CN110395704B - Method for co-producing industrial-grade potassium dihydrogen phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid - Google Patents

Method for co-producing industrial-grade potassium dihydrogen phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid Download PDF

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CN110395704B
CN110395704B CN201810373702.2A CN201810373702A CN110395704B CN 110395704 B CN110395704 B CN 110395704B CN 201810373702 A CN201810373702 A CN 201810373702A CN 110395704 B CN110395704 B CN 110395704B
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phosphoric acid
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CN110395704A (en
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杨林
庄海波
张志业
王辛龙
邓强
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/30—Alkali metal phosphates
    • C01B25/301—Preparation from liquid orthophosphoric acid or from an acid solution or suspension of orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C01B25/322—Preparation by neutralisation of orthophosphoric acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/46—Preparation involving solvent-solvent extraction
    • C01B25/461—Preparation involving solvent-solvent extraction the phosphoric acid present in the medium obtained after reaction being first extracted from the liquid phase formed or separated then re-extracted as free acid by using water or as a phosphate by using a basic compound
    • C01B25/462—Preparation involving solvent-solvent extraction the phosphoric acid present in the medium obtained after reaction being first extracted from the liquid phase formed or separated then re-extracted as free acid by using water or as a phosphate by using a basic compound the extracting agent being alcohol or a mixture of alcohols
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/46—Preparation involving solvent-solvent extraction
    • C01B25/461—Preparation involving solvent-solvent extraction the phosphoric acid present in the medium obtained after reaction being first extracted from the liquid phase formed or separated then re-extracted as free acid by using water or as a phosphate by using a basic compound
    • C01B25/463—Preparation involving solvent-solvent extraction the phosphoric acid present in the medium obtained after reaction being first extracted from the liquid phase formed or separated then re-extracted as free acid by using water or as a phosphate by using a basic compound the extracting agent being a ketone or a mixture of ketones
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/46—Preparation involving solvent-solvent extraction
    • C01B25/461—Preparation involving solvent-solvent extraction the phosphoric acid present in the medium obtained after reaction being first extracted from the liquid phase formed or separated then re-extracted as free acid by using water or as a phosphate by using a basic compound
    • C01B25/465—Preparation involving solvent-solvent extraction the phosphoric acid present in the medium obtained after reaction being first extracted from the liquid phase formed or separated then re-extracted as free acid by using water or as a phosphate by using a basic compound the extracting agent being an ester or a mixture of esters
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Abstract

The invention relates to a method for co-producing industrial-grade potassium dihydrogen phosphate and feed-grade calcium hydrophosphate by using wet-process phosphoric acid, belonging to the technical field of chemical production. The technical problem to be solved by the invention is to provide a method for co-producing industrial-grade potassium dihydrogen phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid, which comprises the following steps: a. performing extraction reaction on wet-process phosphoric acid and an extracting agent to obtain an organic phase I and a water phase I; b. carrying out back extraction reaction on the organic phase I and a back extractant to obtain an organic phase II and a water phase II; c. refining the water phase II to obtain an industrial-grade potassium dihydrogen phosphate product; d. performing neutralization reaction on the water phase I and a primary neutralizing agent, and performing solid-liquid separation to obtain a filter cake I and a filtrate I; e. and (3) carrying out neutralization reaction on the filtrate I and a secondary neutralizer, carrying out solid-liquid separation to obtain a filter cake II and a filtrate II, and drying the filter cake II to obtain the feed-grade calcium hydrophosphate product. The invention has simple process, low cost, high utilization rate of phosphorus element and better social and economic benefits.

Description

Method for co-producing industrial-grade potassium dihydrogen phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid
Technical Field
The invention relates to a method for co-producing industrial-grade potassium dihydrogen phosphate and feed-grade calcium hydrophosphate by using wet-process phosphoric acid, belonging to the technical field of chemical production.
Background
Monopotassium phosphate (MKP for short) is one of important products in phosphate industry, and has a chemical formula of KH2PO4It has wide application in agriculture, chemical industry, food and medicine industries. In agricultural fertilizers, the monopotassium phosphate is a high-quality and high-efficiency phosphorus-potassium compound fertilizer and is also an excellent fertilizer variety appointed to be popularized by Ministry of agriculture; potassium dihydrogen phosphate is also used as a buffer, a culture medium, etc. in the chemical industry; in the food field, monopotassium phosphate can also be used as food additive, such as chelating agent, bufferAgents, leavening agents, flavoring agents, and the like. Many methods for producing potassium dihydrogen phosphate are broadly classified into a neutralization method, an extraction method, an ion exchange method, a double decomposition method, a direct method, a crystallization method, an electrolytic method, and the like.
Calcium hydrogen phosphate is a white monoclinic crystalline powder, and is odorless and tasteless. Usually as the dihydrate (of formula CaHPO)4·2H2O) is stable in air, and when heated to 75 ℃ it loses crystal water to form an anhydride, and when heated to a high temperature, it becomes a pyrophosphate. Is easily soluble in dilute hydrochloric acid, dilute nitric acid and dilute acetic acid, is slightly soluble in water, and is insoluble in ethanol. Dibasic calcium phosphate is generally classified into four grades according to use: toothpaste grade calcium hydrophosphate, food grade calcium hydrophosphate, fertilizer grade calcium hydrophosphate and feed grade calcium hydrophosphate. The feed grade calcium hydrophosphate is a bulk phosphorus chemical product with wide prospect, is a poultry and livestock feed additive containing two elements of phosphorus and calcium, and can maintain the phosphorus-calcium ratio in bones, thereby preventing various diseases caused by phosphorus and calcium deficiency of animals and promoting the rapid growth of animal organisms.
