CN109384586A - A kind of alginic acid synergistic carrier preparation method of the urea suitable for corn top dressing - Google Patents

A kind of alginic acid synergistic carrier preparation method of the urea suitable for corn top dressing Download PDF

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Publication number
CN109384586A
CN109384586A CN201811328653.7A CN201811328653A CN109384586A CN 109384586 A CN109384586 A CN 109384586A CN 201811328653 A CN201811328653 A CN 201811328653A CN 109384586 A CN109384586 A CN 109384586A
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weight
parts
alginic acid
urea
temperature
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袁亮
赵秉强
李燕婷
林治安
张水勤
王薇
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Institute of Agricultural Resources and Regional Planning of CAAS
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Institute of Agricultural Resources and Regional Planning of CAAS
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    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES 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
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05BPHOSPHATIC FERTILISERS
    • C05B17/00Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to the urea alginic acid synergistic carrier preparation methods for being suitable for corn top dressing, the preparation method prepares seaweed acid extractant using hydramine, dimethylformamide as primary raw material, further the benzene carboxylic acid containing aromatic ring and the alginic acid of extraction are grafted, the chelated zinc of compatibility corn sensitivity prepares acidic functionality type and content alginic acid synergistic carrier more abundant.After alginic acid synergistic carrier is in conjunction with urea, urea 1cm fertilizer border 0.5~1.3 pH unit of soil pH can be significantly reduced, soil urease liveness averagely reduces by 26.5% compared with commercial urea processing, illustrates that the decomposition of alginic acid urea and conversion rate obviously slow down;Ammonia volatilization nitrogen reduces nearly 60% compared with commercial urea.Relatively control averagely improves 22.6% and 26.9% respectively for maize root system fresh weight and vigor, and the corn yield of alginic acid Urea treatment of the present invention improves 10.1% compared with commercial urea.

Description

A kind of alginic acid synergistic carrier preparation method of the urea suitable for corn top dressing
[technical field]
The invention belongs to technical field of fertilizer production.More particularly it relates to a kind of urea suitable for corn top dressing With alginic acid synergistic carrier preparation method.
[background technique]
Urea is the most important nitrogen fertilizers in China, but because its activity is high, easily conversion loss, this season utilization rate only 30%~ 35%, huge economic loss is caused, and bring serious environmental risk, mass concentration accounting of the ammonia in PM2.5 is 30% Left and right, part heavily contaminated weather is more than 60%.Summer corn top dressing season temperature is high, urease activity is higher, urea conversion is fast, and ammonia is waved Hair loss is big.Slowing down urea decomposition speed, reducing soil urease liveness is the main path for reducing its loss.Contain in alginic acid The functional groups such as quinonyl abundant, ketone group, can inhibit soil urease liveness, to reduce urea loss of nitrogen fertilizer to a certain extent. But the extracting method of traditional alginic acid mainly utilizes the inorganic bases such as sodium hydroxide, potassium hydroxide, ammonium hydroxide to extract, and is formed water-soluble Alginate, since alkalinity is stronger, urea converts the ammonium the to be formed volatilization loss in the form of ammonia quickly, generally should not be in summer corn The upper application of top dressing.
CN102701866A discloses a kind of fermentation liquid seaweed extract material synergist and its production method and purposes, with natural sea Algae is raw material, through microbial fermentation, then taken with alkali carries, the processes such as filters pressing produce seaweed extracted liquor, then to adding chela in liquid State microelement is closed, fermentation alga liquid fertilizer synergist of the invention is obtained.CN 104761413A discloses a kind of with ammonia volatilization Alginic acid fertilizer synergist of inhibiting effect and preparation method thereof, based on kelp, strain, carbon source, nitrogen source, middle microelement etc. Want raw material, the processes preparation such as fermented, extraction, compounding.A kind of whole biologic enzymolysis method of CN107236766A prepares seaweed plants The method of growth regulator, including produce before preparation, the pretreatment of raw material, level-one enzymatic hydrolysis, enzymolysis liquid removal of impurities, enzymolysis liquid homogeneous, Secondary enzymolysis, post-processing, the isolating and purifying of somatotropin, nine steps such as fertilizer is matched eventually.It yet there are no related suitable for jade Patent application and its related data of the urea of rice top dressing with alginic acid synergistic carrier.
Therefore, the present inventor, for technical problem of the existing technology, passes through on the basis for summarizing the prior art Lot of experiments and analysis work, complete the present invention finally.
[summary of the invention]
[technical problems to be solved]
The object of the present invention is to provide a kind of urea suitable for corn top dressing alginic acid synergistic carrier preparation methods.
