CN116199536A - Preparation method of acidic water-soluble composite phosphate - Google Patents

Preparation method of acidic water-soluble composite phosphate Download PDF

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Publication number
CN116199536A
CN116199536A CN202211728218.XA CN202211728218A CN116199536A CN 116199536 A CN116199536 A CN 116199536A CN 202211728218 A CN202211728218 A CN 202211728218A CN 116199536 A CN116199536 A CN 116199536A
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Prior art keywords
phosphoric acid
acidic water
slurry
composite phosphate
soluble composite
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CN202211728218.XA
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Inventor
刘旭
马培根
陶绍程
赵强
汤建伟
刘松林
付勇
文小兵
谢娟
杨俊�
张俊
张群
王凤霞
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Wengfu Dazhou Chemical Co ltd
Zhengzhou University
Wengfu Group Co Ltd
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Wengfu Dazhou Chemical Co ltd
Zhengzhou University
Wengfu Group Co Ltd
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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
    • C05G1/00—Mixtures of fertilisers belonging individually to different subclasses of C05
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B11/00—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes
    • C05B11/04—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid
    • C05B11/10—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid using orthophosphoric acid
    • 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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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Soil Sciences (AREA)
  • Fertilizers (AREA)

Abstract

The invention discloses a preparation method of an acidic water-soluble composite phosphate, which specifically comprises the following steps: step 1: mixing phosphoric acid or/and a phosphorus-containing compound solution with urea and an additive; control P 2 O 5 : the molar ratio of N is 0.5-1.5; p (P) 2 O 5 M is the sum of the mole numbers of sulfate radical, chloride ion and nitrate radical, wherein the mole ratio of M is 2-10; heating at 50-100 ℃ until urea is completely dissolved to obtain mixed slurry; step 2: concentrating the slurry obtained in the step 1 at 60-130 ℃ and 0.01-0.1Mpa until the mass percentage of free water in the slurry is 3-5%; step 3: and (3) cooling the concentrated slurry obtained in the step (2) to 40-95 ℃. The invention can effectively solve the technical problem of low phosphorus yield in the prior art; at the same time, phosphorus in phosphoric acid can be neutralizedThe prepared acidic water-soluble composite phosphate is fully water-soluble phosphate, can greatly improve work efficiency, and can be widely applied to improvement of alkaline soil due to acid development.