The production process of the traditional feed grade calcium hydrophosphate comprises the following steps: directly reacting phosphate rock with the quality requirement reaching the standard with sulfuric acid to obtain wet-process phosphoric acid, then carrying out two-stage neutralization by using lime milk, wherein the filter cake obtained by the one-stage neutralization is used for producing low-value white fertilizer, and the filter cake obtained by the two-stage neutralization is dried to obtain a feed-grade calcium hydrophosphate product; the consumption of the lime milk in the process accounts for about 50% of the consumption of the lime milk in the whole feed-grade calcium hydrophosphate production process, and about 20-30% of wet-process phosphoric acid is lost in the form of phosphate.
At present, most of domestic potassium dihydrogen phosphate is prepared by performing neutralization reaction on purified phosphoric acid obtained after purification treatment of phosphoric acid prepared by a wet-process phosphoric acid process and corresponding potassium-containing raw materials, but the production cost of the whole high-quality potassium dihydrogen phosphate product is high due to high production cost and high purification difficulty of the purified phosphoric acid raw materials. In order to reduce the production cost, research institutions and enterprises have developed the research of directly preparing potassium dihydrogen phosphate by using wet-process phosphoric acid, and the prior art uses the method for preparing potassium dihydrogen phosphate by using wet-process phosphoric acid include neutralization method, electrolytic method, ion exchange method, double decomposition method, multi-step method and the like.
In recent years, a method for coproducing industrial-grade potassium dihydrogen phosphate and feed-grade calcium phosphate by using wet-process phosphoric acid as a raw material appears in China, and for example, an invention patent with the application number of 201410134882.0 discloses a method for coproducing feed-grade calcium phosphate and potassium dihydrogen phosphate by defluorination of wet-process phosphoric acid. However, this process requires the wet phosphoric acid to be defluorinated beforehand, which undoubtedly increases the cost; impurities except fluorine in the wet-process phosphoric acid affect the potassium dihydrogen phosphate product, so that the purity of the product is difficult to reach the standard; in addition, calcium phosphate salt contains a large amount of impurity precipitates, calcium hydrophosphate has low purity, and can only be used as an agricultural low-end fertilizer, so the economic value is low.
Disclosure of Invention
Aiming at the defects, the technical problem solved by the invention is to provide the method for co-producing the industrial-grade potassium dihydrogen phosphate and the feed-grade calcium hydrophosphate by the wet-process phosphoric acid, the raw materials used in the method do not need to be defluorinated in advance, the production cost is greatly reduced, and the utilization value of the wet-process phosphoric acid is improved.
The invention discloses a method for co-producing industrial-grade potassium dihydrogen phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid, which comprises the following steps:
a. extraction and separation: performing extraction reaction on wet-process phosphoric acid and an extracting agent, standing and phase splitting to obtain an organic phase I and a water phase I; wherein the extractant is at least one of organic ketone extractant, organic ester extractant, organic alcohol extractant, organic ether extractant and organic amine extractant; wherein the content of P in the wet-process phosphoric acid is P2O515-60 wt% and F content of 0.50-1.80 wt%;
b. back extraction and separation: mixing the organic phase I and a stripping agent solution in the step a for stripping, standing and phase splitting to obtain an organic phase II and a water phase II; wherein the back extractant is at least one of potassium hydroxide, potassium bicarbonate and potassium carbonate;
c. preparing potassium dihydrogen phosphate: refining the water phase II obtained in the step b to obtain industrial-grade potassium dihydrogen phosphate;
d. primary neutralization: performing a neutralization reaction on the water phase I and a primary neutralizer, and controlling the pH value of a reaction end point to be 2.8-3.6; carrying out solid-liquid separation to obtain a filter cake I and a filtrate I; wherein the primary neutralizing agent is at least one of calcium oxide, calcium hydroxide and calcium carbonate;
e. and (3) secondary neutralization: neutralizing the filtrate I with a secondary neutralizer in the step d, and controlling the pH value of the reaction end point to be 5.5-6.0; performing solid-liquid separation to obtain a filter cake II and a filtrate II, wherein the secondary neutralizing agent is at least one of calcium oxide, calcium hydroxide and calcium carbonate; and drying the filter cake II to obtain the feed grade calcium hydrophosphate.
Preferably, in step a, the extractant is methyl isobutyl ketone, cyclohexanone, tributyl phosphate, dimethylheptyl methylphosphonate, trioctylphosphine oxide, n-butanol, n-octanol, isobutanol, cyclobutanol, benzyl alcohol, isoamyl alcohol, diisopropyl ether, diethyl ether, dibutyl ether or trioctyl tertiary amine.
Preferably, in the step a, the temperature of the extraction reaction is 30-70 ℃, and the time of the extraction reaction is 1-50 min; the temperature of the extraction reaction is preferably 60 ℃ and the time of the extraction reaction is preferably 30 min.
Preferably, in the step a, the volume ratio of the wet-process phosphoric acid to the extracting agent is 1: 1-3; the volume ratio of the wet-process phosphoric acid to the extracting agent is preferably 1: 3.
