CN109369225A - A kind of phosphorus ammonium Humic acid synergistic support preparation method suitable for basic soil - Google Patents
A kind of phosphorus ammonium Humic acid synergistic support preparation method suitable for basic soil Download PDFInfo
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- CN109369225A CN109369225A CN201811328682.3A CN201811328682A CN109369225A CN 109369225 A CN109369225 A CN 109369225A CN 201811328682 A CN201811328682 A CN 201811328682A CN 109369225 A CN109369225 A CN 109369225A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
- C05F11/02—Other organic fertilisers from peat, brown coal, and similar vegetable deposits
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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
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- C05G3/80—Soil conditioners
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Abstract
The present invention relates to a kind of phosphorus ammonium Humic acid synergistic support preparation method suitable for basic soil, which includes the preparation of humic acid organic extractant, the preparation of humic acid extracting solution and the preparation of Humic acid synergistic carrier.Humic acid synergistic carrier of the present invention in conjunction with urea after can significantly slow the fixation of phosphorus ammonium in alkaline soils by influencing fertilizer border pH, raising P availability can also supplement Available phosphate.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 35% or more.Compared with commercially available phosphorus ammonium, the wheat yield of humic acid-ammonium phosphate of the present invention averagely improves 12.6%, and phosphate fertilizer utilization efficiency improves 9.34 percentage points.
Description
[technical field]
The present invention relates to technical field of fertilizer production.More particularly it relates to a kind of phosphorus ammonium suitable for basic soil
With Humic acid synergistic support 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 pH6~7, available phosphorus
Concentration highest.The calcium and magnesium ion content of basic soil is high, is 80% or more to be fixed after phosphorus enters soil, in 3 days, cannot be by
Crop is absorbed and utilized.By greatly improving phosphate fertilizer utilization efficiency, Phosphorus Fertilizer Rates are reduced, are to promote China's phosphate fertilizer resources
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 humic acid, can be certain
Phosphorus is reduced in degree to fix, and improves phosphorus amount.But the extracting method of traditional humic acid mainly utilizes sodium hydroxide, hydrogen-oxygen
Change the inorganic bases such as potassium, ammonium hydroxide to extract, forms fulvo acid salt through kickback, humic acid original structure is destroyed, simultaneously
Since alkalinity is stronger, should not generally be applied on basic soil.
CN103274798A discloses a kind of Humic acid synergistic ammonium phosphate and preparation method thereof, with sig water extract weathered coal/
Lignite humic acid prepares Humic acid synergistic liquid, by it in conjunction with ammonium phosphate production process, produces Humic acid synergistic ammonium phosphate, has suppression
System reduces the fixed effect of phosphorus.But it yet there are no the phosphorus ammonium Humic acid synergistic carrier patent Shen in relation to being suitable for basic soil
Please and its related data.
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 phosphorus ammonium Humic acid synergistic support preparation methods suitable for basic soil.
[technical solution]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of phosphorus ammonium Humic acid synergistic support preparation methods suitable for basic soil.
The step of preparation method, is as follows:
A, prepared by humic 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 rotten plant
Sour organic extractant；
B, prepared by humic acid extracting solution
It is organic that 100 parts by weight humic acid minerals raw materials are added to the humic acid that 800~1500 parts by weight are obtained in step A
In extractant, its temperature is then gradually increased to 90 DEG C under stiring, and keeps 40~60min at this temperature, it is then cold
But it to room temperature, is centrifugated, sediment discards, and obtains the humic acid extracting solution；
C, prepared by Humic 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 humic 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, and it is rotten to obtain a kind of phosphorus ammonium suitable for basic soil
Phytic acid 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 the conditions of 60~180rpm of revolving speed
It dissolves obtained solution 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 humic acid minerals raw material is weathered coal
Or lignite, their granularity are 150~300 mesh.
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 phosphorus ammonium Humic acid synergistic support preparation methods suitable for basic soil.
The step of preparation method, is as follows:
A, the preparation of humic 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 rotten plant
Sour organic 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 humic acid minerals raw material, the water solubility of this raw material be improved, to facilitate
Improve the recovery rate that humic acid is extracted from humic acid minerals raw material.
The hydramine is one or more selected from monoethanolamine, diethanol amine, triethanolamine or N methyldiethanol amine
Hydramine.The hydramine is all current market sales of product, such as 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)
The product of sale.