[technical solution]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of urea suitable for corn top dressing alginic acid synergistic carrier preparation methods, it is characterised in that should The step of preparation method, is as follows:
A, prepared by seaweed acid extractant
20~50 parts by weight hydramine, 5~10 parts by weight dimethylformamides and 5~10 parts by weight ethylene glycol are added to 1000 In the water that~2000 parts by weight temperature are 60~70 DEG C, stirring and dissolving is cooling, obtains the seaweed acid extractant;
B, prepared by alginic acid extracting solution
100 parts by weight seawood meals are added to 800~1500 parts by weight in the seaweed acid extractant that step A is obtained, so Its temperature is gradually increased to 70~90 DEG C under stiring afterwards, and keeps 6~12h at this temperature, is then cooled to room temperature, from Heart separation, sediment discard, and obtain the alginic acid extracting solution;
C, chelating zinc solution preparation
100 parts by weight of lemon acid potassium, 20 parts by weight D-sorbites, 50 parts by weight diethanol amine are added with 30 parts by weight of glycerin In the water for being 50 DEG C to 1000 parts by weight temperature, dissolution adds 200 parts by weight white vitriols, is uniformly mixed, by its solution 80 DEG C of temperature are heated to, stirring and dissolving obtains the chelating zinc solution;
D, prepared by alginic acid synergistic carrier
10~20 parts by weight benzene carboxylic acids and 0.02~0.10 parts by weight polyethylene glycol are added to 100 parts by weight to obtain in step B To alginic acid extracting solution in, be then heated to temperature 50 C, add 2~3 parts by weight cumyl peroxides, continue to heat To 100 DEG C of temperature, 60~120min is reacted at this temperature, adds 3~8 parts by weight of polyoxyethylene ethers and 0.5~2.0 weight Part O-phthalic alkanol amides are measured, it is cooling, its pH value is adjusted to 4.5~5.5 using peroxophosphoric acid aqueous solution, adds 100 The chelating zinc solution that parts by weight are obtained in step C then obtains the urea suitable for corn top dressing and is carried with alginic acid synergy Body.
A preferred embodiment of the invention, in step, hydramine, dimethylformamide, ethylene glycol and water Weight ratio is 24~42:6~9:6~9:1200~1800.
According to another preferred method of implementation of the present invention, in step, the hydramine is one or more to be selected from one Ethanol amine, diethanol amine, triethanolamine or N methyldiethanol amine hydramine.
According to another preferred method of implementation of the present invention, in step, it will be stirred under conditions of 60~180rpm of revolving speed It mixes the solution that dissolution obtains and is cooled to 30 DEG C of temperature or less.
According to another preferred method of implementation of the present invention, in stepb, the seaweed is brown alga, bulk kelp or bubble leaf Algae.
According to another preferred method of implementation of the present invention, in stepb, the granularity of the seawood meal is less than 2mm.
According to another preferred method of implementation of the present invention, in stepb, under conditions of 1000~5000rpm of revolving speed It is centrifugated 10~30min.
According to another preferred method of implementation of the present invention, in step D, the benzene carboxylic acid be benzoic acid, phenylacetic acid, Salicylic acid or acetylsalicylic acid.
According to another preferred method of implementation of the present invention, in step D, polyoxyethylene ether and phthalic acid alkane is added Its solution is cooled to 15~30 DEG C of temperature after base amide.
According to another preferred method of implementation of the present invention, in step D, the concentration of the peroxophosphoric acid aqueous solution be 1~ 5mol/L。
The present invention is described in more detail below.
The present invention relates to a kind of urea suitable for corn top dressing alginic acid synergistic carrier preparation methods.
The step of urea alginic acid synergistic carrier preparation method, is as follows:
A, prepared by seaweed acid extractant
20~50 parts by weight hydramine, 5~10 parts by weight dimethylformamides and 5~10 parts by weight ethylene glycol are added to 1000 In the water that~2000 parts by weight temperature are 60~70 DEG C, stirring and dissolving is cooling, obtains the seaweed acid extractant;
The hydramine that the present invention uses is a kind of using the nitrogen-atoms of ammonia as core, and the chemical combination that the hydrogen atom of ammonia is replaced by alcohol Object, it can be chelated with calcium, magnesium, the iron plasma in seaweed powder raw material, the water solubility of this raw material be improved, to help to improve The recovery rate of alginic acid is extracted from seaweed powder raw material.
The hydramine that the present invention uses is one or more selected from monoethanolamine, diethanol amine, triethanolamine or N- methyl two The hydramine of ethanol amine.The hydramine is all current market sales of product, for example, by Shanghai Min Chen Chemical Co., Ltd. with Trade name monoethanolamine (MEA) sale product, by Chemical Co., Ltd., Guoan, Zouping County with trade name N methyldiethanol amine (MDEA) product sold.
In the present invention, dimethylformamide is a kind of organic base, it can be acid with carboxyl, phenolic hydroxyl group in alginic acid etc. Group is reacted and generates water-soluble alginic acid, so as to extract alginic acid, and it from acid starting material containing seaweed It also can increase methyl, methoxy functional mass contg in alginic acid.The dimethylformamide that the present invention uses is existing market The product of upper sale, such as the production sold by Nanjing Ke Zheng Chemical Co., Ltd. with trade name n,N-Dimethylformamide (DMF) Product.
Ethylene glycol can enhance due to the good intersolubility of water and low temperature resistance alginic acid extractant liquid stability and Mobility.The ethylene glycol that the present invention uses is current market sales of product, such as the limited public affairs of chemical products are just being risen by Zhengzhou Take charge of the product sold with trade name anti-icing fluid spent glycol.
In the present invention, when other raw material dosages are in the range, if the dosage of hydramine is lower than 20 parts by weight, Alginic acid recovery rate can then be reduced;If the dosage of hydramine is higher than 50 parts by weight, it is excessive to will lead to alginic acid liquid bubble, Tiny impurity is mixed in alginic acid liquid, the alginic acid purity liquid decline of extraction;Therefore, the dosage of hydramine is 20~50 weights Amount part is suitable, preferably 24~42 parts by weight, more preferably 30~36 parts by weight.
