate and potassium hydroxide, right
Toluenesulfonic acid accounts for urea phosphate mass ratio as 1.5%.
The first step, prepares high molecular slow-release liquid fertilizer, weighs polyvinyl alcohol, adds flask, adds distilled water, 90 DEG C of conditions
Lower stirring to polyvinyl alcohol dissolves;Add urea phosphate and p-methyl benzenesulfonic acid, under the conditions of 100-120 DEG C, react 100-150min;
Potassium hydroxide is added, under the conditions of 90-100 DEG C, 80-100min is reacted, after reaction, obtains high molecular slow-release liquid fertilizer;
Second step, prepares 3% boric acid calcium chloride solution;
3rd step, high molecular slow-release liquid fertilizer and sodium alginate are uniformly mixed, obtain mixed solution;
The mixed solution that 3rd step obtains, is added dropwise to 3% boric acid calcium chloride solution of second step by the 4th step, immersion
60min, obtains the slow-release fertilizer of natural polymer subbase.
In 3rd step, the mass ratio of sodium alginate and high molecular slow-release liquid fertilizer is 1:40~45.
In 4th step, the volume ratio of mixed solution and 3% boric acid calcium chloride solution is 1:20.
Nutritional ingredient is as follows in test gained fertilizer:N:7.1%、P(P2O5):19.5%、K(K2O):1.8%.
As the reaction time increases, gel particle nutrient content is reduced, nutrient content highest when reacting 30min, the reason is that
During due to being reacted in calcium chloride/boric acid solution, small molecule nutrient can be flowed into solution by the path of network structure, during reaction
Between it is longer, nutrient loss is more.After stopping reaction, in drying course, network path shrinks closure, and nutrient has been wrapped in solidifying
In glue.
By the high molecular slow-release liquid fertilizer of embodiment 1, the release of N, P, K in the soil is tested.
The native natural air drying of experiment, crosses 50 mesh sieves.Weigh 100g soil to be put into graduated cylindrical separatory funnel, precise
10ml high molecular slow-release liquid fertilizers are poured into soil, then add the distilled water for accounting for native weight 15%, during test, toward tubular scale liquid separation
100ml distilled water is added in funnel, opens the switch of funnel bottom, releases aqueous solution, N, P, the K measured in soil leachates contains
Amount, while the blank control of chemical fertilizer is not added with, every test in 5 days once.The measure of nitrogen uses Nessler reagent methods;Available phosphorus
Measure use molybdenum antimony resistance colorimetric method;The measure of available potassium uses flame spectrometry.
As seen from Figure 4, the nutrient-lapsed time of product in the soil is 90 days, between 0 ~ 20 day rate of release compared with
Slowly, 20 ~ 70 days rate of release gradually increase, and peak at 70 days, and rate of release tends to be steady after 70 days, therefore whole
A acquisition time can be divided into lag period, constant release phase and decline phase three phases.
Claims (5)
- A kind of 1. preparation method of the slow-release fertilizer of natural polymer subbase, it is characterised in that:Include the following steps:The first step, prepares high molecular slow-release liquid fertilizer, weighs polyvinyl alcohol, adds flask, adds distilled water, stirred under the conditions of 90 DEG C Mix to polyvinyl alcohol and dissolve;Add urea phosphate and p-methyl benzenesulfonic acid, under the conditions of 100-120 DEG C, react 100-150min;Again plus Enter potassium hydroxide, under the conditions of 90-100 DEG C, react 80-100min, after reaction, obtain high molecular slow-release liquid fertilizer;Second step, prepares 3% boric acid calcium chloride solution;3rd step, high molecular slow-release liquid fertilizer and sodium alginate are uniformly mixed, obtain mixed solution;The mixed solution that 3rd step obtains, is added dropwise to 3% boric acid calcium chloride solution of second step by the 4th step, soaks 30- 60min, obtains the slow-release fertilizer of natural polymer subbase.
- A kind of 2. preparation method of the slow-release fertilizer of natural polymer subbase according to claim 1, it is characterised in that:The first step In, the mass ratio of polyvinyl alcohol, urea phosphate and potassium hydroxide is 1:21.35:1.25.
- A kind of 3. preparation method of the slow-release fertilizer of natural polymer subbase according to claim 1, it is characterised in that:The first step In, p-methyl benzenesulfonic acid accounts for urea phosphate mass ratio as 1.5%.
- A kind of 4. preparation method of the slow-release fertilizer of natural polymer subbase according to claim 1, it is characterised in that:3rd step In, the mass ratio of sodium alginate and high molecular slow-release liquid fertilizer is 1:40~45.
- A kind of 5. preparation method of the slow-release fertilizer of natural polymer subbase according to claim 1, it is characterised in that:4th step In, the volume ratio of mixed solution and 3% boric acid calcium chloride solution is 1:20.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110563524A (en) * | 2019-10-17 | 2019-12-13 | 安徽省聚科石墨烯科技股份公司 | Polyvinyl alcohol/graphene coated controlled-release fertilizer |
CN111410584A (en) * | 2020-05-20 | 2020-07-14 | 吉林大学 | Microbial slow-release compound fertilizer and preparation method thereof |
CN114890841A (en) * | 2022-03-24 | 2022-08-12 | 武汉绿农瑞益生物科技有限公司 | Long-acting microbial compound fertilizer and preparation method thereof |
CN114933509A (en) * | 2022-05-09 | 2022-08-23 | 武汉绿农瑞益生物科技有限公司 | Slow-release compound fertilizer and preparation method thereof |
CN115160059A (en) * | 2022-06-27 | 2022-10-11 | 浙江大学 | Fertilizer carrier formula capable of performing extrusion type 3D printing and production method |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110563524A (en) * | 2019-10-17 | 2019-12-13 | 安徽省聚科石墨烯科技股份公司 | Polyvinyl alcohol/graphene coated controlled-release fertilizer |
CN111410584A (en) * | 2020-05-20 | 2020-07-14 | 吉林大学 | Microbial slow-release compound fertilizer and preparation method thereof |
CN114890841A (en) * | 2022-03-24 | 2022-08-12 | 武汉绿农瑞益生物科技有限公司 | Long-acting microbial compound fertilizer and preparation method thereof |
CN114933509A (en) * | 2022-05-09 | 2022-08-23 | 武汉绿农瑞益生物科技有限公司 | Slow-release compound fertilizer and preparation method thereof |
CN115160059A (en) * | 2022-06-27 | 2022-10-11 | 浙江大学 | Fertilizer carrier formula capable of performing extrusion type 3D printing and production method |
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Application publication date: 20180413 |