Potassium citrate is to increase humic acid COO preparing the basic role in humic acid organic extractant-Functional group improves
Humic acid recovery rate.The potassium citrate that the present invention uses is current market sales of product, such as by Xi'an favour nation biology work
The product that journey Co., Ltd is sold with trade name potassium citrate.
Potassium salicylate is to increase the carboxyl structure containing aromatic ring preparing the basic role in humic acid organic extractant, makes corruption
Phytic acid carrier has anti-adversity.The potassium salicylate that the present invention uses is current market sales of product, such as by Wuhan shellfish
The product that Er Ka biological medicine Co., Ltd is sold with trade name potassium salicylate.
Ethylene glycol can enhance humic 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,
Humic 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 humic acid liquid bubble,
Tiny impurity is mixed in humic acid liquid, the humic acid liquid purity 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 humic 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 humic 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 humic acid carrier effect effect is limited；If the dosage of potassium salicylate is higher than 10 parts by weight, it is organic humic 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 humic 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 humic 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.
When other raw material dosages are in the range, if the dosage of water is lower than 1000 parts by weight, it can be planted because of corruption
Sour organic extractant excessive concentration, water consumption is low, and solubility is limited, extracts the decline of humic acid efficiency；If the dosage of water is higher than
, then can be too low because of humic acid organic extractant concentration when 2000 parts by weight, also result in the decline of humic 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 humic acid organic extractant stability and subsequent quantizatiion preparation.
B, the extraction of humic acid
It is organic that 100 parts by weight humic acid minerals raw materials are added to the humic acid that 800~1500 parts by weight are obtained in step A
In extractant, its temperature is then gradually increased to 90 DEG C under stiring, and keeps 40~60min at this temperature, it is then cold
But it to room temperature, is centrifugated, sediment discards, and obtains the humic acid extracting solution.
According to the present invention, the humic acid minerals raw material is weathered coal or lignite.
Weathered coal be earth's surface or shallow-layer lignite, bituminous coal and anthracite be subjected to for a long time atmosphere, sunlight, sleet, underground water with
And the product of the comprehensive functions such as minerals erosion.Weathered coal humic acid total content is usually 30~70%, reach as high as 80% with
On.
Lignite is the minimum pit coal of degree of coalification, a kind of brownish black between peat and pitch coal, lacklustre
Rudimentary coal.
According to the present invention, weathered coal or lignite are crushed using existing conventional crushing plant, collect granularity be 150~
The humic acid minerals raw material of 300 mesh carries out preparing humic acid extracting solution.
In the present invention, when humic acid minerals raw material is 100 parts by weight, if the humic acid organic extractant dosage is low
In 800 parts by weight, then it will lead to that liquid is thick to be difficult to carry out subsequent centrifugal treating；If the humic acid organic extractant dosage
Higher than 1500 parts by weight, then the water content that will lead to the humic acid extracting solution of extraction is high, influences Humic acid synergistic carrier in urea
In application.Therefore, it is appropriate that the humic acid organic extractant dosage, which is 800~1500 parts by weight,.
In this step, in the case where revolving speed is the stirring of 100~200rpm that humic acid minerals raw material and humic acid is organic
The temperature of extractant mixture is gradually increased to 90 DEG C, and keeps 40~60min at this temperature.When its Extracting temperature and extraction
Between be more than the range be worthless.If extraction time is shorter than 40min, humic acid is extracted not exclusively, causes humic acid
Loss；If extraction time is more than 60min, the energy consumption for extracting humic acid is caused to increase, increased costs.Therefore, humic acid mentions
Take the time be 40~60min be feasible.
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 is the product sold on existing market, such as by ShangHai City centrifugal Machine Institute
Co., Ltd separates the product of sleeping spiral shell sedimentation centrifuge sale with trade name two-phase.
C, the preparation of Humic 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 humic 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, and it is rotten to obtain a kind of phosphorus ammonium suitable for basic soil
Phytic acid synergistic carrier
In the present invention, in the presence of with cumyl peroxide initiator and polyglycol surfactants, benzene carboxylic
The humic acid in humic acid extracting solution that acid is obtained with step B carries out graft reaction, then further increases the acidity of humic acid
Functional group's type and quantity, 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
Decomposition rate in earth.