It is right if the dosage of dimethylformamide is lower than 5 parts by weight when other raw material dosages are in the range It improves seaweed acid methyl and methoxyl content effect is unobvious;If the dosage of dimethylformamide is higher than 10 parts by weight, Because of the methyl and methoxyl content height in seaweed extracted liquor, alginic acid carboxyl itself and hydroxy functional group are reduced to a certain extent Activity;Therefore, it is suitable, preferably 6~9 parts by weight that the dosage of dimethylformamide, which is 5~10 parts by weight,.
It, can be to low temperature if the dosage of ethylene glycol is lower than 5 parts by weight when other raw material dosages are in the range Shi Tigao alginic acid liquid stability effect is unobvious;It, can be because of its hydroxyl if the dosage of ethylene glycol is higher than 10 parts by weight Content is higher, may cause part alginic acid precipitating with storage time extension;Therefore, the dosage of ethylene glycol is 5~10 parts by weight It is appropriate, preferably 6~9 parts by weight.
It, can be because extracting if the dosage of water is lower than 1000 parts by weight when other raw material dosages are in the range Agent excessive concentration, water consumption is low, and seaweed acid solubility is limited, extracts the decline of alginic acid efficiency;If the dosage of water is higher than 2000 , then can be too low because of Extractant concentration when parts by weight, also result in the decline of alginic acid recovery rate;Therefore, the dosage of water be 1000~ 2000 parts by weight are suitable, preferably 1200~1800 parts by weight, more preferably 1400~1600 parts by weight.
Preferably, the weight ratio of hydramine, dimethylformamide, ethylene glycol and water be 24~42:6~9:6~9:1200~ 1800。
It is highly preferred that hydramine, dimethylformamide, ethylene glycol and water weight ratio be 30~36:7~8:7~8:1400 ~1600.
According to the present invention, stirring and dissolving is obtained under conditions of 60~180rpm of revolving speed by raw materials such as dimethylformamides Solution is cooled to 30 DEG C of temperature or less.
B, prepared by alginic acid extracting solution
100 parts by weight seawood meals are added to 800~1500 parts by weight in the seaweed acid extractant that step A is obtained, so Its temperature is gradually increased to 70~90 DEG C under stiring afterwards, and keeps 6~12h at this temperature, is then cooled to room temperature, from Heart separation, sediment discard, and obtain the alginic acid extracting solution;
According to the present invention, the seaweed is brown alga, bulk kelp or yellow tang, and the seaweed that the present invention uses all is existing market The product of upper sale, such as the brown alga that the present invention uses is the brown alga sold by the friendly company of Yantai Long Island three with trade name kelp; The bulk kelp that the present invention uses is the bulk kelp sold by Shaanxi Si Nuote Bioisystech Co., Ltd with trade name bulk kelp original powder.
According to the present invention, brown alga, bulk kelp or yellow tang are crushed using existing conventional crushing plant, it is small collects granularity Alginic acid extracting solution is prepared as raw material in the seawood meal of 2mm.
In the present invention, when seawood meal is 100 parts by weight, if the seaweed acid extractant dosage is lower than 800 parts by weight, It then will lead to that liquid is thick to be difficult to carry out subsequent centrifugal treating;If the seaweed acid extractant dosage is higher than 1500 parts by weight, The water content that then will lead to alginic acid extracting solution is high, influences application of the alginic acid synergistic carrier in urea.Therefore, the seaweed The dosage of acid extractant is that 800~1500 parts by weight are appropriate.
In this step, in the case where revolving speed is the stirring of 100~160rpm by seawood meal and alginic acid extractant mixture Temperature be gradually increased to 70~90 DEG C, and at this temperature keep 6~12h.Its Extracting temperature and extraction time are more than described Range is worthless.If extraction time is shorter than 6h, alginic acid is extracted not exclusively, and alginic acid is caused to lose;If extracted Time is more than 12h, then causes the energy consumption for extracting alginic acid to increase, increased costs.Therefore, alginic acid extraction time is that 6~12h is It is feasible.
According to the present invention, the extract being cooled to room temperature using centrifuge under conditions of 1000~5000rpm of revolving speed from The heart separates 10~30min.The centrifuge that the present invention uses is the product sold on existing market, such as by Shanghai City centrifugal machine Co., Ltd, research institute separates the product of sleeping spiral shell sedimentation centrifuge sale with trade name two-phase.
C, chelating zinc solution preparation
100 parts by weight of lemon acid potassium, 20 parts by weight D-sorbites, 50 parts by weight diethanol amine are added with 30 parts by weight of glycerin In the water for being 50 DEG C to 1000 parts by weight temperature, dissolution adds 200 parts by weight white vitriols, is uniformly mixed, by its solution 80 DEG C of temperature are heated to, stirring and dissolving obtains the chelating zinc solution;
Potassium citrate, D-sorbite, diethanol amine, glycerol and the white vitriol that the present invention uses all are currently on the market The product of sale.
