CN109369290A - A kind of alginic acid synergistic carrier preparation method of the phosphorus ammonium suitable for basic soil - Google Patents
A kind of alginic acid synergistic carrier preparation method of the phosphorus ammonium suitable for basic soil Download PDFInfo
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- CN109369290A CN109369290A CN201811328499.3A CN201811328499A CN109369290A CN 109369290 A CN109369290 A CN 109369290A CN 201811328499 A CN201811328499 A CN 201811328499A CN 109369290 A CN109369290 A CN 109369290A
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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
- C05G3/80—Soil conditioners
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
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Abstract
The present invention relates to a kind of alginic acid synergistic carrier preparation method of the phosphorus ammonium suitable for basic soil, the preparation method include the preparation of alginic acid organic extractant, the preparation of alginic acid extracting solution and alginic acid synergistic carrier preparation and etc..After alginic acid synergistic carrier is in conjunction with phosphorus ammonium, the fixation of phosphorus ammonium in alkaline soils can be significantly slowed by influencing fertilizer border pH, improve P availability, Available phosphate can also be supplemented.The more commercially available phosphorus ammonium of soil pH in fertile border 1cm reduces by 0.3~1.4 unit, soil Ca2- P and Ca8Average more commercially available phosphorus ammonium improves 22% and 16% to-P respectively.Wheat root weight and vigor improve 30% or more, and compared with commercially available phosphorus ammonium, the wheat yield of alginic acid phosphorus ammonium of the present invention averagely improves 13.4%, and phosphate fertilizer utilization efficiency improves 9.9 percentage points.
Description
[technical field]
The invention belongs to technical field of fertilizer production.More particularly it relates to a kind of phosphorus ammonium suitable for basic soil
With alginic acid synergistic carrier preparation method.
[background technique]
The 5.5% of the world phosphor resource reserves Jin Zhan of China gross reserves, the per-capita quantity of the resources is only the 39% of world average level.
Phosphorus ammonium is the most important phosphate fertilizer variety in China, but because its enter soil after easily fixed by metal ions such as calcium, magnesium, iron, aluminium, this season
Utilization rate only 20% or so, causes huge economic loss and the wasting of resources.Soil is only in the case where 6~7 pH, effectively
Phosphorus concentration highest.The calcium and magnesium ion content of basic soil is high, after phosphorus enters soil, 80% or more is fixed in 3 days, cannot
It is absorbed by crops utilization.By greatly improving phosphate fertilizer utilization efficiency, Phosphorus Fertilizer Rates are reduced, are to promote the sustainable benefit of China's phosphate fertilizer resource
With important technology approach.
Reducing the approach that phosphate fertilizer utilization efficiency was fixed, improved to phosphorus mainly has the metal adjusted in soil pH, reduction phosphorus and soil
Ions binding quantity promotes crop to absorb.The acidic functionalities such as carboxyl rich in, phenolic hydroxyl group in alginic acid, can be certain
Phosphorus is reduced in degree to fix, and improves phosphorus amount.But the extracting method of traditional alginic acid mainly utilizes sodium hydroxide, hydrogen-oxygen
Change the inorganic bases such as potassium, sodium carbonate to extract, forms water soluble algae hydrochlorate through kickback, alginic acid original structure is destroyed, together
When due to alkalinity it is stronger, should not generally be applied on basic soil.
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.A kind of whole biological enzymolysis legal system of CN107236766A
The method of standby seaweed plants growth regulator, including preparation, the pretreatment of raw material, level-one enzymatic hydrolysis, enzymolysis liquid removal of impurities, enzyme before producing
Solution 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
Guan Shi is suitable for patent application and its related data of the phosphorus ammonium of basic soil 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 alginic acid synergistic carrier preparation methods of the phosphorus ammonium suitable for basic soil.
[technical solution]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of alginic acid synergistic carrier preparation methods of the phosphorus ammonium suitable for basic soil, it is characterised in that should
The step of preparation method, is as follows:
A, prepared by alginic acid organic extractant
By 20~50 parts by weight hydramine, 5~10 parts by weight of lemon acid potassium, 5~10 parts by weight potassium salicylates and 5~10 weight
Part ethylene glycol is added in the water that 1000~2000 parts by weight temperature are 60~70 DEG C, and stirring and dissolving is cooling, obtains the seaweed
Sour organic extractant；
B, prepared by alginic acid extracting solution
100 parts by weight seawood meals are added to the alginic acid organic extractant that 800~1500 parts by weight are obtained in step A
In, its temperature is then gradually increased to 70~90 DEG C under stiring, and keep 6~12h at this temperature, is then cooled to room
Temperature, centrifuge separation, sediment discard, and obtain the alginic acid extracting solution；
C, prepared by alginic acid synergistic carrier
10~20 parts by weight benzene carboxylic acids, 5~10 parts by weight sulfonic acid and 0.02~0.05 parts by weight polyethylene glycol are added to
100 parts by weight are heated to temperature 50 C in the alginic acid extracting solution that step B is obtained, and add 2~3 parts by weight peroxidating two
Isopropylbenzene is then heated to 100 DEG C of temperature, reacts 60~120min at this temperature, adds 2~6 parts by weight polyoxy second
Alkene ether, cooling, its pH value is adjusted to 4.5~5.5 by used phosphate aqueous solution, obtains the phosphorus ammonium alginic acid suitable for basic soil
Synergistic carrier.