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), it can enhance humic acid
The water-soluble 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 to sell currently on the market
Product, such as sold by Shanghai Yi He Biotechnology Co., Ltd with trade name benzene sulfonic acid product, by Shanghai shriek chemical industry
Product that Co., Ltd is sold with trade name 2- naphthalene sulfonic acids, by Wuhan sea Dehua work Development Co., Ltd with trade name methane sulfonic acid
The product of sale, the product sold by Jiangsu Cai Wei Biotechnology Co., Ltd with trade name β-aminoethanesulfonic acid.
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 humic acid to precipitate；
Therefore, it is appropriate that benzene carboxylic acid dosage, which is 10~20 parts by weight,；
It, can be to raising humic acid 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, benzene carboxylic acid dosage is 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 humic 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
The metal ion that one step slows down, reduces in the soil liquid is contacted with phosphorus ammonium.Peroxophosphoric acid is that one kind contains phosphoric acid and several polyphosphoric acids
Mineral acid, it has extremely strong sequestering power to foreign metal ion, therefore, the pH of its not only adjustable system, but also can
To enhance the stability of Humic acid synergistic carrier by calcium, the magnesium plasma in chelating humic acid.
In Humic acid synergistic carrier preparation, polyoxyethylene ether dosage is 2~6 parts by weight, if polyoxyethylene ether is used
Amount 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, synergistic 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 10~40 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 Humic acid synergistic carrier of the present invention is as follows:
During existing production of ammonium phosphate, the obtained Humic 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 carrier containing Humic acid synergistic
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 Humic acid synergistic carriers.If
Humic 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 Humic 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, Humic acid synergistic carrier of the present invention organic acidity functional group abundant can reduce particle phospho-ammonium fertilizer border pH0.3~
1.4 units, the resiliency of enhanced fertilizer border soil；
2, Humic acid synergistic carrier of the present invention can reduce the fixation of phosphorus in the soil, soil in conjunction with the metal ions such as calcium, magnesium
23% and 16% is respectively increased in two phosphorus of earth calcium and eight phosphorus of calcium, and phosphorus and middle microelement in activating soil.
3, Humic acid synergistic carrier of the present invention stimulates root growth, improves root activity, promotes absorption of the crop to phosphorus element,
Further increase phosphate fertilizer utilization efficiency.Wheat root weight and vigor improve 35% or more.Compared with commercially available phosphorus ammonium, the present invention is rotten
The wheat yield of phytate phosphorus ammonium averagely improves 12.6%, and phosphate fertilizer utilization efficiency improves 9.34 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 Humic acid synergistic carrier
The implementation steps of the embodiment are as follows:
A, prepared by humic 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 humic acid organic extractant；
B, prepared by humic acid extracting solution
The weathered coal humic acid raw mineral materials that 100 parts by weight granularities are 150 mesh is added to 1250 parts by weight to obtain in step A
To humic acid organic extractant in, its temperature is then gradually increased to 90 DEG C in the case where revolving speed is the stirring of 100rpm, and at this
40min is kept at a temperature, is then cooled to room temperature, 10min is centrifugated under conditions of revolving speed 3000rpm, sediment is abandoned
It goes, obtains the humic acid extracting solution；
C, prepared by Humic 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 humic 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 Humic acid synergistic carrier.
Embodiment 2: it is suitable for basic soil phosphorus ammonium and is prepared with Humic acid synergistic carrier
The implementation steps of the embodiment are as follows:
A, prepared by humic 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 120rpm, obtained solution is cooled to temperature
40 DEG C hereinafter, obtain the humic acid organic extractant；
B, prepared by humic acid extracting solution
The lignite humic acid raw mineral materials that 100 parts by weight granularities are 200 mesh is added to 800 parts by weight to obtain in step A
Humic acid organic extractant in, its temperature is then gradually increased to 90 DEG C in the case where revolving speed is the stirring of 130rpm, and at this
At a temperature of keep 48min, be then cooled to room temperature, be centrifugated 60min under conditions of revolving speed 1000rpm, sediment discards,
Obtain the humic acid extracting solution；
C, prepared by Humic 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 humic 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 20 DEG C of temperature, 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 Humic acid synergistic carrier.