D, prepared by alginic acid synergistic carrier
10~20 parts by weight benzene carboxylic acids and 0.02~0.10 parts by weight polyethylene glycol are added to 100 parts by weight to obtain in step B To alginic acid extracting solution in, be then heated to temperature 50 C, add 2~3 parts by weight cumyl peroxides, then heat To 100 DEG C of temperature, 60~120min is reacted at this temperature, adds 3~8 parts by weight of polyoxyethylene ethers and 0.5~2.0 weight Part O-phthalic alkanol amides are measured, it is cooling, its pH value is adjusted to 4.5~5.5 using peroxophosphoric acid aqueous solution, adds 100 The chelating zinc solution that parts by weight are obtained in step C then obtains the urea suitable for corn top dressing and is carried with alginic acid synergy Body.
In the present invention, in cumyl peroxide initiator and in the presence of polyglycol surfactants, benzene carboxylic acid with Alginic acid in the alginic acid extracting solution that step B is obtained carries out graft reaction, then further increases alginic acid acidic functionality Type and quantity, the purpose is to make alginic acid even closer in conjunction with the amino in urea molecule, hence it is evident that delay urea in soil In decomposition rate.
In the present invention, the benzene carboxylic acid is benzoic acid, phenylacetic acid, salicylic acid or acetylsalicylic acid;They are all mesh Preceding product available on the market, such as the product sold with trade name benzoic acid by Jiangsu Shun Feng Chemical Co., Ltd., Shandong are new Product that Hua Longxin Chemical Co., Ltd. is sold with trade name sublimed salicylic acid, by Zhengzhou Jia Hong Chemical Co., Ltd. with trade name The product of acetylsalicylic acid sale.
Similarly, when other raw material dosages are in the range, if benzene carboxylic acid dosage is lower than 10 parts by weight, benzene carboxyl Functional group's incrementss are relatively low;If benzene carboxylic acid dosage is higher than 20 parts by weight, part alginic acid can be caused to precipitate;Therefore, benzene carboxylic Sour dosage is that 10~20 parts by weight are appropriate;
When other raw material dosages are in the range, if cumyl peroxide dosage is lower than 2 parts by weight, it will lead to Grafting efficiency is low;If cumyl peroxide dosage is higher than 3 parts by weight, it is too fast to will lead to reaction;Therefore, peroxidating two is different Propyl benzene dosage is that 2~3 parts by weight are feasible;
It, can be because of dispersion if polyethylene glycol dosage is lower than 0.02 parts by weight when other raw material dosages are in the range Property is low, and graft effect is undesirable;If polyethylene glycol dosage is higher than 0.1 parts by weight, macromolecular mass will form, influence grafting effect Fruit;Therefore, it is feasible that polyethylene glycol dosage, which is 0.02~0.1 parts by weight,;
This graft reaction carries out 60~120min at 100 DEG C of temperature, if the reaction time is shorter than 60min, benzene Carboxylic acid and alginic acid combination stability are inadequate;If the reaction time is longer than 120min, energy consumption increases obvious.Therefore, this Reaction time is that 60~120min is feasible.
Polyoxyethylene ether has both resin and nonionic surfactant performance in the present invention, it can not only be used for stationary phase into One step slows down urea and moves in the soil liquid, but also as bleeding agent, promotes alginic acid in conjunction with urea.
O-phthalic alkanol amides nonionic surfactant can enhance the infiltration of polyoxyethylene ether in the present invention Effect, and the stability of alginic acid synergistic carrier can be improved.
Peroxophosphoric acid in the present invention both adjustable pH, formed buffer system, strength of urea particles can also be increased, slowed down Dissolution and rate of release of the urea in the soil liquid.
In the present invention, polyoxyethylene ether dosage is 3~8 parts by weight.If polyoxyethylene ether dosage is lower than 3 parts by weight, Then dispersion and permeance property are unobvious;If polyoxyethylene ether dosage is higher than 8 parts by weight, synergistic carrier viscosity is excessively high;Therefore, Polyoxyethylene ether dosage is that 3~8 parts by weight are appropriate.
Similarly, O-phthalic alkanol amides dosage is 0.5~2.0 parts by weight.If O-phthalic alkanol amides Dosage is lower than 0.5 parts by weight, then not significant to the osmotic effect for strengthening polyoxyethylene ether;If O-phthalic alkanol amides are used Amount is higher than 2 parts by weight, then influences the dispersion performance of polyoxyethylene ether;Therefore, O-phthalic alkanol amides dosage be 0.5~ 2.0 parts by weight are appropriate.
According to the present invention, the concentration of the peroxophosphoric acid aqueous solution is 1~5mol/L.
According to the present invention, be added after polyoxyethylene ether and O-phthalic alkanol amides by its solution be cooled to temperature 15~ 30℃。
Polyethylene glycol, cumyl peroxide, polyoxyethylene ether, O-phthalic alkanol amides and the mistake that the present invention uses Phosphoric acid is all current market sales of product, such as by Shaanxi dual force Chemical Co., Ltd. with trade name cumyl peroxide The product of DCP sale, the product sold with trade name polyoxyethylene ether polyoxyethylene nonylphenol ether -7 by Jiangsu Hai'an Petrochemical Plant, by The product that Guangzhou Zong Yu Chemical Industry Science Co., Ltd is sold with trade name suspension stabilizer TAB-2 O-phthalic alkanol amides.
The present invention, which prepares alginic acid synergistic carrier, to produce high nitrogen in conjunction with urea production process or granular urea product The new urea product of fertile utilization rate.