A preferred embodiment of the invention, in step, the hydramine are one or more to be selected from a second
Hydramine, 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 60~240rpm of revolving speed
It mixes the solution that dissolution obtains and is cooled to 40 DEG C of temperature or less.
According to another preferred method of implementation of the present invention, in step, hydramine, potassium citrate, potassium salicylate, second two
The weight ratio of alcohol and water is 28~42:6~9:6~9:6~9:1200~1800.
According to another preferred method of implementation of the present invention, in stepb, the seaweed is brown alga, bulk kelp or bubble leaf
Algae；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 1000~3000rpm of revolving speed
It is centrifugated 10~60min.
According to another preferred method of implementation of the present invention, in step C, 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 C, the sulfonic acid is benzene sulfonic acid, naphthalene sulfonic acids, first
Base sulfonic acid or tarine.
According to another preferred method of implementation of the present invention, in step C, the concentration of the peroxophosphoric acid aqueous solution is 1~
5mol/L。
According to another preferred method of implementation of the present invention, after addition polyoxyethylene ether that its solution is cooling in step C
To 10~40 DEG C of temperature.
The present invention is described in more detail below.
The present invention relates to a kind of alginic acid synergistic carrier preparation methods of the phosphorus ammonium suitable for basic soil, it is characterised in that should
The step of preparation method, is as follows:
A, prepared by alginic acid organic extractant
By 20~50 parts by weight hydramine, 5~10 parts by weight of lemon acid potassium, 5~10 parts by weight potassium salicylates and 5~10 weight
Part ethylene glycol is added in the water that 1000~2000 parts by weight temperature are 60~70 DEG C, and stirring and dissolving is cooling, obtains the seaweed
Sour organic extractant；
In the present invention, hydramine is a kind of using the nitrogen-atoms of ammonia as core, and the compound that the hydrogen atom of ammonia is replaced by alcohol,
It can be chelated with calcium, magnesium, the iron plasma in seawood meal, the water solubility of this raw material be improved, to help to improve from seaweed
The recovery rate of alginic acid is extracted in powder.
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. of Guoan of Zouping County with trade name N methyldiethanol amine
(MDEA) product sold.
In the present invention, potassium citrate is to increase alginic acid COO preparing the basic role in alginic acid organic extractant-
Alginic acid recovery rate improves in functional group.The potassium citrate that the present invention uses is current market sales of product, such as by Xi'an
The product that Hui Bang bioengineering Co., Ltd is sold with trade name potassium citrate.
In the present invention, potassium salicylate is to increase the carboxylic containing aromatic ring preparing the basic role in alginic acid organic extractant
Based structures make seaweed acid vectors have anti-adversity.The potassium salicylate that the present invention uses is current market sales of product, example
The product such as sold by Wuhan Bell card biological medicine Co., Ltd with trade name potassium salicylate.
Ethylene glycol can enhance alginic acid organic extractant liquid stabilising due to the good intersolubility of water and low temperature resistance
Property and mobility.The ethylene glycol that the present invention uses is current market sales of product, such as is just rising chemical products by Zhengzhou and have
The product that limit company is 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 28~42 parts by weight, more preferably 30~36 parts by weight.
It, can be to mentioning if the dosage of potassium citrate is lower than 5 parts by weight when other raw material dosages are in the range
High alginic acid extraction rate impact is unobvious；If the dosage of potassium citrate is higher than 10 parts by weight, it is organic to will lead to alginic acid
Extractant alkalinity is excessively high；Therefore, it is appropriate, preferably 6~9 parts by weight that the dosage of potassium citrate, which is 5~10 parts by weight,.
It, can be to increasing if the dosage of potassium salicylate is lower than 5 parts by weight when other raw material dosages are in the range
Strong alginic acid carrier effect effect is limited；If the dosage of potassium salicylate is higher than 10 parts by weight, it is organic alginic acid to be improved
The alkalinity of extractant, and increased costs；Therefore, the dosage of potassium salicylate be 5~10 parts by weight be it is appropriate, preferably 6~9
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 extracting solution stabilizing effect is unobvious；It, can be because of 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 suitable, preferably 6~9 parts by weight.