Embodiment 3: it is suitable for basic soil phosphorus ammonium and is prepared with Humic acid synergistic carrier
The implementation steps of the embodiment are as follows:
A, prepared by humic 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 humic acid organic extractant；
B, prepared by humic acid extracting solution
The lignite humic acid raw mineral materials that 100 parts by weight granularities are 250 mesh is added to 1500 parts by weight to obtain in step A
Humic acid organic extractant in, its temperature is then gradually increased to 90 DEG C in the case where revolving speed is the stirring of 180rpm, and at this
At a temperature of keep 60min, be then cooled to room temperature, be centrifugated 40min under conditions of revolving speed 1600rpm, sediment discards,
Obtain the humic acid extracting solution；
C, prepared by Humic 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 humic 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 30
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 Humic acid synergistic carrier.
Embodiment 4: it is suitable for basic soil phosphorus ammonium and is prepared with Humic acid synergistic carrier
The implementation steps of the embodiment are as follows:
A, prepared by humic 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 240rpm, and obtained solution is cooling
To 40 DEG C of temperature hereinafter, obtaining the humic acid organic extractant；
B, prepared by humic acid extracting solution
The weathered coal humic acid raw mineral materials that 100 parts by weight granularities are 300 mesh is added to 1050 parts by weight to obtain in step A
To humic acid organic extractant in, its temperature is then gradually increased to 90 DEG C in the case where revolving speed is the stirring of 200rpm, and at this
55min is kept at a temperature, is then cooled to room temperature, 30min is centrifugated under conditions of revolving speed 2400rpm, sediment is abandoned
It goes, obtains the humic acid extracting solution；
C, prepared by Humic 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 humic 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,
40 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 Humic acid synergistic carrier.
Two, test example
Test example 1: influence of the Humic acid synergistic carrier of the present invention to phospho-ammonium fertilizer border soil pH and available phosphorus
Sample preparation: the method described according to this specification, the corruption prepared using embodiment 1, embodiment 2 and embodiment 3
Phytic acid synergistic carrier prepares the phosphorus ammonium containing the by weight 5% Humic acid synergistic carrier respectively.150g preparation is weighed respectively
Phosphorus ammonium particle, be placed in length × width × height=5cm × 5cm × 5cm, aperture is to obtain just in the stainless steel cloth mold of 0.5mm
Cube humic acid-ammonium phosphate A (embodiment 1), square humic acid-ammonium phosphate B (embodiment 2), square humic acid-ammonium phosphate C (embodiment
3) sample.(phosphorylcholine group, P are opened in Guizhou with commercially available phosphorus ammonium2O5Content 46%) it is control sample P.
Test procedure: control sample P, humic acid-ammonium phosphate A, B, C are placed in the stone that water content is by weight 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 temperature.After culture,
It is cut out respectively with blade apart from square humic acid-ammonium phosphate edge 1.5-2.0cm, 1.0-1.5cm, 0.5-1.0cm, 0-0.5cm
Soil.According to (for example female " soil agrochemistry analysis method " Beijing, Shandong: Chinese agriculture Science Press, 2000.) standard scores
Analysis method tests pH, available phosphorus content in these square phospho-ammonium fertilizer border soil.Its testing result is listed in Table 1 below.
Table 1: the fertile border soil pH of humic acid-ammonium phosphate and commercially available phosphorus ammonium, available phosphorus content testing result
Fertile border is the initial period of fertilizer conversion, decides the phosphorus fixed ammonium process in later period.These test results show this
The Humic acid synergistic carrier of invention preparation can significantly reduce the soil within phospho-ammonium fertilizer border soil pH, especially reduction fertilizer border 1cm
PH reduces by 0.3~1.4 pH unit of amplitude, i.e., the H in the fertile border soil liquid+Concentration improves 3~14 times；Soil in fertile border 2cm
Available phosphorus content is significantly higher than commercially available phosphorus ammonium processing, illustrates that the fixed speed of humic acid-ammonium phosphate obviously slows down.
