CN108751154B - Preparation method of monocalcium phosphate - Google Patents
Preparation method of monocalcium phosphate Download PDFInfo
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- CN108751154B CN108751154B CN201810563762.0A CN201810563762A CN108751154B CN 108751154 B CN108751154 B CN 108751154B CN 201810563762 A CN201810563762 A CN 201810563762A CN 108751154 B CN108751154 B CN 108751154B
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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
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
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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
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/10—Compounds containing silicon, fluorine, and other elements
- C01B33/103—Fluosilicic acid; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
Abstract
The invention discloses a preparation method of monocalcium phosphate, which comprises the steps of utilizing organic extraction to purify raffinate acid and membrane filtration to purify concentrated phosphoric acid to decompose phosphorite in a grading manner, converting insoluble calcium in the phosphorite into water-soluble calcium, and obtaining an MCP product through membrane filtration purification, neutralization purification and impurity removal and back-regulation of the concentrated acid. The problems that the utilization efficiency of the extraction residual acid is low, the harm to soil is large when the byproduct waste residue is used as a fertilizer, the utilization rate of calcium fluoride resources in phosphorite is low and the like in the prior art are solved; the method realizes the high-efficiency recovery of calcium and fluorine resources in the raffinate acid and the phosphorite, and the calcium and fluorine resources are used for producing feed-grade monocalcium phosphate and villaumite products, thereby improving the resource utilization rate, greatly reducing the emission of phosphogypsum, and relieving the economic and environmental protection pressure of enterprises.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a preparation method of monocalcium phosphate.
Background
In recent years, with the gradual maturity of wet-process phosphoric acid purification technology, industrial-grade and even food-grade phosphate products can be produced by using wet-process phosphoric acid, the production cost of the phosphate products is obviously lower than that of a hot-process phosphoric acid production technology, and the market competitiveness of fine phosphate products produced by using the purification wet-process phosphoric acid is larger and larger.
The wet-process phosphoric acid purification mostly adopts an organic solvent extraction method at present, the process can obtain high-quality purified phosphoric acid, the yield is about 50 percent generally, impurity ions in the residual 50 percent phosphoric acid (namely raffinate acid) are enriched, and the process is mostly used for producing agricultural phosphate fertilizers. However, with the increasing concern of people about the safety of fertilizer application, raffinate acid with high impurity mass fraction is used for producing fertilizer products, particularly fluorine impurities in phosphoric acid, has great hidden danger when entering the fertilizer, and the development of a new way for efficiently utilizing the raffinate acid has become a technical problem of important industry.
Disclosure of Invention
The invention aims to provide a method for preparing monocalcium phosphate, which solves the problems that the utilization efficiency of raffinate acid is low and the harm to soil is large when byproduct waste residues are used as fertilizers in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of monocalcium phosphate is characterized by comprising the following steps: the method comprises the following steps:
step 1: the extraction spent acid is used for reacting with the thick slurry-1, and the generated phosphogypsum is separated to obtain clear liquid-1;
step 2: mixing the clear liquid-1, phosphorite and phosphoric acid and reacting to obtain slurry-2;
and step 3: carrying out solid-liquid separation on the slurry-2, wherein the solid-liquid separation can be carried out by adopting a thickener to obtain clear liquid-2 and thick slurry-1, and returning the thick slurry-1 to the step 1 for use;
and 4, step 4: separating the clear liquid-2 by a nanofiltration membrane to obtain clear liquid-3 with relatively low cation mass fraction and clear liquid-4 with relatively high cation mass fraction;
and 5: adding calcium carbonate slurry into the clear liquid-4 for reaction, and performing solid-liquid separation on the product to obtain clear liquid-5 and thick slurry-2;
step 6: adding calcium hydroxide slurry into the clear liquid-5 for reaction, and performing solid-liquid separation on the product to obtain clear liquid-6 and a DCP solid phase;
and 7: and reacting the DCP solid phase with phosphoric acid to obtain MCP slurry.
Preferably, in the step 2, the mass ratio of the clear liquid-1 to the phosphate rock to the phosphoric acid is 1-20: 1: 1-10, wherein the mass ratio of the phosphogypsum to the dry phosphorus ore is 0.5-1: 1.
Preferably, in the step 2, the reaction time is 30-120 min, and the reaction temperature is 70-90 ℃.
Preferably, in the step 5, the reaction pH value is 2.0-3.5, the reaction temperature is 60-75 ℃, and the reaction time is 60-120 min.