It, can be because of seaweed if the dosage of water is lower than 1000 parts by weight when other raw material dosages are in the range
Sour organic extractant excessive concentration, water consumption is low, and solubility is limited, extracts the decline of alginic acid efficiency；If the dosage of water is higher than
, then can be too low because of alginic acid organic extractant concentration when 2000 parts by weight, also result in the decline of alginic acid recovery rate；Therefore, water
Dosage be 1000~2000 parts by weight be suitable, preferably 1200~1800 parts by weight, more preferably 1400~
1600 parts by weight.
Preferably, the weight ratio of hydramine, potassium citrate, potassium salicylate, ethylene glycol and water is 28~42:6~9:6~9:6
~9:1200~1800.
In this step, the solution that stirring and dissolving obtains under conditions of 60~240rpm of revolving speed is cooled to temperature 40
DEG C hereinafter, main purpose be guarantee alginic acid organic extractant stability and subsequent quantizatiion preparation.
B, prepared by alginic acid extracting solution
100 parts by weight seawood meals are added to the alginic acid organic extractant that 800~1500 parts by weight are obtained in step A
In, its temperature is then gradually increased to 70~90 DEG C under stiring, and keep 6~12h at this temperature, is then cooled to room
Temperature, centrifuge 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 alginic acid organic extractant dosage is lower than 800 weights
Part is measured, then will lead to that liquid is thick to be difficult to carry out subsequent centrifugal treating；If the alginic acid organic extractant dosage is higher than
1500 parts by weight, then the alginic acid extracting solution water content that will lead to extraction is high, influences the application in urea.Therefore, the sea
Alginic acid organic extractant dosage is that 800~1500 parts by weight are appropriate.
In this step, seawood meal and alginic acid organic extractant are mixed in the case where revolving speed is the stirring of 100~200rpm
The temperature for closing object is gradually increased to 70~90 DEG C, and keeps 6~12h at this temperature.Its extraction time is more than that the range is
It is worthless.If extraction time is shorter than 6h, alginic acid is extracted not exclusively, and alginic acid is caused to lose；If extraction time is super
12h is crossed, then causes the energy consumption for extracting alginic acid to increase, increased costs.Therefore, it is feasible that alginic acid extraction time, which is 6~12h,
's.
According to the present invention, the extract being cooled to room temperature using centrifuge under conditions of 1000~3000rpm of revolving speed from
The heart separates 10~60min.The centrifuge that the present invention uses is current market sales of product, such as by Shanghai City centrifugal machine
Co., Ltd of research institute separates the product of sleeping spiral shell sedimentation centrifuge sale with trade name two-phase.
C, prepared by alginic acid synergistic carrier
10~20 parts by weight benzene carboxylic acids, 5~10 parts by weight sulfonic acid and 0.02~0.05 parts by weight polyethylene glycol are added to
100 parts by weight are heated to temperature 50 C in the alginic acid extracting solution that step B is obtained, and add 2~3 parts by weight peroxidating two
Isopropylbenzene is then heated to 100 DEG C of temperature, reacts 60~120min at this temperature, adds 2~6 parts by weight polyoxy second
Alkene ether, cooling, its pH value is adjusted to 4.5~5.5 by used phosphate aqueous solution, obtains the phosphorus ammonium alginic acid suitable for basic soil
Synergistic carrier.
In the present invention, in the presence of cumyl peroxide initiator and polyglycol surfactants, benzene carboxylic acid
Alginic acid in the alginic acid extracting solution obtained with step B carries out graft reaction, then further increases the acid official of alginic acid
Type and quantity can be rolled into a ball, the purpose is to even closer with the amino reaction bonded in phosphorus ammonium molecule, hence it is evident that delay phosphorus ammonium 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.
Sulfonic acid is one kind organic compound made of sulfo group is connected with alkyl (including aryl).In the present invention, it can
Enhance the water solubility of alginic acid and its sequestering power with metal ion.The sulfonic acid is benzene sulfonic acid, naphthalene sulfonic acids, methane sulfonic acid
Or tarine, they are all current market sales of products, such as by Shanghai Yi He Biotechnology Co., Ltd with quotient
The name of an article benzene sulfonic acid sale product, sold by Shanghai shriek Chemical Co., Ltd. with trade name 2- naphthalene sulfonic acids product, by Wuhan
Product that extra large Dehua work Development Co., Ltd is sold with trade name methane sulfonic acid, by Jiangsu Cai Wei Biotechnology Co., Ltd with quotient
The product of name of an article β-aminoethanesulfonic acid sale.