The application method of alginic acid synergistic carrier of the present invention is as follows:
First method: in urea production process, the alginic acid synergy of 5~50 parts by weight the method for the present invention preparation is carried Body is added in 1000 parts by weight of urea molten liquids, sprays to obtain the granular urea of synergistic carrier containing alginic acid through high tower.
Second method: 5~50 parts by weight step C alginic acid synergistic carrier prepared is added to the heating of 1000 parts by weight Into 40~75 DEG C of granular ureas, 2min is quickly stirred, is dried after mixing in 100 DEG C, obtains synergistic carrier containing alginic acid Grain urea.
[beneficial effect]
The beneficial effects of the present invention are:
1, organic acidity functional group abundant can react to form long-chain compound with the amido of urea in the synergistic carrier, subtract Slow urea decomposition speed;Fertile border soil urease averagely reduces by 25% or more, to slow down conversion of the urea to ammonium;
2,0.5~1.3 unit of granular urea fertilizer border pH is reduced, fixing has converted the ammonium of formation, reduces ammoniacal nitrogen volatilization Lose nearly 60%;
3, maize root system fresh weight increases by 20% or more, improves 25% or more root activity, from the angle for promoting Nutrient Absorption Utilization rate of fertilizer is improved, the corn yield of alginic acid Urea treatment of the present invention improves 10.1% compared with commercial urea.
4, the function of the phosphorus in activating soil, potassium and middle microelement further promotes the application effect of synergistic carrier.
[specific embodiment]
It will be better understood that the present invention by following embodiments.
One, embodiment is prepared
Embodiment 1: prepared by the urea alginic acid synergistic carrier suitable for corn top dressing
The implementation steps of the embodiment are as follows:
A, prepared by seaweed acid extractant
30 parts by weight monoethanolamines, 8 parts by weight dimethylformamides and 8 parts by weight ethylene glycol are added to 2000 parts by weight temperature Degree is in 60 DEG C of water, stirring and dissolving under conditions of revolving speed 60rpm, obtained solution is cooled to 30 DEG C of temperature hereinafter, obtaining The seaweed acid extractant;
B, prepared by alginic acid extracting solution
Wild kelp brown alga powder raw material by 100 parts by weight granularities less than 2mm is added to 1200 parts by weight and obtains in step A Seaweed acid extractant in, its temperature is then gradually increased to 80 DEG C in the case where revolving speed is the stirring of 140rpm, and in this temperature Lower holding 6h, is then cooled to room temperature, is centrifugated 18min under conditions of revolving speed 3800rpm, and precipitating discards, and obtains described Alginic acid extracting solution;
C, chelating zinc solution preparation
100 parts by weight of lemon acid potassium, 20 parts by weight D-sorbites, 50 parts by weight diethanol amine are added with 30 parts by weight of glycerin In the water for being 50 DEG C to 1000 parts by weight temperature, dissolution adds 200 parts by weight white vitriols, is uniformly mixed, by its solution 80 DEG C of temperature are heated to, stirring and dissolving obtains the chelating zinc solution;
D, prepared by alginic acid synergistic carrier
16 parts by weight benzene carboxylic acids and 0.02 parts by weight polyethylene glycol are added to what 100 parts by weight were obtained in step B In alginic acid extracting solution, it is then heated to temperature 50 C, 2.0 parts by weight cumyl peroxides is added, continues to be heated to temperature 100 DEG C of degree, reacts 60min at this temperature, adds 3 parts by weight of polyoxyethylene ethers and 0.5 parts by weight phthalic acid alkane Base amide is cooled to 15 DEG C of temperature, its pH value is adjusted to 4.5 using the peroxophosphoric acid aqueous solution that concentration is 4mol/L, is added The chelating zinc solution that 100 parts by weight are obtained in step C then obtains the urea alginic acid synergy suitable for corn top dressing Carrier.
Embodiment 2: prepared by the urea alginic acid synergistic carrier suitable for corn top dressing
The implementation steps of the embodiment are as follows:
A, prepared by seaweed acid extractant
20 parts by weight diethanol amine, 5 parts by weight dimethylformamides and 5 parts by weight ethylene glycol are added to 1400 parts by weight temperature Degree is in 64 DEG C of water, stirring and dissolving under conditions of revolving speed 100rpm, obtained solution is cooled to 30 DEG C of temperature hereinafter, obtaining The seaweed acid extractant;
B, prepared by alginic acid extracting solution
Yellow tang powder raw material by 100 parts by weight granularities less than 2mm is added to the seaweed that 1500 parts by weight are obtained in step A In acid extractant, its temperature is then gradually increased to 80 DEG C in the case where revolving speed is the stirring of 200rpm, and keep at this temperature 12h is then cooled to room temperature, is centrifugated 30min under conditions of revolving speed 5000rpm, and precipitating discards, and obtains the seaweed Sour extracting solution;
C, chelating zinc solution preparation
100 parts by weight of lemon acid potassium, 20 parts by weight D-sorbites, 50 parts by weight diethanol amine are added with 30 parts by weight of glycerin In the water for being 50 DEG C to 1000 parts by weight temperature, dissolution adds 200 parts by weight white vitriols, is uniformly mixed, by its solution 80 DEG C of temperature are heated to, stirring and dissolving obtains the chelating zinc solution;
D, prepared by alginic acid synergistic carrier
20 parts by weight phenylacetic acid benzene carboxylic acids and 0.05 parts by weight polyethylene glycol are added to what 100 parts by weight were obtained in step B In alginic acid extracting solution, it is then heated to temperature 50 C, 2.4 parts by weight cumyl peroxides is added, continues to be heated to temperature 100 DEG C of degree, reacts 80min at this temperature, adds 4 parts by weight of polyoxyethylene ethers and 1.0 parts by weight phthalic acid alkane Base amide is cooled to 20 DEG C of temperature, its pH value is adjusted to 5.0 using the peroxophosphoric acid aqueous solution that concentration is 1mol/L, is added The chelating zinc solution that 100 parts by weight are obtained in step C then obtains the urea alginic acid synergy suitable for corn top dressing Carrier.