Preferably, in the step b, the concentration of the stripping agent solution is 1-60 wt%; preferably, when the back extraction agent is potassium hydroxide, the mass concentration of the potassium hydroxide is 1-30 wt%, when the back extraction agent is potassium bicarbonate, the mass concentration of the potassium bicarbonate is 1-40%, and when the back extraction agent is potassium carbonate, the mass concentration of the potassium carbonate is 1-60%.
Preferably, in the step b, the addition amount of the stripping agent is 0.8-1.2: 1 in terms of molar ratio of K in the stripping agent to P in the organic phase I; the stripping agent is preferably added in an amount of 1.0:1 in terms of molar ratio of K in the stripping agent to P in the organic phase i.
Preferably, in the step b, the temperature of the back extraction reaction is 30-70 ℃, and the time of the back extraction reaction is 1-50 min; preferably, the back extraction temperature is 60 ℃ and the back extraction time is 30 min.
Preferably, the refining method in step c is as follows: concentrating, cooling, crystallizing, filtering and drying the water phase II to obtain an industrial-grade potassium dihydrogen phosphate product;
or the water phase II in the step b is directly cooled, crystallized, filtered and dried to obtain an industrial-grade potassium dihydrogen phosphate product;
or concentrating the water phase II in the step b and then carrying out spray drying to obtain an industrial-grade potassium dihydrogen phosphate product;
or the water phase II in the step b is directly sprayed and dried to obtain the industrial-grade potassium dihydrogen phosphate product.
Preferably, in the step d, the reaction temperature is 30-100 ℃, the reaction time is 10-60 min, and in the step e, the reaction temperature is 30-100 ℃, and the reaction time is 10-60 min; preferably, in the step d, the reaction temperature is 60-70 ℃, and the reaction time is 40 min; in the step e, the reaction temperature is 60-70 ℃, and the reaction time is 40 min.
Preferably, the organic phase II in the step b is returned to the step a to be used as an extracting agent; and e, returning the filtrate II to the phosphorite slurry workshop section for utilization.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention directly takes wet-process phosphoric acid as a raw material, does not need to be defluorinated in advance, has low requirement on the quality of the raw material wet-process phosphoric acid, and replaces hot-process phosphoric acid with the wet-process phosphoric acid to produce the monopotassium phosphate, thereby reducing the production cost.
2. The method divides the wet-process phosphoric acid into two parts in an extraction and separation mode, and the phosphoric acid with high quality is used for producing the monopotassium phosphate, thereby reducing the influence of impurities on the monopotassium phosphate and ensuring the quality of monopotassium phosphate products; the phosphoric acid with low quality is used for producing feed grade calcium hydrophosphate, only part of the phosphoric acid needs to be neutralized, the dosage of a primary neutralizer and a secondary neutralizer is greatly reduced, and the utilization value of the phosphoric acid is improved.
3. In the method, after the back extraction reaction is finished, the potassium dihydrogen phosphate crude solution can be directly cooled, crystallized or spray-dried, so that the step of evaporation and concentration is omitted, the process route is simplified, the energy is saved, and the production cost is reduced.
4. The method has simple process, and P carried in the white fertilizer2O5Low content, high utilization rate of phosphorus element, and good social and economic benefits.
Drawings
FIG. 1 is a process flow chart of the present invention for co-production of industrial-grade potassium dihydrogen phosphate and feed-grade calcium hydrogen phosphate by wet-process phosphoric acid.
Detailed Description
The invention discloses a method for co-producing industrial-grade potassium dihydrogen phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid, which comprises the following steps:
a. extraction and separation: performing extraction reaction on wet-process phosphoric acid and an extracting agent, standing and phase splitting to obtain an organic phase I and a water phase I; wherein the extractant is at least one of organic ketone extractant, organic ester extractant, organic alcohol extractant, organic ether extractant and organic amine extractant; wherein the content of P in the wet-process phosphoric acid is P2O515-60 wt% and F content of 0.50-1.80 wt%;
b. back extraction and separation: mixing the organic phase I and a stripping agent solution in the step a for stripping, standing and phase splitting to obtain an organic phase II and a water phase II; wherein the back extractant is at least one of potassium hydroxide, potassium bicarbonate and potassium carbonate;
c. preparing potassium dihydrogen phosphate: refining the water phase II obtained in the step b to obtain industrial-grade potassium dihydrogen phosphate;
d. primary neutralization: performing a neutralization reaction on the water phase I and a primary neutralizer, and controlling the pH value of a reaction end point to be 2.8-3.6; carrying out solid-liquid separation to obtain a filter cake I and a filtrate I; the filter cake I is a white fertilizer, wherein the primary neutralizing agent is at least one of calcium oxide, calcium hydroxide and calcium carbonate;
e. and (3) secondary neutralization: neutralizing the filtrate I with a secondary neutralizer in the step d, and controlling the pH value of the reaction end point to be 5.5-6.0; performing solid-liquid separation to obtain a filter cake II and a filtrate II, wherein the secondary neutralizing agent is at least one of calcium oxide, calcium hydroxide and calcium carbonate; and drying the filter cake II to obtain the feed grade calcium hydrophosphate.