Preferably, in the step 6, the reaction pH value is 5.5-6.5, the reaction temperature is 60-75 ℃, and the reaction time is 30-90 min. Preferably, P in the raffinate2O515-30% of SO30.5-4% of F, 0.3-1.0% of F, and Fe2O3Mass fraction of 0.5~2%，Al2O30.5-2% of mass fraction and 1-4% of MgO mass fraction.
Preferably, the clear liquid-3 is concentrated to obtain phosphoric acid, the phosphoric acid is recycled in the step 2 and the step 7, and the DCP solid phase and the phosphoric acid in the step 7 are mixed according to the ratio of Ca/P = 0.58-0.64.
Preferably, the vacuum degree of the concentration step is-60 to-80 kPa, and the temperature is 70 to 90 ℃.
Preferably, the gas phase overflowed in the concentration process is absorbed by water circulation to obtain the fluosilicic acid.
Preferably, the clear liquid-6 is used for preparing calcium carbonate slurry and calcium hydroxide slurry.
The mass ratio of the phosphorite in the step 2 to the phosphogypsum in the step 1 is 1: 0.5-1, and P in the phosphogypsum2O5The mass fraction is 0.5-1.0%;
the clear liquid-3 is composed of P2O510-25% of mass fraction, 0.1-0.3% of CaO, 0.5-1.5% of F, and Fe2O30.01-0.05% of Al2O30.01-0.05% of mass fraction, and 0.1-0.5% of MgO mass fraction; clear liquid-4 composition is P2O520-30% of mass fraction, 2-4% of CaO, 0.2-0.5% of F, and Fe2O30.5-2% by mass of Al2O30.5-2% of mass fraction and 1-4% of MgO mass fraction;
said thick paste-2 can be used as slow-release phosphate fertilizer, its P2O535-40% of CaO, 25-30% of CaO, 0.5-2.0% of F, and Fe2O31-4% by mass of Al2O31-4% of MgO by mass and 1-4% of MgO by mass;
the MCP slurry is feed-grade MCP, wherein P2O552 percent of CaO, 19.5 percent of CaO, 0.1 percent of F, and Fe2O30.3-0.6% of Al2O30.3-0.6% of mass fraction and 0.5-2% of MgO mass fraction;
the invention has the beneficial effects that:
(1) the extraction spent acid is efficiently utilized: the raffinate acid contains SO3、F、Fe2O3、Al2O3And MgO and other impurities, and the phosphoric acid quality is different from that of the existing wet-process phosphoric acid greatly, so that the MCP product is difficult to directly produce.
(2) And (3) separating anions and cations step by step: the invention adopts the reaction of the raffinate acid and the phosphorite and utilizes the free sulfuric acid in the raffinate acid to decompose the phosphorite, thereby not only saving the sulfuric acid, but also effectively reducing the SO in the raffinate acid3Mass fraction; secondly, a nanofiltration membrane filtering technology is adopted to realize the selective separation of phosphoric acid molecules, fluorine ions and the like, and F in the slurry is separated and then is separated and recovered through concentration; thirdly, calcium carbonate is adopted for further neutralization and purification, the pH value of the slurry is increased, and therefore citrate-soluble ferric aluminum phosphate in the raffinate acid is efficiently separated, and the solid phase can be used as a slow-release phosphate fertilizer.
(3) And (3) efficiently recovering fluorine: the method for removing fluorine in phosphoric acid mostly adopts a neutralization precipitation method and a concentration chemical precipitation method, the mass fraction of fluorine in the byproduct waste residue is as high as 5-20%, and the mass fraction of fluorine in soil is greatly increased by applying the method as a fertilizer, which may cause adverse effect on the growth of crops; the invention adopts the nanofiltration membrane purification and concentration defluorination technology for coupling, realizes the separation and recovery of small molecular fluorine in phosphoric acid, and effectively controls the mass fraction of fluorine in the slow-release phosphate fertilizer.
(4) The yield of phosphorus is improved: by adopting the raffinate acid and phosphoric acid two-stage ore dissolving technology, the dissolving rate of the phosphorite is greatly improved, the phosphorus yield in the phosphorite is improved to 98.5 percent from the average level of 97 percent in the current industry, and the phosphorus loss in the phosphorite extraction process is further reduced; in addition, the synergy of the nanofiltration membrane purification technology and the calcium carbonate neutralization purification technology is adopted, the phosphorus yield in the neutralization process is improved to 90 percent from the average industrial level of 85 percent, and the total phosphorus yield is obviously improved.