Embodiment 3: prepared by the urea alginic acid synergistic carrier suitable for corn top dressing
The implementation steps of the embodiment are as follows:
A, prepared by seaweed acid extractant
40 parts by weight N methyldiethanol amines, 10 parts by weight dimethylformamides and 10 parts by weight ethylene glycol are added to 1000 In the water that parts by weight temperature is 67 DEG C, stirring and dissolving under conditions of revolving speed 180rpm, obtained solution is cooled to 30 DEG C of temperature Hereinafter, obtaining the seaweed acid extractant;
B, prepared by alginic acid extracting solution
Bulk kelp original powder by 100 parts by weight granularities less than 2mm is added to 800 parts by weight and mentions in the alginic acid that step A is obtained It takes in agent, its temperature is then gradually increased to 70 DEG C in the case where revolving speed is the stirring of 100rpm, and keep 8h at this temperature, connect Be cooled to room temperature, be centrifugated 10min under conditions of revolving speed 2400rpm, precipitating discards, and obtains the alginic acid and extracts Liquid;
C, chelating zinc solution preparation
100 parts by weight of lemon acid potassium, 20 parts by weight D-sorbites, 50 parts by weight diethanol amine are added with 30 parts by weight of glycerin In the water for being 50 DEG C to 1000 parts by weight temperature, dissolution adds 200 parts by weight white vitriols, is uniformly mixed, by its solution 80 DEG C of temperature are heated to, stirring and dissolving obtains the chelating zinc solution;
D, prepared by alginic acid synergistic carrier
10 parts by weight salicylic acid benzene carboxylic acids and 0.08 parts by weight polyethylene glycol are added to what 100 parts by weight were obtained in step B In alginic acid extracting solution, it is then heated to temperature 50 C, 3.0 parts by weight cumyl peroxides is added, continues to be heated to temperature 100 DEG C of degree, reacts 100min at this temperature, adds 6 parts by weight of polyoxyethylene ethers and 1.5 parts by weight phthalic acid alkane Base amide is cooled to 25 DEG C of temperature, its pH value is adjusted to 5.5 using the peroxophosphoric acid aqueous solution that concentration is 2mol/L, is added The chelating zinc solution that 100 parts by weight are obtained in step C then obtains the urea alginic acid synergy suitable for corn top dressing Carrier.
Embodiment 4: prepared by the urea alginic acid synergistic carrier suitable for corn top dressing
The implementation steps of the embodiment are as follows:
A, prepared by seaweed acid extractant
50 parts by weight triethanolamines, 6 parts by weight dimethylformamides and 6 parts by weight ethylene glycol are added to 1600 parts by weight temperature Degree is in 70 DEG C of water, stirring and dissolving under conditions of revolving speed 140rpm, obtained solution is cooled to 30 DEG C of temperature hereinafter, obtaining The seaweed acid extractant;
B, prepared by alginic acid extracting solution
Kelp brown alga powder raw material by 100 parts by weight granularities less than 2mm is added to 1000 parts by weight in the sea that step A is obtained In alginic acid extractant, its temperature is then gradually increased to 90 DEG C in the case where revolving speed is the stirring of 180rpm, and protect at this temperature 10h is held, room temperature is then cooled to, is centrifugated 26min under conditions of revolving speed 1000rpm, precipitating discards, and obtains the sea Alginic acid extracting solution;
C, chelating zinc solution preparation
100 parts by weight of lemon acid potassium, 20 parts by weight D-sorbites, 50 parts by weight diethanol amine are added with 30 parts by weight of glycerin In the water for being 50 DEG C to 1000 parts by weight temperature, dissolution adds 200 parts by weight white vitriols, is uniformly mixed, by its solution 80 DEG C of temperature are heated to, stirring and dissolving obtains the chelating zinc solution;
D, prepared by alginic acid synergistic carrier
13 parts by weight acetylsalicylic acid benzene carboxylic acids and 0.10 parts by weight polyethylene glycol are added to 100 parts by weight to obtain in step B To alginic acid extracting solution in, be then heated to temperature 50 C, add 2.8 parts by weight cumyl peroxides, continue to heat To 100 DEG C of temperature, 120min is reacted at this temperature, adds 8 parts by weight of polyoxyethylene ethers and 2.0 parts by weight O-phthalics Alkanol amides are cooled to 30 DEG C of temperature, its pH value is adjusted to 5.0 using the peroxophosphoric acid aqueous solution that concentration is 5mol/L, then The chelating zinc solution that 100 parts by weight are obtained in step C is added, then obtains the urea alginic acid suitable for corn top dressing Synergistic carrier.