In the present invention, when other raw material dosages are in the range, if benzene carboxylic acid dosage is lower than 10 parts by weight, it
Keep benzene carboxyl functional group incrementss relatively low；If benzene carboxylic acid dosage is higher than 20 parts by weight, it can cause part alginic acid to precipitate；
Therefore, it is appropriate that benzene carboxylic acid dosage, which is 10~20 parts by weight,；
It, can be to raising seaweed sour water if sulfonic acid dosage is lower than 5 parts by weight when other raw material dosages are in the range
Dissolubility effect is unobvious；If sulfonic acid dosage is higher than 10 parts by weight, increased costs can be made excessively high；Therefore, sulfonic acid dosage be 5~
10 parts by weight are appropriate；
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 0.05 parts by weight, graft effect will affect；Therefore, benzene carboxylic
Sour dosage is that 0.02~0.05 parts by weight are feasible；
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 appropriate.
This reaction carries out 60~120min at 100 DEG C of temperature, if the reaction time is shorter than 60min, benzene carboxylic acid,
Sulfonic 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.
In the present invention, polyoxyethylene ether has both resin and nonionic surfactant performance in the present invention, it both may be used
The metal ion further slow down as stationary phase, reduced in the soil liquid is contacted with phosphorus ammonium.
Peroxophosphoric acid is a kind of mineral acid containing phosphoric acid and several polyphosphoric acids, it has extremely strong chela to foreign metal ion
Conjunction ability, therefore, the pH of its not only adjustable system, but also calcium, magnesium plasma in chelating alginic acid, enhancing sea can be passed through
The stability of alginic acid synergistic carrier.
In alginic acid synergistic carrier of the present invention preparation, polyoxyethylene ether dosage is 2~6 parts by weight, if polyoxyethylene
Ether dosage is lower than 2 parts by weight, then dispersion and permeance property are unobvious；If polyoxyethylene ether dosage is higher than 6 parts by weight, synergy
Carrier viscosity is excessively high；Therefore, it is appropriate that polyoxyethylene ether dosage, which is 2~6 parts by weight,.
In this step, it is added after polyoxyethylene ether and its solution is cooled to 10~30 DEG C of temperature.
According to the present invention, the concentration of the peroxophosphoric acid aqueous solution is 1~5mol/L.
Polyethylene glycol, cumyl peroxide, polyoxyethylene ether and the peroxophosphoric acid that the present invention uses all are currently on the market
The product of sale, for example, sold by Shaanxi dual force Chemical Co., Ltd. with trade name cumyl peroxide DCP product, by river
The product that the Hai'an Su Sheng petrochemical plant is sold with trade name polyoxyethylene ether polyoxyethylene nonylphenol ether -7.
The application method of alginic acid synergistic carrier of the present invention is as follows:
During existing production of ammonium phosphate, the obtained alginic acid synergistic carrier of 10~100 parts by weight step C is added to
It in 1000 parts by weight of phosphoric acid cleaning solutions, is reacted in tubular reactor with liquefied ammonia, obtains the synergistic carrier containing alginic acid
Phosphorus ammonium.
Existing production of ammonium phosphate process and its equipment used specifically may refer to " Modern Phosphating work technology and application ",
2013, Chemical Industry Press.
In this step, 1000 parts by weight of phosphoric acid cleaning solutions add 10~100 parts by weight alginic acid synergistic carriers.If
Alginic acid synergistic carrier additive amount is lower than 10 parts by weight, then it is not significant to reduce the fixed effect of phosphorus；If alginic acid synergistic carrier
Additive amount is higher than 100 parts by weight, then causes phosphorus ammonium water content excessively high, increases drying process pressure.
[beneficial effect]
The beneficial effects of the present invention are:
1, synergistic carrier of the present invention organic acidity functional group abundant can reduce particle phospho-ammonium fertilizer border pH0.3~1.4 list
Position, the resiliency of enhanced fertilizer border soil, soil fertilizer border available phosphorus content improve 50% or more；
2, the fixation of phosphorus in the soil, two phosphorus of soil calcium and eight phosphorus of calcium difference can be reduced in conjunction with the metal ions such as calcium, magnesium
Improve 23% and 16%, and phosphorus and middle microelement in activating soil.
3, root growth is stimulated, root activity is improved, promotes absorption of the crop to phosphorus element, further increases phosphate fertilizer utilization
Rate.Wheat root weight and vigor improve 30% or more, compared with commercially available phosphorus ammonium, the wheat yield of alginic acid phosphorus ammonium of the present invention
13.4% is averagely improved, phosphate fertilizer utilization efficiency improves 9.9 percentage points.
[specific embodiment]
It will be better understood that the present invention by following embodiments.