(5) The calcium in the phosphorite is efficiently utilized: phosphoric acid by wet process producing 1 ton phosphoric acid per ton (as P)2O5Calculated), 3.1t of phosphorite is consumed, 5.5t of byproduct gypsum is obtained (1.77 t of phosphorite byproduct phosphogypsum is consumed in a conversion mode), 0.5-1.0 t of byproduct gypsum is obtained when 1t of phosphorite is decomposed, the gypsum yield is reduced by 40-70%, and the method does not need to be used for preparing the gypsumOnly calcium in the phosphorite is converted into an MCP product, meanwhile, the gypsum emission is greatly reduced, and the environmental protection and economic pressure of enterprises is relieved.
Compared with the prior art: the raffinate acid in the method can be directly utilized without concentration, the energy consumption is low, and the raffinate acid can be fully recycled; the whole process flow does not need high-temperature heating, and the reaction is environment-friendly; the process meets the environmental protection requirements of energy conservation and emission reduction.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A method for preparing monocalcium phosphate, comprising:
step 1: the extraction spent acid reacts with the thick slurry returned in the step 3, the generated phosphogypsum is separated to obtain clear liquid-1, the ratio of the dry basis weight of the phosphogypsum to the consumed phosphate ore in the step 2 is 0.5:1, and P in the phosphogypsum is2O51.0 percent of mass fraction;
step 2: mixing the clear liquid-1 obtained in the step 1, phosphorite and phosphoric acid obtained in the step 9 according to the mass ratio of 1:1:10, reacting for 30min, and reacting at the temperature of 90 ℃;
and step 3: thickening the slurry obtained in the step 2 by using a thickener to obtain clear liquid-2 and thick slurry at the bottom layer, and returning the thick slurry to the step 1 for use;
and 4, step 4: the clear liquid-2 is separated and purified by a nanofiltration membrane to obtain clear liquid-3 with low cation mass fraction, and the clear liquid-4 with high cation mass fraction is conveyed to the step 9 and the step 5;
and 5: adopting calcium carbonate slurry and clear liquid-4 to react, purify and remove impurities, controlling the reaction pH value to be 2.0, controlling the reaction temperature to be 60 ℃, reacting for 60min, separating a solid phase into a slow-release phosphate fertilizer after the reaction is finished, and conveying the clear liquid-5 to the step 6;
step 6: the clear liquid-5 and calcium hydroxide slurry are further reacted, the reaction pH value is controlled to be 5.5, the reaction temperature is 60 ℃, the reaction time is 30min, DCP solid phase is obtained after the reaction is finished, and the clear liquid-6 is returned to be used for preparing calcium carbonate slurry and calcium hydroxide slurry;
and 7: mixing the solid phase obtained in the step 6 with the phosphoric acid obtained in the step 9 according to the ratio of Ca/P =0.58 to obtain MCP slurry;
and 8: drying and curing the MCP slurry, and packaging to obtain a feed-grade MCP product;
and step 9: concentrating the clear liquid-3 with low mass fraction of cations obtained in the step 4 to obtain phosphoric acid, wherein the concentration vacuum degree is-60 kPa, the temperature is 70 ℃, and the mass fraction of fluorine is 0.15 percent, and P is obtained2O5Phosphoric acid with mass fraction of 40% is respectively used for dissolving phosphorite and back-regulating DCP, and gas phase overflowed in the concentration process is circularly absorbed by water to obtain fluosilicic acid with concentration of 12%, and the fluosilicic acid can be used for producing sodium fluosilicate products.