Two, test example
Test example 1: alginic acid synergistic carrier of the present invention is to urea fertilizer border soil pH and urease activity and ammonia volatilization It influences
Sample preparation: alginic acid synergistic carrier prepared by embodiment 1, embodiment 2 and embodiment 3 is according to it and weight of urea It is respectively added to than 2:100 in the fusing urea that three temperature are 118 DEG C, allows it to react 5min at this temperature, by seaweed Uraturia element molten liquid and commercial urea (production of Group Plc, Rising, nitrogen content 46%) molten liquid are poured into length respectively In × wide × height=5cm × 5cm × 5cm stainless steel mould, after cooling, takes out, obtain square urea U, square seaweed Uraturia element A, B, C.
Test procedure:
(1) square urea U, square alginic acid urea A, B, C fertile border test: are placed in the stone of water content 18% respectively In ash moisture soil (Shandong Dezhou), compacting soil to bulk density 1.3 is cultivated 12 hours at 25 ± 2 DEG C of Yu Wendu.Terminate in culture Afterwards, the soil apart from urea sample edge 1.5-2.0cm, 1.0-1.5cm, 0.5-1.0cm, 0-0.5cm is cut out respectively with blade. According to (Lu Rukun " soil agrochemistry analysis method " Beijing: Chinese agriculture Science Press, 2000.) standard method of analysis Test square urea fertilizer border soil pH, urease activity.
(2) ammonia volatilization test: by the dosage of 0.5g urea N/kg soil weigh respectively control sample U, alginic acid urea A, B, C is mixed with Fluvo-Aquic Soils, is placed in culture bottle, the small beaker for filling 2% boric acid solution is put into culture bottle, uses plastics Diaphragm seal is cultivated at 25 ± 2 DEG C of Yu Wendu 24 hours, and 3 drop bromocresol greens-methyl red instruction is then added into boric acid solution 0.01M1/2H is used in agent2SO4Standard solution titrates the ammonia that boric acid absorbs.The results are shown in Table 1 for the testing inspection.
Table 1: alginic acid urea is compared with the fertile border soil pH of commercial urea, urease activity, ammonia volatilization nitrogen
The temperature in summer corn top dressing season is higher, soil urease liveness is relatively high, urea conversion ammonium that is fast, therefore generating Readily volatilized loss.Fertile border is the initial period of fertilizer conversion, decides the urea conversion and loss process in later period.These tests The result shows that can to significantly reduce urea 1cm fertilizer border 0.5~1.3 pH of soil pH mono- for alginic acid synergistic carrier prepared by the present invention Position, i.e. H in the soil liquid of fertilizer border+Concentration improves 5~13 times;Soil urease liveness is flat compared with commercial urea processing in fertile border 1cm 26.5% is reduced, illustrates that the decomposition of alginic acid urea and conversion rate obviously slow down;Ammonia volatilization nitrogen is average to be subtracted compared with commercial urea Few nearly 60%.
Test example 2: influence of the alginic acid synergistic carrier of the present invention to Maize Roots and vigor
Test specimen: alginic acid synergistic carrier prepared by embodiment 1, embodiment 2 and embodiment 4.
Test procedure: additive amount of the alginic acid synergistic carrier of the present invention in Huo Gelan nutrient solution is 0.2g/L, is remembered respectively For A, B, C.The quartz sand handled well is attached in 500mL Pei Yang Portland (drainage hole is arranged at bottom), Ju Li Portland is along 2~3cm.It will processing Good crop is colonized in Pei Yang Portland, and each processing is repeated 6 times.Every 1 nutrient solution of pouring in 4 days, each 100mL, to keep Certain humidity and nutrient density.
Testing inspection: emerging the 21st day sampling and measuring root system fresh weight in crop, using " plant physiology experiment guidance " (China Southern BJ Universithy of Polytech Press, 2015) routine colorimetric method measurement TTC vigor.Testing result is listed in Table 2 below.
Table 2: influence of the alginic acid synergistic carrier of the present invention to Maize Roots and vigor
The absorbability of crop root is an important factor for determining utilization rate of fertilizer.The result listed by table 2 is it is found that seaweed Relatively control averagely improves 22.6% and 26.9% to the maize root system fresh weight and vigor of sour synergistic carrier A, B, C processing respectively.
Test example 3: influence of the alginic acid urea of the present invention to yield of Summer Corn
Test arrangement carries out in Zhumadian prefecture, Henan province city, the township Shun He, Station City.Experimental field it is located at the hills Plain of Huaihe's Upper Reaches Area has a moderate climate, abundant rainfall, and illumination is sufficient, and for average temperature of the whole year at 15 DEG C or so, average annual rainfall is 850~960 millis Rice.It is to dredge single 20 for examination corn variety, planting density is 4500 plants/acre.
For trying fertilizer: commercial urea U and alginic acid urea AU (the seaweed acid vectors of embodiment 2), nitrogen content is 46.0%.Phosphate fertilizer selects P2O5The calcium superphosphate that content is by weight 12.5%, potash fertilizer select K2O content is by weight 60% potassium chloride.Whole phosphorus, potash fertilizer and 40% nitrogenous fertilizer make base fertilizer, and 60% nitrogenous fertilizer corn big bell mouth stage does top dressing.