One, embodiment is prepared
Embodiment 1: it is suitable for basic soil phosphorus ammonium and is prepared with alginic acid synergistic carrier
The implementation steps of the embodiment are as follows:
A, prepared by alginic acid organic extractant
30 parts by weight monoethanolamines, 8 parts by weight of lemon acid potassium, 8 parts by weight potassium salicylates are added to 8 parts by weight ethylene glycol
In the water that 2000 parts by weight temperature are 60 DEG C, stirring and dissolving under conditions of revolving speed 60rpm, obtained solution is cooled to temperature 40
DEG C hereinafter, obtaining the alginic acid organic 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 to be had in the alginic acid that step A is obtained
In machine extractant, its temperature is then gradually increased to 70 DEG C under stiring, and keep 12h at this temperature, be then cooled to
Room temperature is centrifugated 60min under conditions of revolving speed 1000rpm, and sediment discards, and obtains the alginic acid extracting solution；
C, prepared by alginic acid synergistic carrier
16 parts by weight, 8 parts by weight benzene sulfonic acids and 0.02 parts by weight polyethylene glycol are added to 100 parts by weight in step
In the alginic acid extracting solution that B is obtained, be then heated to temperature 50 C, add 2.0 parts by weight cumyl peroxides, then plus
Heat reacts 60min to 100 DEG C of temperature at this temperature, adds 2 parts by weight of polyoxyethylene ethers, is cooled to 10 DEG C of temperature, makes
Its pH value is adjusted to 4.5 by the peroxophosphoric acid aqueous solution for being 1mol/L with concentration, then obtains described being suitable for basic soil phosphorus ammonium
With alginic acid synergistic carrier.
Embodiment 2: it is suitable for basic soil phosphorus ammonium and is prepared with alginic acid synergistic carrier
The implementation steps of the embodiment are as follows:
A, prepared by alginic acid organic extractant
20 parts by weight diethanol amine, 5 parts by weight of lemon acid potassium, 5 parts by weight potassium salicylates are added to 5 parts by weight ethylene glycol
In the water that 1400 parts by weight temperature are 64 DEG C, stirring and dissolving under conditions of revolving speed 240rpm, obtained solution is cooled to temperature
40 DEG C hereinafter, obtain the alginic acid organic 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 organic extractant, its temperature is then gradually increased to 90 DEG C under stiring, and keep 6h at this temperature, it is then cold
But to room temperature, it is centrifugated 10min under conditions of revolving speed 3000rpm, sediment discards, and obtains the alginic acid and extracts
Liquid；
C, prepared by alginic acid synergistic carrier
20 parts by weight phenylacetic acids, 5 parts by weight naphthalene sulfonic acids and 0.05 parts by weight polyethylene glycol are added to 100 parts by weight in step
In the alginic acid extracting solution that B is obtained, be then heated to temperature 50 C, add 2.4 parts by weight cumyl peroxides, then plus
Heat reacts 80min to 100 DEG C of temperature at this temperature, adds 4 parts by weight of polyoxyethylene ethers, is cooled to temperature 60 C, makes
Its pH value is adjusted to 5.0 by the peroxophosphoric acid aqueous solution for being 2mol/L with concentration, then obtains described being suitable for basic soil phosphorus ammonium
With alginic acid synergistic carrier.
Embodiment 3: it is suitable for basic soil phosphorus ammonium and is prepared with alginic acid synergistic carrier
The implementation steps of the embodiment are as follows:
A, prepared by alginic acid organic extractant
By 40 parts by weight triethanolamines, 10 parts by weight of lemon acid potassium, 10 parts by weight potassium salicylates and 10 parts by weight ethylene glycol
It is added in the water that 1000 parts by weight temperature are 67 DEG C, stirring and dissolving under conditions of revolving speed 180rpm, obtained solution is cooled to
40 DEG C of temperature is hereinafter, obtain the alginic acid organic 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 sour organic extractant, its temperature is then gradually increased to 80 DEG C under stiring, and keep 10h at this temperature, it is then cold
But to room temperature, it is centrifugated 45min under conditions of revolving speed 2000rpm, sediment discards, and obtains the alginic acid and extracts
Liquid；
C, prepared by alginic acid synergistic carrier
10 parts by weight salicylic acids, 10 parts by weight methane sulfonic acids and 0.03 parts by weight polyethylene glycol are added to 100 parts by weight to exist
In the alginic acid extracting solution that step B is obtained, it is then heated to temperature 50 C, 3.0 parts by weight cumyl peroxides is added, connects
Be heated to 100 DEG C of temperature, react 100min at this temperature, add 6 parts by weight of polyoxyethylene ethers, be cooled to temperature 20
DEG C, its pH value is adjusted to 5.5 using the peroxophosphoric acid aqueous solution that concentration is 4mol/L, then obtains described being suitable for basic soil
Phosphorus ammonium alginic acid synergistic carrier.