Test example 2: influence of the Humic acid synergistic carrier of the present invention to soil inorganic P form
Humic acid-ammonium phosphate 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.It is repeated 4 times, gravimetric method is used to adjust soil moisture content to weight
Meter 20%, seal culture cup, be placed in temperature be 25 DEG C growth cabinet keep humidity culture, after incubation 3d, 42d,
97d sampling, according to (for example female " soil agrochemistry analysis method " Beijing, Shandong: Chinese agriculture Science Press, 2000.) standard
Analysis method measures various forms content of inorganic phosphorus.These testing results are 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, Al-P generation
Phosphorus, Fe-P of the table in conjunction with aluminium represent phosphorus, Ca in conjunction with iron10- P represents the phosphorus for being difficult to discharge from soil.
The result listed by table 2 is it is found that in culture the 3rd, 42 and 97 day, the soil Ca of humic acid-ammonium phosphate processing2- P difference
19%, 29% and 22% is averagely improved than commercially available phosphorus ammonium；Ca8- P averagely improves 8%, 24% and 14% respectively.It can be seen that rotten
Phytate phosphorus 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 Humic acid synergistic carrier of the present invention to growth of wheat roots and vigor
The Humic acid synergistic carrier prepared using embodiment 1, embodiment 2 and embodiment 4 studies rotten plant using sand culture test
Influence of the sour synergistic carrier to growth of wheat roots and vigor.Additive amount of the synergistic carrier in Huo Gelan nutrient solution is 0.2g/
L is denoted as A, B, C respectively, compares as 0g/L.The quartz sand of processing is attached in 500mL Pei Yang Portland (drainage hole is arranged at bottom), distance
Portland is along 2~3cm.The crop of processing is colonized in Pei Yang Portland, is repeated 6 times.Every 1 nutrient solution of pouring in 4 days, each 100mL,
To keep certain humidity and nutrient density.21 days after crop emergence, according to " plant physiology experiment guidance " (south China science and engineering
University press, 2015) root system fresh weight and TTC vigor is measured by sampling in standard method.Its testing result is listed in Table 3 below.
Table 3: influence of the Humic acid synergistic carrier of the present invention 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 rotten plant
The wheat root fresh weight and vigor of sour synergistic carrier A, B, C processing averagely improve 46.5% and 35.2% than compareing respectively.
Test example 4: influence of the humic acid-ammonium phosphate of the present invention to wheat yield and phosphate fertilizer utilization efficiency
For examination fertilizer be using by embodiment 1,2,4 humic acid carrier prepare humic acid-ammonium phosphate (be denoted as respectively A, B,
C) and commercially available phosphorus ammonium (Guizhou open phosphorylcholine group production, contain P2O546%, it is denoted as P) as control sample.Test uses earth pillar cultivation side
Formula is selected the pvc pipe of internal diameter 25cm and high 100cm, its pipe is buried in the earth, 2cm above ground level suitable for reading prevents rainfall runoff stream
Enter, lower open-ended is directly contacted with natural soils, simulates field cultivation state.Each earth pillar fills soil 55kg.Humic acid of the present invention
Phosphorus ammonium and commercially available phosphorus ammonium by etc. full phosphorus amount the commitment principle design different Supplied P levels, it is all uniformly mixed to impose on earth pillar 0~30cm soil
In layer；By sufficient supply principle design, nitrogenous fertilizer is urea for nitrogenous fertilizer, potash fertilizer, and amount of application is N0.2g/kg soil, and potash fertilizer is potassium sulfate,
Amount of application is K2O0.3g/kg soil.Nitrogenous fertilizer, phosphate fertilizer, potash fertilizer are used as base manure disposably to mix and apply in 0~30cm soil.
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 humic acid-ammonium phosphate 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 | 78.54 | 33.42 |
| B | 83.00 | 41.67 |
| C | 81.09 | 34.12 |
The result listed by table 4 utilizes the phosphorus humic acid phosphorus of humic acid carrier of the present invention preparation it is found that compared with commercially available phosphorus ammonium
The wheat yield of ammonium A, B, C averagely improve 12.6%, and phosphate fertilizer utilization efficiency improves 9.34 percentage points.
It can be seen that after Humic 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.Humic acid of the present invention
Synergistic carrier can promote crop root growth, improve root activity, by enhancing Nutrient Absorption, improve phosphate fertilizer utilization efficiency.