TABLE 1 raw material, intermediate and end product control index
| Name of material | P2O5/% | SO3/% | CaO/% | F/% | Fe2O3/% | Al2O3/% | MgO/% |
| Raffinate acid | 15 | 0.5 | 0.3 | 0.5 | 0.5 | 1 | |
| Clear liquid-3 | 10 | 0.1 | 0.5 | 0.01 | 0.01 | 0.1 | |
| Clear liquid-4 | 20 | 2 | 0.2 | 0.5 | 0.5 | 1 | |
| Slow-release phosphate fertilizer | 40 | 30 | 0.5 | 1 | 1 | 1 | |
| MCP product | 52.1 | 19.5 | 0.1 | 0.3 | 0.3 | 0.5 |
Example 2
A method for preparing monocalcium phosphate, comprising:
step 1: the extraction spent acid reacts with the thick slurry returned in the step 3, the generated phosphogypsum is separated to obtain clear liquid-1, the ratio of the dry basis weight of the phosphogypsum to the consumed phosphate ore in the step 2 is 0.6:1, and P in the phosphogypsum is2O5The mass fraction is 0.75 percent;
step 2: mixing the clear liquid-1 obtained in the step 1, phosphorite and phosphoric acid obtained in the step 9 according to the mass ratio of 10:1:5, reacting for 60min at the reaction temperature of 80 ℃;
and step 3: thickening the slurry obtained in the step 2 by using a thickener to obtain clear liquid-2 and thick slurry at the bottom layer, and returning the thick slurry to the step 1 for use;
and 4, step 4: the clear liquid-2 is separated and purified by a nanofiltration membrane to obtain clear liquid-3 with low cation mass fraction, and the clear liquid-4 with high cation mass fraction is conveyed to the step 9 and the step 5;
and 5: adopting calcium carbonate slurry and clear liquid-4 to react, purify and remove impurities, controlling the reaction pH value to be 2.5, controlling the reaction temperature to be 65 ℃, reacting for 90min, separating a solid phase after the reaction is finished to be a slow-release phosphate fertilizer, and conveying the clear liquid-5 to the step 6;
step 6: the clear liquid-5 and calcium hydroxide slurry are further reacted, the reaction pH value is controlled to be 5.8, the reaction temperature is 65 ℃, the reaction time is 60min, DCP solid phase is obtained after the reaction is finished, and the clear liquid-6 is returned to be used for preparing calcium carbonate slurry and calcium hydroxide slurry;
and 7: mixing the solid phase obtained in the step 6 with the phosphoric acid obtained in the step 9 according to the ratio of Ca/P =0.60 to obtain MCP slurry;
and 8: drying and curing the MCP slurry, and packaging to obtain a feed-grade MCP product;
and step 9: concentrating the clear liquid-3 with low mass fraction of cations obtained in the step 4 to obtain phosphoric acid, wherein the concentration vacuum degree is-70 kPa, the temperature is 75 ℃, and the mass fraction of fluorine is 0.12 percent, and P is obtained2O5Phosphoric acid with the mass fraction of 45 percent is respectively used for dissolving phosphorite and back-regulating DCP, and gas phase overflowed in the concentration process is absorbed by adopting water circulation to obtain fluosilicic acid with the concentration of 12 percent, and the fluosilicic acid can be used for producing sodium fluosilicate products.
TABLE 2 raw material, intermediate and end product control index
| Name of material | P2O5/% | SO3/% | CaO/% | F/% | Fe2O3/% | Al2O3/% | MgO/% |
| Raffinate acid | 20 | 2 | 0.5 | 1.0 | 1.1 | 2.1 | |
| Clear liquid-3 | 15 | 0.2 | 1.0 | 0.03 | 0.04 | 0.2 | |
| Clear liquid-4 | 25 | 3 | 0.3 | 1.0 | 1.1 | 2 | |
| Slow-release phosphate fertilizer | 38 | 29 | 1.0 | 2 | 2 | 2 | |
| MCP product | 52.2 | 19.4 | 0.1 | 0.4 | 0.4 | 1.0 |
Example 3
A method for preparing monocalcium phosphate, comprising:
step 1: the extraction spent acid reacts with the thick slurry returned in the step 3, the generated phosphogypsum is separated to obtain clear liquid-1, the ratio of the dry basis weight of the phosphogypsum to the consumed phosphate ore in the step 2 is 0.8:1, and P in the phosphogypsum is2O5The mass fraction is 0.65 percent;
step 2: mixing clear liquid-1 obtained in the step 1, phosphorite and phosphoric acid obtained in the step 9 according to the mass ratio of 15:1:3, reacting for 90min, and reacting at the temperature of 80 ℃;
and step 3: thickening the slurry obtained in the step 2 by using a thickener to obtain clear liquid-2 and thick slurry at the bottom layer, and returning the thick slurry to the step 1 for use;
and 4, step 4: the clear liquid-2 is separated and purified by a nanofiltration membrane to obtain clear liquid-3 with low cation mass fraction, and the clear liquid-4 with high cation mass fraction is conveyed to the step 9 and the step 5;