Embodiment 4: it is suitable for basic soil phosphorus ammonium and is prepared with alginic acid synergistic carrier
The implementation steps of the embodiment are as follows:
A, prepared by alginic acid organic extractant
By 50 parts by weight N methyldiethanol amines, 6 parts by weight of lemon acid potassium, 6 parts by weight potassium salicylates and 6 parts by weight second two
Alcohol is added in the water that 1600 parts by weight temperature are 70 DEG C, stirring and dissolving under conditions of revolving speed 120rpm, and obtained solution is cooling
To 40 DEG C of temperature hereinafter, obtaining the alginic acid organic 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
Alginic acid organic extractant in, its temperature is then gradually increased to 80 DEG C under stiring, and keep 8h at this temperature, connect
Be cooled to room temperature, be centrifugated 15min under conditions of revolving speed 2500rpm, sediment discards, and obtains the alginic acid and mentions
Take liquid；
C, prepared by alginic acid synergistic carrier
13 parts by weight acetylsalicylic acid benzene carboxylic acids, 6 parts by weight tarines and 0.04 parts by weight polyethylene glycol are added to
100 parts by weight are then heated to temperature 50 C in the alginic acid extracting solution that step B is obtained, and add 2.8 parts by weight peroxidating
Diisopropylbenzene (DIPB) is then heated to 100 DEG C of temperature, reacts 120min at this temperature, adds 5 parts by weight of polyoxyethylene ethers,
15 DEG C of temperature are cooled to, its pH value is adjusted to 5.0 using the peroxophosphoric acid aqueous solution that concentration is 5mol/L, is then obtained described
Suitable for basic soil phosphorus ammonium alginic acid synergistic carrier.
Two, test example
Test example 1: influence of the alginic acid synergistic carrier of the present invention to phospho-ammonium fertilizer border soil pH and available phosphorus
Sample preparation: alginic acid synergistic carrier prepared by embodiment 1, embodiment 2 and embodiment 3 is according to it and urea
Weight ratio 5:100 is added in phosphorus ammonium, and the alginic acid phosphorus ammonium particle and commercially available phosphorus ammonium for weighing 150g preparation respectively (open phosphorus collection in Guizhou
Group, P2O5Content is 46%), to be placed in length × width × height=5cm × 5cm × 5cm, and aperture is the stainless steel cloth mold of 0.5mm
In, obtain square square phosphorus ammonium P, square alginic acid phosphorus ammonium A, square alginic acid phosphorus ammonium B, square alginic acid phosphorus ammonium
C。
Phosphorus ammonium sample P, A, B, C: being placed in the Fluvo-Aquic Soils (Shandong Dezhou) of water content 18% by test procedure respectively,
Compacting soil is cultivated 12 hours at 25 ± 2 DEG C of temperature to bulk density 1.3.After culture, cut out respectively with blade apart from phosphorus ammonium
The soil of sample edge 1.5-2.0cm, 1.0-1.5cm, 0.5-1.0cm, 0-0.5cm.According to (for example female " soil agrochemistry in Shandong
Analysis method " Beijing: Chinese agriculture Science Press, 2000.) in standard method of analysis test square phospho-ammonium fertilizer border soil
PH, available phosphorus content.Testing result is listed in Table 1 below.
Table 1: alginic acid phosphorus ammonium is compared with the fertile border soil pH of commercially available phosphorus ammonium, available phosphorus content
Fertile border is the initial period of fertilizer conversion, decides the phosphorus fixed ammonium process in later period.Test result shows the present invention
The alginic acid synergistic carrier of preparation can significantly reduce the soil pH within phospho-ammonium fertilizer border soil pH, especially reduction fertilizer border 1cm, drop
0.3~1.4 pH unit of low amplitude, i.e. H in the soil liquid of fertilizer border+Concentration improves 3~14 times；Soil is effective in fertile border 2cm
Phosphorus content is significantly higher than commercially available phosphorus ammonium processing 56.3%, illustrates that the fixed speed of alginic acid phosphorus ammonium obviously slows down.
Test example 2: influence of the alginic acid synergistic carrier of the present invention to soil inorganic P form
Alginic acid phosphorus ammonium and commercially available phosphorus ammonium prepared by test example 1 is by equivalent chemical fertilizer phosphorus (P2O50.30g/kg is air-dried
Soil) the commitment principle design experiment, (Fluvo-Aquic Soils, mountain will be air-dried with the 100g for crossing 2mm sieve respectively for examination fertilizer (P, A, B, C)
East Germany state) it is uniformly mixed for examination soil, it is packed into plastic culture cup.Each processing is repeated 4 times, and is contained with adding water weight method to adjust soil
Water seals culture cup, is placed in 25 DEG C of temperature of growth cabinet and keeps humidity culture, according to (Shandong is such as to by weight 20%
Female " soil agrochemistry analysis method " Beijing: Chinese agriculture Science Press, 2000.) standard method of analysis is in culture the
3d, 42d, 97d measure the various forms content of inorganic phosphorus in soil.Testing result is listed in Table 2 below.