Description

Preparation method of acidic water-soluble composite phosphate
Technical Field
The invention relates to the technical field of preparation of composite phosphate, in particular to a preparation method of acidic water-soluble composite phosphate.
Background
The fertilizer grade phosphoric acid, the raffinate phosphoric acid and the urea phosphate mother liquor contain a large amount of hetero ions, and the water-soluble fertilizer prepared by taking the hetero ions as raw materials is usually prepared into ammonium polyphosphate by adopting a neutralization, extraction, crystallization and other impurity removal modes. By adopting the impurity removal modes, on one hand, a large amount of low-value phosphate fertilizer, raffinate acid or mother liquor is produced, and the low-value byproducts have high phosphorus content, but poor water solubility and extremely low economic value; on the other hand, a large amount of medium trace elements in the raw materials are transferred to byproducts in the impurity removal process. Because the content of impurity cations in the raffinate acid and the urea phosphate mother solution is more, the chelating ability of ammonium polyphosphate is limited, and the impurity cations can not be completely chelated, so that the water solubility of the prepared product is poor. Meanwhile, the existing urea phosphate preparation generally adopts cooling crystallization, and on one hand, the cooling crystallization is difficult to treat due to low crystallization yield to generate a large amount of mother liquor; on the other hand, the impurity ions are enriched in the mother solution, so that the product is difficult to reach the standard, the mother solution is discharged, and the yield of phosphorus is reduced.
The publication number is: the invention of CN102674284A discloses a method for producing industrial monoammonium phosphate and co-producing fertilizer-grade monoammonium phosphate by using raffinate acid, wherein the extract Yu Suan is subjected to ammoniation reaction with ammonia, slurry is filtered, filtrate is concentrated and crystallized to obtain monoammonium phosphate, and filter residues are dried to obtain agricultural monoammonium phosphate. The method generates a large amount of fertilizer-grade monoammonium phosphate, so that the phosphorus yield of the water-soluble monoammonium phosphate is lower, and a large amount of medium trace elements in the raffinate acid enter the fertilizer-grade monoammonium phosphate to be converted into an inefficient utilization form.
The publication number is: the invention of CN113248322A discloses a preparation method of a soluble medium trace element fertilizer, which is characterized in that medium trace elements are added into urea phosphate mother liquor, and condensed at high temperature under the action of condensing agent urea to obtain the soluble medium trace element fertilizer. The method for treating the urea phosphate mother liquor has the advantages of higher temperature requirement, higher energy consumption, release of a large amount of ammonia gas and carbon dioxide, lower urea rate, poor economical efficiency and environmental protection, and poor water solubility of the obtained ammonium polyphosphate product.
In the experimental study of urea phosphate and phosphorus magnesium fertilizer prepared from the byproduct raffinate acid of wet phosphoric acid solvent extraction in the prior art, urea phosphate is prepared by taking the raffinate acid as a raw material through a crystallization method, the primary crystallization yield is 57.33, the secondary crystallization yield is 17%, and the crystallization time is 8 hours. The method adopts the raffinate acid to prepare the urea phosphate water-soluble fertilizer, which has long time, low phosphorus yield and a large amount of mother liquor to be treated by preparing the phosphorus-magnesium fertilizer.
Disclosure of Invention
The invention aims to provide a preparation method of an acidic water-soluble composite phosphate, which can effectively solve the technical problems of more low-value byproducts, low phosphorus yield and incapability of water-soluble and efficient utilization of trace elements in a phosphorus source in the existing phosphorus water-soluble fertilizer technology.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the acidic water-soluble composite phosphate comprises the following steps:
step 1:
mixing phosphoric acid or/and a phosphorus-containing compound solution with urea and an additive;
control P 2 O 5 : the molar ratio of N is 0.5-1.5;
P 2 O 5 m is the sum of the mole numbers of sulfate radical, chloride ion and nitrate radical, wherein the mole ratio of M is 2-10;
heating at 50-100 ℃ until urea is completely dissolved to obtain mixed slurry;
step 2:
concentrating the slurry obtained in the step 1 at 60-130 ℃ and 0.01-0.1Mpa until the mass percentage of free water in the slurry is 3-5%;
step 3:
cooling the concentrated slurry obtained in the step 2 to 40-95 ℃, adding a curing agent for mixing, wherein the addition amount is 0-10% of the concentrated slurry, and cooling and curing for 5-120min to obtain a semi-finished product;
step 4:
and (3) drying the semi-finished product obtained in the step (3) at 50-90 ℃ under normal pressure until the free water content is 2-3%, crushing and packaging to obtain the powder acidic water-soluble composite phosphate product with the pH value of 1.8-3.5.
In the step 1, phosphoric acid is one or a mixture of industrial grade phosphoric acid, fertilizer grade phosphoric acid and raffinate phosphoric acid, and the raffinate phosphoric acid is a byproduct of the process of purifying and preparing the industrial grade phosphoric acid by a wet-process phosphoric acid solvent extraction method.
Wherein, in the step 1, the phosphorus-containing compound solution is urea phosphate mother liquor which is a byproduct when phosphoric acid is used for preparing urea phosphate products.
Further defined, the additive is one or more of hydrochloric acid, hydrochloride, sulfuric acid, sulfate, nitric acid, nitrate.
In the step 2, the slurry obtained in the step 1 is concentrated under the conditions that the temperature is 100 ℃ and the pressure is 0.01-0.1Mpa, and the concentration is carried out until the mass percentage of free water in the slurry is 4%.
In the step 3, the curing agent is as follows: NH (NH) 4 H 2 PO 4 、Na 2 CO 3 、NaHCO 3 、NH 4 Cl、(NH 4 ) 2 HPO 4 、CaCO 3 、NH 4 NO 3 、MgCO 3 、(NH 4 ) 2 SO 4 、NH 4 HCO 3 One or more of the following.
Compared with the prior art, the invention has the following beneficial effects:
the slurry is directly solidified after being concentrated, medium trace element ions rich in the raw materials completely enter the product, and the acid development performance of the product keeps good water solubility under the condition of rich medium trace elements. On the other hand, the phosphoric acid with proper impurity content can be directly used for preparing the acidic water-soluble composite phosphate product which mainly contains nitrogen and phosphorus nutrients and is rich in medium and trace elements under the condition that no mother liquor is produced by the method, so that the current production process of the phosphorus water-soluble fertilizer is rebuilt, the process flow is shortened, and the phosphorus yield is improved.
Meanwhile, the invention can fully utilize phosphorus in phosphoric acid and various medium and trace elements, and the prepared acidic water-soluble composite phosphate is full-water-soluble phosphate, so that the utilization rate can be greatly improved, and the acidic water-soluble composite phosphate can be widely applied to the improvement of alkaline soil due to the acid development.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram of the present invention.