The wet-process phosphoric acid in the step a is crude phosphoric acid produced by a wet-process phosphoric acid process, pre-defluorination is not needed, most of the phosphoric acid is extracted by the extraction in the step a, an extract phase (namely, an organic phase I) contains high-purity phosphoric acid and is used for preparing industrial-grade monopotassium phosphate, and a raffinate acid (namely, a water phase I) contains a small amount of phosphorus and impurities and is used for preparing feed-grade calcium hydrophosphate.
Extractants commonly used in the art are suitable for use in the present invention. Preferably, in step a, the extractant is an organic ketone extractant, such as methyl isobutyl ketone, cyclohexanone, etc., a phosphate extractant, such as tributyl phosphate (TBP), dimethylheptyl methylphosphonate (P350), trioctylphosphine oxide (TOPO), etc., an organic alcohol extractant, such as N-butanol, N-octanol, isobutanol, cyclobutanol, benzyl alcohol, isoamyl alcohol, etc., an organic ether extractant, such as diisopropyl ether, diethyl ether, dibutyl ether, etc., an organic amine extractant, such as trioctyl tertiary amine (N235), etc.
In order to improve the reaction efficiency, in the step a, the temperature of the extraction reaction is preferably 30-70 ℃, and the time of the extraction reaction is preferably 1-50 min. More preferably, the temperature of the extraction reaction is 60 ℃ and the time of the extraction reaction is 30 min.
Preferably, in the step a, the volume ratio of the wet-process phosphoric acid to the extracting agent is 1: 1-3. More preferably, the volume ratio of wet-process phosphoric acid to the extracting agent is 1: 3.
And b, after the step a, dividing the wet-process phosphoric acid into two parts, and respectively preparing potassium dihydrogen phosphate and calcium hydrogen phosphate. In the method, the step b and the step c are technical processes for preparing monopotassium phosphate, the step d and the step e are technical processes for preparing calcium hydrophosphate, the steps b and c are not in time sequence, and the steps d and e can be carried out firstly; steps d and e may be performed first, and then steps b and c may be performed, or steps d and e may be performed simultaneously with steps b and c.
In the step b, a stripping agent solution (namely, an aqueous solution of a stripping agent) is added into the organic phase I to obtain a potassium dihydrogen phosphate crude solution, wherein the chemical reactions mainly occur as follows:
H3PO4+K+＝KH2PO4+H+
the concentration of the stripping agent solution has a certain influence on the stripping. Preferably, the concentration of the stripping agent solution is 1-60 wt%. More preferably, the mass concentration of the potassium hydroxide is 1-30 wt% when the stripping agent is potassium hydroxide, the mass concentration of the potassium bicarbonate is 1-40% when the stripping agent is potassium bicarbonate, and the mass concentration of the potassium carbonate is 1-60% when the stripping agent is potassium carbonate.
Further, in order to improve the stripping effect and save the consumption of the stripping agent, preferably, the addition amount of the stripping agent in the step b is 0.8-1.2: 1 in terms of molar ratio of potassium element K in the stripping agent to P in the organic phase i. More preferably, the addition amount of the stripping agent in the step b is that the molar ratio of potassium element K in the stripping agent to P in the organic phase I is 1: 1; in order to ensure the product quality without introducing new impurities, the purity of the stripping agent in step b is preferably more than 95 wt%.
In order to improve the reaction efficiency, preferably, in the step b, the temperature of the back extraction is 30-70 ℃, and the time of the back extraction is 1-50 min. More preferably, the temperature of the back extraction is 60 ℃, and the time of the back extraction is 30 min.
And the organic phase II in the step b is a regenerated extracting agent, and is preferably returned to the step a to be used as the extracting agent, so that the extracting agent can be recycled, and the production cost is reduced.
And c, performing back extraction in the step b to obtain a water phase II, namely the potassium dihydrogen phosphate crude solution. Generally, the concentration of MKP in the crude potassium dihydrogen phosphate solution is high and can reach more than 25%, and the crude potassium dihydrogen phosphate solution can be directly cooled and crystallized or spray-dried in the step c, so that concentration is not needed, and the cost of evaporation concentration is saved.
And step c is a step of preparing a monopotassium phosphate product from the water phase II obtained in the step b. The water phase II is a potassium dihydrogen phosphate crude solution, and the method for preparing the solid from the crude solution, which is commonly used in the field, is suitable for the invention. Preferably, the refining method in step c is as follows: concentrating, cooling, crystallizing, filtering and drying the water phase II to obtain an industrial-grade potassium dihydrogen phosphate product; or the water phase II in the step b is directly cooled, crystallized, filtered and dried to obtain an industrial-grade potassium dihydrogen phosphate product; or concentrating the water phase II in the step b and then carrying out spray drying to obtain an industrial-grade potassium dihydrogen phosphate product; or the water phase II in the step b is directly sprayed and dried to obtain the industrial-grade potassium dihydrogen phosphate product.
The cooling crystallization temperature is preferably 20-55 ℃, and more preferably 25-35 ℃.
In the step d, the water phase I can react with the added primary neutralizing agent to obtain calcium dihydrogen phosphate and calcium phosphate salt precipitates, most of fluorine and other impurities in the water phase I can also react to form precipitates, impurity ions in subsequent reactions are reduced, and the purity of crystals is improved. The reactions that mainly occur during this period are:
Ca2++2H3PO4＝Ca(H2PO4)2+2H+
Fe3++H3PO4+2H2O＝FePO4·2H2O↓+3H+
Al3++H3PO4+2H2O＝AlPO4·2H2O↓+3H+
Mg2++H3PO4+3H2O＝MgHPO4·3H2O↓+2H+
3Ca(OH)2+H2SiF6＝3CaF2↓+SiO2↓+4H2O
Ca2++2H2SO4+2H2O＝CaSO4·2H2O↓+2H+
after primary neutralization reaction, solid-liquid separation is carried out to obtain a filter cake I, namely the white fertilizer.