and 5: adopting calcium carbonate slurry and clear liquid-4 to react, purify and remove impurities, controlling the reaction pH value to be 3.0, controlling the reaction temperature to be 70 ℃, reacting for 90min, separating a solid phase after the reaction is finished to be a slow-release phosphate fertilizer, and conveying the clear liquid-5 to the step 6;
step 6: the clear liquid-5 and calcium hydroxide slurry are further reacted, the reaction pH value is controlled to be 6.0, the reaction temperature is 70 ℃, the reaction time is 60min, DCP solid phase is obtained after the reaction is finished, and the clear liquid-6 is returned to be used for preparing calcium carbonate slurry and calcium hydroxide slurry;
and 7: mixing the solid phase obtained in the step 6 with the phosphoric acid obtained in the step 9 according to the ratio of Ca/P =0.62 to obtain MCP slurry;
and 8: drying and curing the MCP slurry, and packaging to obtain a feed-grade MCP product;
and step 9: concentrating the clear liquid-3 with low mass fraction of cations obtained in the step 4 to obtain phosphoric acid, wherein the concentration vacuum degree is-75 kPa, the temperature is 80 ℃, and the mass fraction of fluorine is 0.10 percent, and P is obtained2O5Phosphoric acid with the mass fraction of 50 percent is respectively used for dissolving phosphorite and back-regulating DCP, and gas phase overflowed in the concentration process is circularly absorbed by water to obtain fluosilicic acid with the concentration of 12 percent, which can be used for producing sodium fluosilicate products.
TABLE 3 raw material, intermediate and end product control index
| Name of material | P2O5/% | SO3/% | CaO/% | F/% | Fe2O3/% | Al2O3/% | MgO/% |
| Raffinate acid | 25 | 3 | 0.7 | 1.5 | 1.3 | 3 | |
| Clear liquid-3 | 20 | 0.3 | 1.0 | 0.04 | 0.03 | 0.4 | |
| Clear liquid-4 | 25 | 3 | 0.35 | 1.1 | 0.9 | 2.1 | |
| Slow-release phosphate fertilizer | 37 | 28 | 1.5 | 3 | 3 | 3 | |
| MCP product | 52.2 | 19.6 | 0.1 | 0.5 | 0.5 | 1.5 |
Example 4
A method for preparing monocalcium phosphate, comprising:
step 1: the extraction spent acid reacts with the thick slurry returned in the step 3, the generated phosphogypsum is separated to obtain clear liquid-1, the ratio of the dry basis weight of the phosphogypsum to the consumed phosphate ore in the step 2 is 1:1, and P in the phosphogypsum is2O5The mass fraction is 0.5 percent;
step 2: mixing the clear liquid-1 obtained in the step 1, phosphorite and phosphoric acid obtained in the step 9 according to the mass ratio of 20:1:1, reacting for 120min at the reaction temperature of 70 ℃;
and step 3: thickening the slurry obtained in the step 2 by using a thickener to obtain clear liquid-2 and thick slurry at the bottom layer, and returning the thick slurry to the step 1 for use;
and 4, step 4: the clear liquid-2 is separated and purified by a nanofiltration membrane to obtain clear liquid-3 with low cation mass fraction, and the clear liquid-4 with high cation mass fraction is conveyed to the step 9 and the step 5;
and 5: adopting calcium carbonate slurry and clear liquid-4 to react, purify and remove impurities, controlling the reaction pH value to be 3.5, controlling the reaction temperature to be 75 ℃, reacting for 120min, separating a solid phase into a slow-release phosphate fertilizer after the reaction is finished, and conveying the clear liquid-5 to the step 6;
step 6: the clear liquid-5 and calcium hydroxide slurry are further reacted, the reaction pH value is controlled to be 6.5, the reaction temperature is 75 ℃, the reaction time is 90min, DCP solid phase is obtained after the reaction is finished, and the clear liquid-6 is returned to be used for preparing calcium carbonate slurry and calcium hydroxide slurry;
and 7: mixing the solid phase obtained in the step 6 with the phosphoric acid obtained in the step 9 according to the ratio of Ca/P =0.64 to obtain MCP slurry;
and 8: drying and curing the MCP slurry, and packaging to obtain a feed-grade MCP product;
and step 9: cation obtained in step 4Concentrating the clear liquid-3 with low mass fraction to obtain phosphoric acid, concentrating at 90 deg.C and vacuum degree of-80 kPa to obtain fluorine mass fraction of 0.05%, and P2O5Phosphoric acid with mass fraction of 55% is respectively used for dissolving phosphorite and back-regulating DCP, gas phase overflowed in the concentration process is circularly absorbed by water to obtain fluosilicic acid with concentration of 12%, and the fluosilicic acid can be used for producing sodium fluosilicate products.