Claims (10)
1. one kind is suitable for basic soil phosphorus ammonium Humic acid synergistic support preparation method, it is characterised in that the step of the preparation method
It is as follows:
A, prepared by humic 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 humic acid has
Machine extractant；
B, prepared by humic acid extracting solution
100 parts by weight humic acid minerals raw materials are added to the organic extraction of humic acid that 800~1500 parts by weight are obtained in step A
In agent, its temperature is then gradually increased to 90 DEG C under stiring, and keeps 40~60min at this temperature, is then cooled to
Room temperature, centrifuge separation, sediment discard, and obtain the humic acid extracting solution
C, prepared by Humic 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 humic 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, obtains a kind of phosphorus ammonium humic acid suitable for basic soil by used phosphate aqueous solution
Synergistic carrier.
2. Humic acid synergistic support preparation method according to claim 1, it is characterised in that in step, the alcohol
Amine is one or more hydramine selected from monoethanolamine, diethanol amine, triethanolamine or N methyldiethanol amine.
3. Humic acid synergistic support 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 60~240rpm is cooled to 40 DEG C of temperature or less.
4. Humic acid synergistic support preparation method according to claim 1, it is characterised in that in step, hydramine, lemon
Sour potassium, potassium salicylate, ethylene glycol and water weight ratio be 28~42:6~9:6~9:6~9:1200~1800.
5. Humic acid synergistic support preparation method according to claim 1, it is characterised in that in stepb, the corruption
Phytic acid raw mineral materials is weathered coal or lignite, their granularity is 150~300 mesh.
6. Humic acid synergistic support preparation method according to claim 1, it is characterised in that in stepb, in revolving speed
10~60min is centrifugated under conditions of 1000~3000rpm.
7. Humic acid synergistic support preparation method according to claim 1, it is characterised in that in stepb, the benzene
Carboxylic acid is benzoic acid, phenylacetic acid, salicylic acid or acetylsalicylic acid.
8. Humic acid synergistic support preparation method according to claim 1, it is characterised in that in step C, the sulphur
Acid is benzene sulfonic acid, naphthalene sulfonic acids, methane sulfonic acid or tarine.
9. Humic acid synergistic support preparation method according to claim 1, it is characterised in that described to cross phosphorus in step C
The concentration of aqueous acid is 1~5mol/L.
10. Humic acid synergistic support preparation method according to claim 1, it is characterised in that in step C, polyoxy is added
Its solution is cooled to 10~40 DEG C of temperature after vinethene.
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| WO2020093847A1 (en) * | 2018-11-09 | 2020-05-14 | 中国农业科学院农业资源与农业区划研究所 | Preparation method for ammonium phosphate containing humic acid synergistic carrier suitable for alkaline soil |
| RU2732814C1 (en) * | 2020-04-02 | 2020-09-22 | Общество с ограниченной ответственностью «ТОРФОПРОДУКТ» | Method for production of liquid extract of vegetal raw materials |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101063037A (en) * | 2007-04-14 | 2007-10-31 | 新疆农业科学院土壤肥料研究所 | Organic macromolecular soil phosphor element activator and preparation method thereof |
| CN103274798A (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 | Humic acid synergistic ammonium phosphate and preparation method thereof |
| CN108503430A (en) * | 2018-04-24 | 2018-09-07 | 吴刚 | A kind of preparation method of humic acid system suspension type liquid fertilizer |
-
2018
- 2018-11-09 CN CN201811328682.3A patent/CN109369225A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101063037A (en) * | 2007-04-14 | 2007-10-31 | 新疆农业科学院土壤肥料研究所 | Organic macromolecular soil phosphor element activator and preparation method thereof |
| CN103274798A (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 | Humic acid synergistic ammonium phosphate and preparation method thereof |
| CN108503430A (en) * | 2018-04-24 | 2018-09-07 | 吴刚 | A kind of preparation method of humic acid system suspension type liquid fertilizer |
Non-Patent Citations (1)
| Title |
|---|
| 化学工业部科学技术情报研究所: "《中国化肥手册 生产 流通 施用》", 31 March 1992 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020093847A1 (en) * | 2018-11-09 | 2020-05-14 | 中国农业科学院农业资源与农业区划研究所 | Preparation method for ammonium phosphate containing humic acid synergistic carrier suitable for alkaline soil |
| RU2732814C1 (en) * | 2020-04-02 | 2020-09-22 | Общество с ограниченной ответственностью «ТОРФОПРОДУКТ» | Method for production of liquid extract of vegetal raw materials |
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