Detailed Description
Hereinafter, only certain exemplary embodiments are briefly described. As will be recognized by those of skill in the pertinent art, the described embodiments may be modified in numerous different ways without departing from the spirit or scope of the embodiments of the present invention.
Example 1
Referring to fig. 1, the embodiment discloses a preparation method of an acidic water-soluble composite phosphate, which specifically comprises the following steps:
step 1: mixing phosphoric acid or/and a phosphorus-containing compound solution with urea and an additive;
control P 2 O 5 : the molar ratio of N is 0.5-1.5;
P 2 O 5 m is the sum of the mole numbers of sulfate radical, chloride ion and nitrate radical, wherein the mole ratio of M is 2-10;
heating at 50-100deg.C until urea is completely dissolved to obtain mixed slurry, preferably 80deg.C;
step 2:
concentrating the slurry obtained in the step 1 at 60-130 ℃ and 0.01-0.1Mpa until the mass percentage of free water in the slurry is not higher than 5%, specifically 3-5%, preferably 4%;
step 3:
cooling the concentrated slurry obtained in the step 2 to 40-95 ℃, adding a curing agent for mixing, wherein the addition amount is 0-10% of the concentrated slurry, and cooling and curing for 5-120min to obtain a semi-finished product;
in this example, the temperature was reduced to 80℃and the curing agent was added in an amount of 5% to the concentrated slurry, with a cooling and curing time of 60 minutes.
Step 4:
drying the semi-finished product obtained in the step 3 at 50-90 ℃, preferably 70 ℃ and normal pressure until the free water content is not higher than 3%, specifically 2-3%, preferably 2.5%, crushing and packaging to obtain the powder acidic water-soluble composite phosphate product with the pH value of 1.8-3.5.
In the step 1, phosphoric acid is one or a mixture of industrial grade phosphoric acid, fertilizer grade phosphoric acid and raffinate phosphoric acid, and the raffinate phosphoric acid is a byproduct of the process of purifying and preparing the industrial grade phosphoric acid by a wet-process phosphoric acid solvent extraction method.
In this example, the phosphoric acid is raffinate phosphoric acid.
Further optimizing, in the step 1, the phosphorus-containing compound solution is urea phosphate mother liquor which is a byproduct when phosphoric acid is used for preparing urea phosphate products.
Wherein the additive is one or more of hydrochloric acid, hydrochloride, sulfuric acid, sulfate, nitric acid and nitrate. In this embodiment, the additive is hydrochloric acid.
Wherein, in the step 2, the slurry obtained in the step 1 is concentrated under the conditions of the temperature of 100 ℃ and the pressure of 0.01-0.1Mpa until the mass percentage of free water in the slurry is 4%.
Further preferably, in step 3, the curing agent is: NH (NH) 4 H 2 PO 4 、Na 2 CO 3 、NaHCO 3 、NH 4 Cl、(NH 4 ) 2 HPO 4 、CaCO 3 、NH 4 NO 3 、MgCO 3 、(NH 4 ) 2 SO 4 、NH 4 HCO 3 One or more of the following; in this embodiment, the curing agent is NH 4 H 2 PO 4 、NaHCO 3 Is in a ratio of 1:1.5.
The invention adjusts the composition by adding auxiliary agent into phosphoric acid or urea phosphate mother liquor, the mixed slurry is concentrated and then added with curing agent to form composite crystal, medium trace element ions rich in raw materials all enter the product, and the acid development performance of the product keeps good water solubility under the condition of rich medium trace elements. On the other hand, the phosphoric acid with proper impurity content can be directly used for preparing the acidic water-soluble composite phosphate product which mainly contains nitrogen and phosphorus nutrients and is rich in medium and trace elements under the condition that no mother liquor is produced by the method, so that the current production process of the phosphorus water-soluble fertilizer is rebuilt, the process flow is shortened, and the phosphorus yield is improved.
Meanwhile, the invention can fully utilize phosphorus in phosphoric acid and various medium and trace elements, and the prepared acidic water-soluble composite phosphate is full-water-soluble phosphate, so that the utilization rate can be greatly improved, and the acidic water-soluble composite phosphate can be widely applied to the improvement of alkaline soil due to the acid development.
The product is prepared by independently using the raffinate acid as a raw material, and the detection results are shown in the following table:
component (A) Content of raffinate acid Composite phosphate content
P 2 O 5 (％) 50.15 38.86
N(％) / 15.19
Fe(％) 0.18 0.18
Ca(％) 0.23 0.15
Mg(％) 3.12 2.39
K(％) 0.21 0.16
Na(％) 0.46 0.29
As(ppm) Not detected Not detected
Water insolubles (%) / Not detected
Based on the above data, it can be known that: preparation of water-soluble composite phosphate total nutrient (P) by using raffinate acid as raw material 2 O 5 +N) reaches 54.05%, the content of medium trace elements (Mg+Fe) in the product is up to 2.47%, and the phosphorus and the medium trace elements in the raffinate acid completely enter the product, so that the utilization rate of the effective components in the raffinate acid is greatly improved. Meanwhile, the water insoluble substances of the product are not detected, so that the good water solubility can not only greatly improve the fertilizer utilization rate, but also greatly improve the production efficiency.
Example two
This example is substantially the same as example one, except that the product is prepared from urea phosphate mother liquor and fertilized acid, and the test results are shown in the following table:
Figure BDA0004027353260000071
from the above data, it can be known that: water-soluble composite phosphate product total nutrient (P) prepared by taking urea phosphate and fertilizer acid as raw materials 2 O 5 +N) reaches 52.89%, and the content of medium trace elements (Mg+Fe) in the product reaches 2.94%. The method realizes the conversion from the liquid fertilizer containing more water insoluble matters to the solid water soluble fertilizer, enriches the application scene of the product, and overcomes the limitations of easy crystallization and separation of urea phosphate mother liquor and use of transportation radius. Meanwhile, compared with urea phosphate mother liquor, the water insoluble matters of the product are obviously reduced, and the requirement of large-scale mechanized fertilization in saline-alkali areas can be well met.
In order to facilitate a further understanding of the invention by those skilled in the art, the invention is further described below in connection with specific examples.
Case one
Step 1, taking 100g of raffinate acid, 10g of 37% HCl and 40g of urea, and stirring at 70 ℃ for 20min to obtain a mixed solution;
step 2, concentrating the slurry obtained in the step 1 in vacuum at 110 ℃ and 0.02MPa for 1.5h to obtain concentrated slurry with free water content of 4%;
step 3, pouring the concentrated slurry obtained in the step 2 into a beaker, and adding 1g CaCO when the slurry is cooled to 60 DEG C 3 And 1g (NH) 4 ) 2 SO 4 Stirring uniformly, standing and solidifying for 10min; and 4, placing the semi-finished product obtained in the step 3 into a blast drying oven at 75 ℃, drying for 2 hours, and crushing after drying to obtain a product.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
The foregoing description of the preferred embodiment of the invention is not intended to be limiting, but rather to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims (6)