In order to improve the reaction efficiency, the reaction temperature in the step d is preferably 30-100 ℃, and the reaction time is 10-60 min. More preferably, the reaction temperature is 60-70 ℃, and the reaction time is 40 min.
D, filtering to obtain filtrate I, wherein the main components of the filtrate I are monocalcium phosphate and phosphoric acid, then performing step e, and adding a secondary neutralizer to perform reaction, wherein the main chemical reactions are as follows:
Ca2++2H3PO4＝Ca(H2PO4)2+2H+
Ca(H2PO4)2+Ca(OH)2+2H2O＝2CaHPO4·2H2O
in order to improve the reaction efficiency, the reaction temperature in the step e is preferably 30-100 ℃, and the reaction time is 10-60 min. More preferably, the reaction temperature is 60-70 ℃, and the reaction time is 40 min.
And e, carrying out solid-liquid separation after the reaction in the step e to obtain a filter cake II and a filtrate II, drying the filter cake II to obtain the feed-grade calcium hydrophosphate, and preferably returning the filtrate II to the phosphorite slurry working section for recycling.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
a、P2O51000g of wet-process phosphoric acid with the concentration of 24.18 wt% and tributyl phosphate (TBP) as an extracting agent are subjected to extraction reaction according to the volume ratio of the wet-process phosphoric acid to the extracting agent of 1:3, the reaction temperature is controlled to be 60 ℃, the reaction time is 30min, and the organic phase I and the water phase I are obtained by standing and phase splitting.
b. B, carrying out back extraction reaction on the organic phase I obtained in the step a and 635.7g of potassium hydroxide solution with the mass fraction of 15 wt%, wherein the addition amount is determined according to the potassium hydroxide in the back extraction agent and the P in the organic phase I2O5The molar ratio of the organic phase to the water phase is 2:1, the reaction temperature is controlled to be 60 ℃, the reaction time is 30min, and the organic phase II and the water phase II are obtained after standing and phase splitting; wherein the organic phase II is a regenerated extracting agent, and the water phase II is a crude solution of potassium dihydrogen phosphate.
c. And directly cooling and crystallizing the water phase II at 30 ℃ to separate out solid, returning the monopotassium phosphate mother liquor to a back extraction section, and drying the solid at 62 ℃ to obtain 234g of industrial monopotassium phosphate.
d. B, performing primary neutralization reaction on the water phase I obtained in the step a and calcium oxide, adjusting the pH of a reaction solution to 2.8, reacting for 50min, controlling the reaction to be finished, and performing solid-liquid separation to obtain a filter cake I and a filtrate I; wherein the filter cake I can be used for producing white fertilizer, and the main components of the filtrate I are calcium dihydrogen phosphate and phosphoric acid.
e. D, carrying out secondary neutralization reaction on the filtrate I obtained in the step d and calcium oxide, adjusting the pH of a reaction solution to 5.5, controlling the reaction temperature to be 60 ℃, reacting for 50min, controlling the reaction to be finished, and carrying out solid-liquid separation to obtain a filter cake II and a filtrate II; wherein the filtrate II returns to the phosphorite slurry working section, and the filter cake II is dried at 95 ℃ to obtain 177.6g of feed-grade calcium hydrophosphate.
The wet-process phosphoric acid comprises the following components in percentage by weight: p2O524.18％，F1.64％，Fe2O30.99％，Al2O30.78％，MgO0.86％。
The feed grade calcium hydrophosphate comprises the following components in percentage by weight: p2O540.84 percent, Ca23 percent and F0.17 percent, which can be known from GB/T22549-2008, reach the standard of feed grade calcium hydrophosphate.
The potassium dihydrogen phosphate comprises the following components in percentage by weight: KH (Perkin Elmer)2PO498.65％，K28.29％，F0.008％。
After the material balance is carried out on the whole process, the utilization rate of the P element in the wet-process phosphoric acid is 79.81%.
Example 2
a、P2O51000g of wet-process phosphoric acid with the concentration of 35.72 wt% and n-butyl alcohol as an extracting agent are subjected to extraction reaction according to the volume ratio of the wet-process phosphoric acid to the extracting agent of 1:3, the reaction temperature is controlled at 60 ℃, and standing and phase separation are carried out to obtain an organic phase I and a water phase I.
b. B, carrying out back extraction reaction on the organic phase I obtained in the step a and 1760.9g of potassium bicarbonate solution with the mass fraction of 20 wt%, wherein the addition amount of the potassium bicarbonate in the back extractant and the P in the organic phase I are determined according to the mass fraction2O5The molar ratio of the organic phase to the water phase is 2:1, the reaction temperature is controlled to be 60 ℃, the reaction time is 30min, and the organic phase II and the water phase II are obtained after standing and phase splitting; wherein the organic phase II is a regenerated extracting agent, and the water phase II is a crude solution of potassium dihydrogen phosphate.
c. And directly cooling and crystallizing the water phase II at 30 ℃ to separate out solid, returning the monopotassium phosphate mother liquor to a back extraction section, and drying the solid at 65 ℃ to obtain 483.3g of industrial monopotassium phosphate.