Processing setting:
Processing 1: control,
Processing 2: alginic acid urea AU,
Processing 3: commercial urea U,
3 processing are set altogether, and each processing is repeated 3 times, and sets 9 cells altogether.Plot area is 6m × 4m, and surrounding sets protection Row, each cell are arranged by random district's groups.
Table 3: influence of the alginic acid urea to maize grain yield and biological character
The result listed by table 3 is it is found that the corn yield of alginic acid Urea treatment of the present invention is improved compared with commercial urea 10.1%, it is main to increase corn yield by increasing spike length and row grain number.
It can be seen that urea can be significantly reduced in summer jade after alginic acid synergistic carrier prepared by the present invention is in conjunction with urea The conversion rate of rice top dressing season soil urease liveness and urea can reduce ammonia loss by volatilization by influencing fertilizer border pH.And it can show It writes and improves maize root system fresh weight and vigor.

Claims (10)

1. a kind of urea suitable for corn top dressing alginic acid synergistic carrier preparation method, it is characterised in that the step of the preparation method It is rapid as follows:
A, prepared by seaweed acid extractant
20~50 parts by weight hydramine, 5~10 parts by weight dimethylformamides and 5~10 parts by weight ethylene glycol are added to 1000~ In the water that 2000 parts by weight temperature are 60~70 DEG C, stirring and dissolving is cooling, obtains the seaweed acid extractant;
B, prepared by alginic acid extracting solution
100 parts by weight seawood meals are added to 800~1500 parts by weight in the seaweed acid extractant that step A is obtained, are then existed Its temperature is gradually increased to 70~90 DEG C under stirring, and keeps 6~12h at this temperature, is then cooled to room temperature, centrifugation point From sediment discards, and obtains the alginic acid extracting solution
C, chelating zinc solution preparation
100 parts by weight of lemon acid potassium, 20 parts by weight D-sorbites, 50 parts by weight diethanol amine are added to 30 parts by weight of glycerin In the water that 1000 parts by weight temperature are 50 DEG C, dissolution adds 200 parts by weight white vitriols, is uniformly mixed, its solution is added For heat to 80 DEG C of temperature, stirring and dissolving obtains the chelating zinc solution;
D, prepared by alginic acid synergistic carrier
10~20 parts by weight benzene carboxylic acids and 0.02~0.10 parts by weight polyethylene glycol are added to what 100 parts by weight were obtained in step B In alginic acid extracting solution, it is then heated to temperature 50 C, 2~3 parts by weight cumyl peroxides is added, continues to be heated to temperature 100 DEG C of degree reacts 60~120min at this temperature, adds 3~8 parts by weight of polyoxyethylene ethers and 0.5~2.0 parts by weight O-phthalic alkanol amides, it is cooling, its pH value is adjusted to 4.5~5.5 using peroxophosphoric acid aqueous solution, adds 100 weight The chelating zinc solution that part obtains in step C then obtains the urea alginic acid synergistic carrier suitable for corn top dressing.
2. alginic acid synergistic carrier preparation method according to claim 1, it is characterised in that in step, hydramine, diformazan The weight ratio of base formamide, ethylene glycol and water is 24~42:6~9:6~9:1200~1800.
3. alginic acid synergistic carrier preparation method according to claim 1 or 2, it is characterised in that in step, described Hydramine is one or more hydramine selected from monoethanolamine, diethanol amine, triethanolamine or N methyldiethanol amine.
4. alginic acid synergistic carrier preparation method according to claim 1, it is characterised in that in step, will be in revolving speed The solution that stirring and dissolving obtains under conditions of 60~180rpm is cooled to 30 DEG C of temperature or less.
5. alginic acid synergistic carrier preparation method according to claim 1, it is characterised in that in stepb, the sea Algae is brown alga, bulk kelp or yellow tang.
6. alginic acid synergistic carrier preparation method according to claim 1, it is characterised in that in stepb, the seaweed The granularity of powder is less than 2mm.
7. alginic acid synergistic carrier preparation method according to claim 1, it is characterised in that in stepb, in revolving speed 10~30min is centrifugated under conditions of 1000~5000rpm.
8. alginic acid synergistic carrier preparation method according to claim 1, it is characterised in that in step C, the benzene Carboxylic acid is benzoic acid, phenylacetic acid, salicylic acid or acetylsalicylic acid.
9. alginic acid synergistic carrier preparation method according to claim 1, it is characterised in that in step D, polyoxy is added Its solution is cooled to 15~30 DEG C of temperature after vinethene and O-phthalic alkanol amides.
10. alginic acid synergistic carrier preparation method according to claim 1, it is characterised in that in step D, described to cross phosphorus The concentration of aqueous acid is 1~5mol/L.
CN201811328653.7A 2018-11-09 2018-11-09 A kind of alginic acid synergistic carrier preparation method of the urea suitable for corn top dressing Withdrawn CN109384586A (en)

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CN102701866A (en) * 2012-06-27 2012-10-03 中国农业科学院农业资源与农业区划研究所 Fermented alga liquid fertilizer synergist and production method and application thereof
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CN102515945A (en) * 2011-12-06 2012-06-27 中国农业科学院农业资源与农业区划研究所 Algae-enhanced urea, production method thereof, and purpose thereof
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