1. The preparation method of the acidic water-soluble composite phosphate comprises the following steps:
step 1:
mixing phosphoric acid or/and a phosphorus-containing compound solution with urea and an additive;
control P 2 O 5 : the molar ratio of N is 0.5-1.5;
P 2 O 5 m is the sum of the mole numbers of sulfate radical, chloride ion and nitrate radical, wherein the mole ratio of M is 2-10;
heating at 50-100 ℃ until urea is completely dissolved to obtain mixed slurry;
step 2:
concentrating the slurry obtained in the step 1 at 60-130 ℃ and 0.01-0.1Mpa until the mass percentage of free water in the slurry is 3-5%;
step 3:
cooling the concentrated slurry obtained in the step 2 to 40-95 ℃, adding a curing agent for mixing, wherein the addition amount is 0-10% of the concentrated slurry, and cooling and curing for 5-120min to obtain a semi-finished product;
step 4:
and (3) drying the semi-finished product obtained in the step (3) at 50-90 ℃ under normal pressure until the free water content is 2-3%, crushing and packaging to obtain the powder acidic water-soluble composite phosphate product with the pH value of 1.8-3.5.
2. The method for preparing an acidic water-soluble composite phosphate according to claim 1, wherein: in the step 1, phosphoric acid is one or a mixture of industrial grade phosphoric acid, fertilizer grade phosphoric acid and raffinate phosphoric acid, and the raffinate phosphoric acid is a byproduct of purifying and preparing the industrial grade phosphoric acid by a wet-process phosphoric acid solvent extraction method.
3. The method for preparing an acidic water-soluble composite phosphate according to claim 1, wherein: in the step 1, the phosphorus-containing compound solution is urea phosphate mother liquor which is a byproduct when phosphoric acid is used for preparing urea phosphate products.
4. The method for preparing an acidic water-soluble composite phosphate according to claim 1, wherein: the additive is one or more of hydrochloric acid, hydrochloride, sulfuric acid, sulfate, nitric acid and nitrate.
5. The method for preparing an acidic water-soluble composite phosphate according to claim 1, wherein: in the step 2, the slurry obtained in the step 1 is concentrated under the conditions that the temperature is 100 ℃ and the pressure is 0.01-0.1Mpa, and the concentration is carried out until the mass percentage of free water in the slurry is 4%.
6. The method for preparing an acidic water-soluble composite phosphate according to claim 1, wherein: in the step 3, the curing agent is as follows: NH (NH) 4 H 2 PO 4 、Na 2 CO 3 、NaHCO 3 、NH 4 Cl、(NH 4 ) 2 HPO 4 、CaCO 3 、NH 4 NO 3 、MgCO 3 、(NH 4 ) 2 SO 4 、NH 4 HCO 3 One or more of the following.
CN202211728218.XA 2022-12-29 2022-12-29 Preparation method of acidic water-soluble composite phosphate Pending CN116199536A (en)

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