d. B, performing primary neutralization reaction on the water phase I obtained in the step a and calcium oxide, adjusting the pH of a reaction solution to 3.0, reacting for 50min, controlling the reaction to be finished, and performing solid-liquid separation to obtain a filter cake I and a filtrate I; wherein the filter cake I can be used for producing white fertilizer, and the main components of the filtrate I are calcium dihydrogen phosphate and phosphoric acid.
e. D, carrying out secondary neutralization reaction on the filtrate I obtained in the step d and calcium oxide, adjusting the pH of a reaction solution to 5.7, controlling the reaction temperature to be 60 ℃, reacting for 50min, controlling the reaction to be finished, and carrying out solid-liquid separation to obtain a filter cake II and a filtrate II; wherein the filtrate II returns to the phosphorite slurry working section, and the filter cake II is dried at 95 ℃ to obtain 157.3g of feed-grade calcium hydrophosphate.
The wet-process phosphoric acid comprises the following components in percentage by weight: p2O535.72％，F1.05％，Fe2O30.84％，Al2O30.79％，MgO0.83％。
The feed grade calcium hydrophosphate comprises the following components in percentage by weight: p2O540.86 percent, Ca23.01 percent and F0.16 percent, which can be known from GB/T22549-2008, reach the standard of feed grade calcium hydrophosphate.
The potassium dihydrogen phosphate comprises the following components in percentage by weight: KH (Perkin Elmer)2PO498.92％，K28.31％，F0.006％。
After the material balance is carried out on the whole process, the utilization rate of the P element in the wet-process phosphoric acid is 87.81%.
Example 3
a、P2O51000g of wet-process phosphoric acid with the concentration of 46.25 wt% and diisopropyl ether are adopted as an extracting agent, the extraction reaction is carried out according to the volume ratio of the wet-process phosphoric acid to the extracting agent of 1:3, the reaction temperature is controlled at 60 ℃, and the organic phase I and the water phase I are obtained by standing and phase separation.
b. B, carrying out back extraction reaction on the organic phase I obtained in the step a and 1797.9g of potassium carbonate solution with the mass fraction of 15 wt%, wherein the addition amount of the potassium carbonate and the potassium carbonate in the back extraction agent is determined according to theP in organic phase I2O5The molar ratio of the organic phase to the water phase is 1:1, the reaction temperature is controlled to be 60 ℃, the reaction time is 30min, and the organic phase II and the water phase II are obtained after standing and phase splitting; wherein the organic phase II is a regenerated extracting agent, and the water phase II is a crude solution of potassium dihydrogen phosphate.
c. And directly cooling and crystallizing the water phase II at 30 ℃ to separate out solid, returning the monopotassium phosphate mother liquor to a back extraction section, and drying the solid at 65 ℃ to obtain 535.8g of industrial monopotassium phosphate.
d. B, performing primary neutralization reaction on the water phase I obtained in the step a and calcium oxide, adjusting the pH of a reaction solution to 3.4, reacting for 50min, controlling the reaction to be finished, and performing solid-liquid separation to obtain a filter cake I and a filtrate I; wherein the filter cake I can be used for producing white fertilizer, and the main components of the filtrate I are calcium dihydrogen phosphate and phosphoric acid.
e. D, carrying out secondary neutralization reaction on the filtrate I obtained in the step d and calcium oxide, adjusting the pH of a reaction solution to 5.8, controlling the reaction temperature to be 60 ℃, reacting for 50min, controlling the reaction to be finished, and carrying out solid-liquid separation to obtain a filter cake II and a filtrate II; wherein the filtrate II returns to the phosphorite slurry working section, and the filter cake II is dried at 95 ℃ to obtain 293.8g of feed grade calcium hydrophosphate.
The wet-process phosphoric acid comprises the following components in percentage by weight: p2O546.25％，F1.36％，Fe2O30.87％，Al2O30.76％，MgO0.85％。
The feed grade calcium hydrophosphate comprises the following components in percentage by weight: p2O540.92 percent, Ca23.05 percent and F0.18 percent, which can be known from GB/T22549-2008, reach the standard of feed grade calcium hydrophosphate.
The potassium dihydrogen phosphate comprises the following components in percentage by weight: KH (Perkin Elmer)2PO498.95％，K28.38％，F0.007％。
After the material balance is carried out on the whole process, the utilization rate of the P element in the wet-process phosphoric acid is 85.81%.
Example 4
a、P2O51000g of wet-process phosphoric acid having a concentration of 57.63 wt.%, using methyl isobutyl ketone MIBKAs an extracting agent, carrying out extraction reaction according to the volume ratio of wet-process phosphoric acid to the extracting agent of 1:3, controlling the reaction temperature to be 60 ℃, standing and phase splitting to obtain an organic phase I and a water phase I.
b. B, carrying out back extraction reaction on the organic phase I obtained in the step a and 1212.1g of potassium hydroxide solution with the mass fraction of 15 wt%, wherein the addition amount is determined by the potassium hydroxide in the back extraction agent and the P in the organic phase I2O5The molar ratio of the organic phase to the water phase is 2:1, the reaction temperature is controlled to be 60 ℃, the reaction time is 30min, and the organic phase II and the water phase II are obtained after standing and phase splitting; wherein the organic phase II is a regenerated extracting agent, and the water phase II is a crude solution of potassium dihydrogen phosphate.