Table 2: each form content of inorganic phosphorus in soil when the 3rd day, 42 days, 97 days of culture
In table:
Ca2- P represents available phosphorus, Ca8- P represents potential available phosphorus library, indicates soil P supply ability.It is listed by table 2
As a result it is found that at the 3rd, 42 and 97 day of culture, the soil Ca of alginic acid phosphorus ammonium processing of the present invention2- P average more commercially available phosphorus respectively
Ammonium improves 19%, 29% and 22%；Ca8- P averagely improves 8%, 24% and 14% respectively.It can be seen that alginic acid phosphorus of the present invention
Ammonium can not only reduce phosphorus and fix, and improve soil available phosphorus content, can also supplement Available phosphate.
Test example 3: influence of the alginic acid synergistic carrier of the present invention to growth of wheat roots and vigor
Test specimen: alginic acid synergistic carrier prepared by embodiment 1, embodiment 2 and embodiment 4.Test synergistic carrier exists
Additive amount in Huo Gelan nutrient solution is 0.2g/L, is denoted as A, B, C respectively.
Test procedure: the quartz sand of processing is attached in 500mL Pei Yang Portland (drainage hole is arranged at bottom), Ju Li Portland along 2~
3cm.The crop of processing is colonized in Pei Yang Portland, each processing is repeated 6 times.Every 1 nutrient solution of pouring in 4 days, every time
100mL, to keep certain humidity and nutrient density.
Testing inspection: 21 days after crop emergence, according to " plant physiology experiment guidance ", (South China Science & Engineering University is published
Society, 2015) root system fresh weight and TTC vigor is measured by sampling in standard method.It the results are shown in Table 3.
Influence of the alginic acid synergistic carrier of the present invention of table 3 to growth of wheat roots and vigor
The absorbability of crop root is an important factor for determining utilization rate of fertilizer.The result listed by table 3 is it is found that this hair
Relatively control averagely improves 42.6% and to the wheat root fresh weight and vigor of bright alginic acid synergistic carrier A, B, C processing respectively
33.3%.
Test example 4: influence of the alginic acid phosphorus ammonium of the present invention to wheat yield and phosphate fertilizer utilization efficiency
For trying fertilizer: the alginic acid phosphorus ammonium prepared using the alginic acid synergistic carrier of test example 1,2,4 is denoted as respectively
Humic acid-ammonium phosphate A, humic acid-ammonium phosphate B, humic acid-ammonium phosphate C and commercially available phosphorus ammonium P.
Test procedure: test uses earth pillar planting type, selects the pvc pipe of internal diameter 25cm and high 100cm, its pipe is embedded to
In soil, 2cm above ground level suitable for reading prevents rainfall runoff from flowing into, and lower open-ended is directly contacted with natural soils, and simulation field plants
Training state.Each earth pillar fills soil 55kg.Alginic acid phosphorus ammonium of the present invention and commercially available phosphorus ammonium by etc. full phosphorus amount the commitment principle design it is different
Supplied P level, it is all uniformly mixed to impose in earth pillar 0~30cm soil layer；By sufficient supply principle design, nitrogenous fertilizer is urine for nitrogenous fertilizer, potash fertilizer
Element, amount of application are N 0.2g/kg soil, and potash fertilizer is potassium sulfate, amount of application K2O 0.3g/kg soil.Nitrogenous fertilizer, phosphate fertilizer, potash fertilizer are made
It disposably mixes and is applied in 0~30cm soil for base manure.
Supplied P level is P2O50.10g/kg, 8 repetitions.Full uniform seed is selected, every column sows 30 wheat seeds,
Seedling stage carries out thinning, and every basin finally stays 12 plants.
Phosphate fertilizer utilization efficiency is calculated according to following formula:
Phosphate fertilizer utilization efficiency=(apply phosphorus processing P uptake by plants-and do not apply phosphorus processing P uptake by plants)/phosphorus application amount × 100%].
Its test result is listed in Table 4 below.
Table 4: influence of the alginic acid phosphorus ammonium of the present invention to wheat yield and phosphate fertilizer utilization efficiency
| Processing | Grain yield (g/pot) | Phosphate fertilizer utilization efficiency (%) |
| P | 71.82 | 27.06 |
| A | 78.24 | 33.12 |
| B | 84.00 | 42.67 |
| C | 82.09 | 35.12 |
For the result listed by table 4 it is found that compared with commercially available phosphorus ammonium, the wheat yield of alginic acid phosphorus ammonium A, B, C of the present invention are flat
13.4% is improved, phosphate fertilizer utilization efficiency improves 9.9 percentage points.
It can be seen that after alginic acid synergistic carrier prepared by the present invention is in conjunction with phosphorus ammonium, it can be significant by influencing fertilizer border pH
Slow down the fixation of phosphorus ammonium in alkaline soils, improves P availability, Available phosphate can also be supplemented.Promote crop root
Growth improves root activity, by enhancing Nutrient Absorption, improves phosphate fertilizer utilization efficiency.