TABLE 4 raw material, intermediate and end product control index
| Name of material | P2O5/% | SO3/% | CaO/% | F/% | Fe2O3/% | Al2O3/% | MgO/% |
| Raffinate acid | 30 | 4 | 1.0 | 2 | 2 | 5 | |
| Clear liquid-3 | 25 | 0.3 | 1.5 | 0.05 | 0.05 | 0.5 | |
| Clear liquid-4 | 30 | 4 | 0.5 | 2 | 2 | 4 | |
| Slow-release phosphate fertilizer | 35 | 25 | 2.0 | 4 | 4 | 4 | |
| MCP product | 52.1 | 19.3 | 0.1 | 0.6 | 0.6 | 2 |
Note: the contents and percentages in the application are mass fractions unless specified otherwise.
Although the invention has been described herein with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure. More specifically, various variations and modifications are possible in the component parts and/or arrangements of the subject combination arrangement within the scope of the disclosure, the drawings and the appended claims. In addition to variations and modifications in the component parts and/or arrangements, other uses will also be apparent to those skilled in the art.
Claims (10)
1. A preparation method of monocalcium phosphate is characterized by comprising the following steps: the method comprises the following steps:
step 1: the extraction spent acid is used for reacting with the thick slurry-1, and the generated phosphogypsum is separated to obtain clear liquid-1;
step 2: mixing the clear liquid-1, phosphorite and phosphoric acid and reacting to obtain slurry-2;
and step 3: carrying out solid-liquid separation on the slurry-2 to obtain clear liquid-2 and thick slurry-1, and returning the thick slurry-1 to the step 1 for use;
and 4, step 4: separating the clear liquid-2 by a nanofiltration membrane to obtain clear liquid-3 with relatively low cation content and clear liquid-4 with relatively high cation content;
and 5: adding calcium carbonate slurry into the clear liquid-4 for reaction, and performing solid-liquid separation on the product to obtain clear liquid-5 and thick slurry-2;
step 6: adding calcium hydroxide slurry into the clear liquid-5 for reaction, and performing solid-liquid separation on the product to obtain clear liquid-6 and a DCP solid phase;
and 7: and reacting the DCP solid phase with phosphoric acid to obtain MCP slurry.
2. The preparation method of monocalcium phosphate according to claim 1, wherein in the step 2, the mass ratio of clear liquid-1 to phosphate rock to phosphoric acid is 1-20: 1: 1-10, and the mass ratio of phosphogypsum to dry phosphate rock is 0.5-1: 1.
3. The method for preparing monocalcium phosphate according to claim 1, wherein in the step 2, the reaction time is 30 to 120min, and the reaction temperature is 70 to 90 ℃.
4. The method for preparing monocalcium phosphate according to claim 1, wherein in the step 5, the reaction pH is 2.0 to 3.5, the reaction temperature is 60 to 75 ℃, and the reaction time is 60 to 120 min.
5. The method for preparing monocalcium phosphate according to claim 1, wherein in the step 6, the reaction pH is 5.5 to 6.5, the reaction temperature is 60 to 75 ℃, and the reaction time is 30 to 90 min.
6. The method of claim 1, wherein P is the raffinate2O515-30% of SO30.5-4% of F, 0.3-1.0% of F, and Fe2O30.5-2% by mass of Al2O30.5-2% of mass fraction and 1-4% of MgO mass fraction.
7. The method for preparing monocalcium phosphate according to claim 1, wherein the clear solution-3 is concentrated to obtain phosphoric acid, the phosphoric acid is recycled in step 2 and/or step 7, and the DCP solid phase and the phosphoric acid in step 7 are mixed according to Ca/P = 0.58-0.64.
8. The method for preparing monocalcium phosphate according to claim 7, wherein the concentration step is performed at a vacuum degree of-60 to-80 kPa and a temperature of 70 to 90 ℃.
9. The method for preparing monocalcium phosphate according to claim 7, wherein the gas phase overflowing during concentration is absorbed by circulating water to obtain fluosilicic acid.
10. The method of producing monocalcium phosphate according to claim 1, wherein the clear solution-6 is used for formulating calcium carbonate slurry and calcium hydroxide slurry.
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