c. And directly cooling and crystallizing the water phase II at 30 ℃ to separate out solid, returning the monopotassium phosphate mother liquor to a back extraction section, and drying the solid at 65 ℃ to obtain 445.4g of industrial monopotassium phosphate.
d. B, performing primary neutralization reaction on the water phase I obtained in the step a and calcium oxide, adjusting the pH of a reaction solution to 3.6, reacting for 50min, controlling the reaction to be finished, and performing solid-liquid separation to obtain a filter cake I and a filtrate I; wherein the filter cake I can be used for producing white fertilizer, and the main components of the filtrate I are calcium dihydrogen phosphate and phosphoric acid.
e. D, carrying out secondary neutralization reaction on the filtrate I obtained in the step d and calcium oxide, adjusting the pH of a reaction solution to 6.0, controlling the reaction temperature to be 60 ℃, reacting for 50min, controlling the reaction to be finished, and carrying out solid-liquid separation to obtain a filter cake II and a filtrate II; wherein the filtrate II returns to the phosphorite slurry working section, and the filter cake II is dried at 95 ℃ to obtain 593.27g of feed-grade calcium hydrophosphate.
The wet-process phosphoric acid comprises the following components in percentage by weight: p2O557.63％，F0.85％，Fe2O30.81％，Al2O30.72％，MgO0.80％。
The feed grade calcium hydrophosphate comprises the following components in percentage by weight: p2O540.80 percent, Ca22.99 percent and F0.18 percent, which can be known from GB/T22549-2008, reach the standard of feed grade calcium hydrophosphate.
The potassium dihydrogen phosphate comprises the following components in percentage by weight: KH (Perkin Elmer)2PO498.85％，K28.35％，F0.005％。
After the material balance is carried out on the whole process, the utilization rate of the P element in the wet-process phosphoric acid is 81.85%.
Example 5
a、P2O51000g of wet-process phosphoric acid with the concentration of 15.62 wt% and organic amine extractant N235 are adopted to carry out extraction reaction according to the volume ratio of the wet-process phosphoric acid to the extractant of 1:3, the reaction temperature is controlled to be 60 ℃, the extraction reaction time is 30min, and the organic phase I and the water phase I are obtained by standing and phase splitting.
b. Carrying out back extraction reaction on the organic phase I obtained in the step a and a potassium bicarbonate solution with the mass fraction of 25 wt%, wherein the addition amount of the potassium bicarbonate in the back extractant and the P in the organic phase I2O5The molar ratio of the organic phase to the water phase is 2:1, the reaction temperature is controlled to be 60 ℃, the reaction time is 30min, and the organic phase II and the water phase II are obtained after standing and phase splitting; wherein the organic phase II is a regenerated extracting agent, and the water phase II is a crude solution of potassium dihydrogen phosphate.
c. And directly spray-drying the water phase II to obtain 75.2g of industrial-grade potassium dihydrogen phosphate.
d. B, performing primary neutralization reaction on the water phase I obtained in the step a and calcium oxide, adjusting the pH of a reaction solution to 2.8, controlling the reaction temperature to be 70 ℃, reacting for 50min, controlling the reaction to be finished, and performing solid-liquid separation to obtain a filter cake I and a filtrate I; wherein the filter cake I can be used for producing white fertilizer, and the main components of the filtrate I are calcium dihydrogen phosphate and phosphoric acid.
e. D, carrying out secondary neutralization reaction on the filtrate I obtained in the step d and calcium oxide, adjusting the pH of a reaction solution to 5.5, controlling the reaction temperature to be 70 ℃, reacting for 50min, controlling the reaction to be finished, and carrying out solid-liquid separation to obtain a filter cake II and a filtrate II; wherein the filtrate II returns to the phosphorite slurry working section, and the filter cake II is dried at 95 ℃ to obtain 56.8g of feed grade calcium hydrophosphate.
The wet-process phosphoric acid comprises the following components in percentage by weight: p2O515.62％，F0.57％，Fe2O30.58％，Al2O30.47％，MgO0.62％。
The feed-grade calcium hydrophosphate comprises the following components,all in percentage by weight: p2O540.82 percent, Ca23.00 percent and F0.17 percent, which can be known from GB/T22549-2008, reach the standard of feed grade calcium hydrophosphate.
The potassium dihydrogen phosphate comprises the following components in percentage by weight: KH (Perkin Elmer)2PO498.58％，K28.27％，F0.007％。
After the material balance is carried out on the whole process, the utilization rate of the P element in the wet-process phosphoric acid is 79.53%.