Claims (10)
1. a kind of alginic acid synergistic carrier preparation method of the phosphorus ammonium suitable for basic soil, it is characterised in that the step of the preparation method
It is rapid as follows:
A, prepared by alginic acid organic extractant
By 20~50 parts by weight hydramine, 5~10 parts by weight of lemon acid potassium, 5~10 parts by weight potassium salicylates and 5~10 parts by weight second
Glycol is added in the water that 1000~2000 parts by weight temperature are 60~70 DEG C, stirring and dissolving, cooling, and obtaining the alginic acid has
Machine extractant；
B, prepared by alginic acid extracting solution
100 parts by weight seawood meals are added to 800~1500 parts by weight in the alginic acid organic 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, prepared by alginic acid synergistic carrier
10~20 parts by weight benzene carboxylic acids, 5~10 parts by weight sulfonic acid and 0.02~0.05 parts by weight polyethylene glycol are added to 100 weights
Part is measured in the alginic acid extracting solution that step B is obtained, temperature 50 C is heated to, adds 2~3 parts by weight peroxidating diisopropyls
Benzene is then heated to 100 DEG C of temperature, reacts 60~120min at this temperature, adds 2~6 parts by weight of polyoxyethylene ethers,
Cooling, its pH value is adjusted to 4.5~5.5 by used phosphate aqueous solution, obtains the phosphorus ammonium alginic acid synergy suitable for basic soil
Carrier.
2. phosphorus ammonium preparation method according to claim 1, it is characterised in that in step, the hydramine be it is a kind of or
A variety of hydramine selected from monoethanolamine, diethanol amine, triethanolamine or N methyldiethanol amine.
3. phosphorus ammonium preparation method according to claim 1, it is characterised in that in step, will be in 60~240rpm of revolving speed
Under conditions of the obtained solution of stirring and dissolving be cooled to 40 DEG C of temperature or less.
4. phosphorus ammonium preparation method according to claim 1, it is characterised in that in step, hydramine, potassium citrate, bigcatkin willow
The weight ratio of sour potassium, ethylene glycol and water is 28~42:6~9:6~9:6~9:1200~1800.
5. phosphorus ammonium preparation method according to claim 1, it is characterised in that in stepb, the seaweed is brown alga, huge
Algae or yellow tang；The granularity of the seawood meal is less than 2mm.
6. phosphorus ammonium preparation method according to claim 1, it is characterised in that in stepb, in 1000~3000rpm of revolving speed
Under conditions of be centrifugated 10~60min.
7. phosphorus ammonium preparation method according to claim 1, it is characterised in that in stepb, the benzene carboxylic acid is benzene first
Acid, phenylacetic acid, salicylic acid or acetylsalicylic acid.
8. phosphorus ammonium preparation method according to claim 1, it is characterised in that in step C, the sulfonic acid be benzene sulfonic acid,
Naphthalene sulfonic acids, methane sulfonic acid or tarine.
9. phosphorus ammonium preparation method according to claim 1, it is characterised in that in step C, the peroxophosphoric acid aqueous solution
Concentration is 1~5mol/L.
10. phosphorus ammonium preparation method according to claim 1, it is characterised in that, will after addition polyoxyethylene ether in step C
Its solution is cooled to 10~40 DEG C of temperature.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103274852A (en) * | 2013-06-17 | 2013-09-04 | 中国农业科学院农业资源与农业区划研究所 | Algae synergistic ammonium phosphate fertilizer and preparation method thereof |
| CN104478597A (en) * | 2014-12-16 | 2015-04-01 | 五洲丰农业科技有限公司 | Process for producing ureaformaldehyde slow release fertilizer with co-production of alginic acid liquid fertilizer |
| CN107337504A (en) * | 2017-06-13 | 2017-11-10 | 安徽奥利休闲农业发展有限公司 | Excellent magnet organic fertilizer material containing sodium alginate of a kind of retain water and nutrients and preparation method thereof |
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2018
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274852A (en) * | 2013-06-17 | 2013-09-04 | 中国农业科学院农业资源与农业区划研究所 | Algae synergistic ammonium phosphate fertilizer and preparation method thereof |
| CN104478597A (en) * | 2014-12-16 | 2015-04-01 | 五洲丰农业科技有限公司 | Process for producing ureaformaldehyde slow release fertilizer with co-production of alginic acid liquid fertilizer |
| CN107337504A (en) * | 2017-06-13 | 2017-11-10 | 安徽奥利休闲农业发展有限公司 | Excellent magnet organic fertilizer material containing sodium alginate of a kind of retain water and nutrients and preparation method thereof |
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