Claims (16)

1. The method for co-producing industrial-grade potassium dihydrogen phosphate and feed-grade calcium hydrophosphate by using wet-process phosphoric acid is characterized by comprising the following steps of:
a. extraction and separation: performing extraction reaction on wet-process phosphoric acid and an extracting agent, standing and phase splitting to obtain an organic phase I and a water phase I; wherein the extractant is at least one of organic ketone extractant, organic ester extractant, organic alcohol extractant, organic ether extractant and organic amine extractant; wherein the content of P in the wet-process phosphoric acid is P2O515-60 wt% and F content of 0.50-1.80 wt%;
b. back extraction and separation: mixing the organic phase I and a stripping agent solution in the step a for stripping, standing and phase splitting to obtain an organic phase II and a water phase II; wherein the back extractant is at least one of potassium hydroxide, potassium bicarbonate and potassium carbonate;
c. preparing potassium dihydrogen phosphate: refining the water phase II obtained in the step b to obtain industrial-grade potassium dihydrogen phosphate;
d. primary neutralization: performing a neutralization reaction on the water phase I and a primary neutralizer, and controlling the pH value of a reaction end point to be 2.8-3.6; carrying out solid-liquid separation to obtain a filter cake I and a filtrate I; wherein the primary neutralizing agent is at least one of calcium oxide, calcium hydroxide and calcium carbonate;
e. and (3) secondary neutralization: neutralizing the filtrate I with a secondary neutralizer in the step d, and controlling the pH value of the reaction end point to be 5.5-6.0; performing solid-liquid separation to obtain a filter cake II and a filtrate II, wherein the secondary neutralizing agent is at least one of calcium oxide, calcium hydroxide and calcium carbonate; and drying the filter cake II to obtain the feed grade calcium hydrophosphate.
2. The method for co-producing industrial-grade monopotassium phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid according to claim 1, characterized in that: in the step a, the extractant is methyl isobutyl ketone, cyclohexanone, tributyl phosphate, dimethylheptyl methylphosphonate, trioctylphosphine oxide, n-butanol, n-octanol, isobutanol, cyclobutanol, benzyl alcohol, isoamyl alcohol, diisopropyl ether, diethyl ether, dibutyl ether or trioctyl tertiary amine.
3. The method for co-producing industrial-grade monopotassium phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid according to claim 1, characterized in that: in the step a, the temperature of the extraction reaction is 30-70 ℃, and the time of the extraction reaction is 1-50 min.
4. The method for co-producing industrial-grade monopotassium phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid according to claim 3, characterized in that: in the step a, the temperature of the extraction reaction is 60 ℃, and the time of the extraction reaction is 30 min.
5. The method for co-producing industrial-grade monopotassium phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid according to claim 1, characterized in that: in the step a, the volume ratio of the wet-process phosphoric acid to the extracting agent is 1: 1-3.
6. The method for co-producing industrial-grade monopotassium phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid according to claim 5, characterized in that: in the step a, the volume ratio of the wet-process phosphoric acid to the extracting agent is 1: 3.
7. The method for co-producing industrial-grade monopotassium phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid according to claim 1, characterized in that: in the step b, the concentration of the stripping agent solution is 1-60 wt%.
8. The method for co-producing industrial-grade monopotassium phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid according to claim 7, wherein the method comprises the following steps: in the step b, when the stripping agent is potassium hydroxide, the mass concentration of the potassium hydroxide is 1-30 wt%, when the stripping agent is potassium bicarbonate, the mass concentration of the potassium bicarbonate is 1-40%, and when the stripping agent is potassium carbonate, the mass concentration of the potassium carbonate is 1-60%.
9. The method for co-producing industrial-grade monopotassium phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid according to claim 1, characterized in that: in the step b, the addition amount of the stripping agent is 0.8-1.2: 1 in terms of molar ratio of K in the stripping agent to P in the organic phase I.
10. The method for co-producing industrial-grade monopotassium phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid according to claim 9, wherein the method comprises the following steps: in the step b, the addition amount of the stripping agent is 1:1 in terms of the molar ratio of K in the stripping agent to P in the organic phase I.
11. The method for co-producing industrial-grade monopotassium phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid according to claim 1, characterized in that: in the step b, the temperature of the back extraction reaction is 30-70 ℃, and the time of the back extraction reaction is 1-50 min.
12. The method for co-producing industrial-grade monopotassium phosphate and feed-grade calcium hydrophosphate by wet process phosphoric acid according to claim 11, wherein the method comprises the following steps: in the step b, the back extraction temperature is 60 ℃, and the back extraction time is 30 min.
13. The method for co-producing industrial-grade monopotassium phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid according to claim 1, characterized in that: the refining method in the step c comprises the following steps: concentrating, cooling, crystallizing, filtering and drying the water phase II to obtain an industrial-grade potassium dihydrogen phosphate product;
or the water phase II in the step b is directly cooled, crystallized, filtered and dried to obtain an industrial-grade potassium dihydrogen phosphate product;
or concentrating the water phase II in the step b and then carrying out spray drying to obtain an industrial-grade potassium dihydrogen phosphate product;
or the water phase II in the step b is directly sprayed and dried to obtain the industrial-grade potassium dihydrogen phosphate product.
14. The method for co-producing industrial-grade monopotassium phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid according to claim 1, characterized in that: in the step d, the reaction temperature is 30-100 ℃, the reaction time is 10-60 min, and in the step e, the reaction temperature is 30-100 ℃, and the reaction time is 10-60 min.
15. The method for co-producing industrial-grade monopotassium phosphate and feed-grade calcium hydrophosphate by wet process phosphoric acid according to claim 14, wherein the method comprises the following steps: in the step d, the reaction temperature is 60-70 ℃, and the reaction time is 40 min; in the step e, the reaction temperature is 60-70 ℃, and the reaction time is 40 min.
16. The method for co-producing industrial-grade monopotassium phosphate and feed-grade calcium hydrophosphate by wet-process phosphoric acid according to claim 1, characterized in that: b, returning the organic phase II to the step a to be used as an extracting agent; and e, returning the filtrate II to the phosphorite slurry workshop section for utilization.
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