CN108249415B - Method and device for processing monocalcium phosphate - Google Patents

Method and device for processing monocalcium phosphate Download PDF

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CN108249415B
CN108249415B CN201711462623.0A CN201711462623A CN108249415B CN 108249415 B CN108249415 B CN 108249415B CN 201711462623 A CN201711462623 A CN 201711462623A CN 108249415 B CN108249415 B CN 108249415B
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calcium
mcp
ferrous
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phosphoric acid
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CN108249415A (en
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付全军
王力刚
盛勇
刘庭兵
马先林
曾斌
周佩
张继松
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Zhong Hua Yunlong Co Ltd
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Sinochem Yunlong Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00Phosphorus; Compounds thereof
    • C01B25/16Oxyacids of phosphorus; Salts thereof
    • C01B25/26Phosphates
    • C01B25/32Phosphates of magnesium, calcium, strontium, or barium
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K20/00Accessory food factors for animal feeding-stuffs
    • A23K20/20Inorganic substances, e.g. oligoelements
    • A23K20/26Compounds containing phosphorus
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K20/00Accessory food factors for animal feeding-stuffs
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    • A23K20/30Oligoelements
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00Phosphorus; Compounds thereof
    • C01B25/16Oxyacids of phosphorus; Salts thereof
    • C01B25/26Phosphates
    • C01B25/32Phosphates of magnesium, calcium, strontium, or barium
    • C01B25/321Methods for converting an alkaline earth metal ortho-phosphate into another ortho-phosphate

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Abstract

The invention discloses a processing method of monocalcium phosphate, which comprises the following steps: reacting defluorinated phosphoric acid with calcium carbonate or calcium hydrophosphate slurry, drying by a spray drying tower to obtain a powdery MCP product, and using part of the powdery product and collected dust as return materials for producing granular MCP products; defluorinated phosphoric acid is directly reacted with calcium carbonate or calcium hydrogen phosphate powder, a return material, a small amount of granulation regulator and ferrous stabilizer are added, and granular MCP products are obtained after granulation by a granulator, drying and screening. The method realizes the co-production of powdery and granular feed-grade MCP, efficiently recycles dust materials, improves the strength and uniformity of particles, avoids the pulverization of particles, effectively relieves the blockage of material screening and crushing equipment, and simultaneously obtains granular MCP products with the function of supplementing phosphorus, calcium and iron.

Description

Method and device for processing monocalcium phosphate
Technical Field
The invention relates to the technical field of phosphorus chemical industry, in particular to a method and a device for processing monocalcium phosphate.
Background
Phosphorus is an important life element, and calcium phosphate salt is used as an important feed additive to provide enough calcium and phosphorus elements for the growth of animal bones. The calcium dihydrogen phosphate is used as a feed-grade calcium phosphate salt additive with the best solubility and the highest animal absorption efficiency, and is widely popularized and applied in the feed industry.
Feed-grade monocalcium phosphate (MCP) is produced by a plurality of methods, and at present, wet-process phosphoric acid, calcium hydrophosphate and calcium carbonate are mostly used as raw materials, and the production methods can be divided into a slurry spray drying method and a dry powder direct granulation method.
A slurry spray drying method is a main method for producing MCP products at present, and is characterized in that purified phosphoric acid and slurry of calcium hydrophosphate or calcium carbonate are mainly adopted to react to prepare MCP slurry, and the MCP slurry after reaction is granulated by spray drying to obtain the MCP products. The products obtained by the process technology are all powder, and the product index is stable; however, since a large amount of dust is generated in the spray drying process, enterprises generally directly mix and package the collected dust with the product, so that the product is easy to agglomerate.
Phosphoric acid reacts with calcium carbonate powder, the reacted materials are mixed with return materials for granulation, and the product is obtained by drying and screening, but the product index is easy to be unstable due to incomplete reaction of dry powder, particularly, the phosphorus content of fine powder materials is low, so that the product quality is influenced; in addition, because MCP contains a small amount of free phosphoric acid, the viscosity of the material is high, and large-particle materials easily block a sieve plate and a crusher, so that the operation stability of the device is seriously influenced.
With the improvement of the requirements of feed production enterprises on indexes such as MCP index stability, fluidity, uniformity and the like, particularly the market demand of granular MCP products is increased year by year, and the existing production technology can not completely meet the customer demand. Aiming at the defects of the prior production technology, the problems that the utilization of the byproduct dust material in the slurry spray drying method is difficult, the product quality of the dry powder direct granulation method is unstable, the production system is operated unstably and the like are urgently needed to be solved.
Disclosure of Invention
The invention aims to provide a method and a device for processing monocalcium phosphate, which can solve the problems of large dust amount and easy caking of products in a slurry spray drying method and the problems of poor product quality and poor device operation stability in a dry powder direct granulation method.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for processing monocalcium phosphate, comprising:
step a: taking phosphoric acid and calcium-containing slurry as raw materials, obtaining a powdery MCP product by adopting a spray drying method, recovering a dust material A in dried tail gas, and mixing the dust material A and the powdery MCP product to obtain a return material B;
step b: the method comprises the steps of taking phosphoric acid, calcium-containing powder, an auxiliary agent and a return material C as raw materials, reacting to obtain a material D, mixing the material D with the return material B, reacting, granulating, drying and screening the product in sequence to obtain a granular MCP product meeting the requirement of the specified particle size, and crushing the material exceeding the specified particle size to the particle size of less than 40 meshes and more than 80%, and mixing the crushed material with the material smaller than the specified particle size to obtain the return material C.
P in the above-mentioned returned material C2O522.0-22.5 percent of Ca, 13-15 percent of Ca and 0.5-4.0 percent of water, wherein the mass proportion of the material with the particle size of more than 0.45mm is 5-35 percent, the mass proportion of the material with the particle size of 0.45-0.20 mm is 30-40 percent, and the mass proportion of the material with the particle size of less than 0.20mm is 25-65 percent; p in the above-mentioned returned material B2O522.5-23.0% of Ca, 13-15% of Ca and 0.5-1.5% of water, wherein the mass proportion of the material with the particle size of more than 0.45mm is 0-10%, the mass proportion of the material with the particle size of 0.45-0.20 mm is 60-80%, and the mass proportion of the material with the particle size of less than 0.20mm is 10-40%; the powdery MCP product P2O522.5-23.0 percent of Ca, 13-15 percent of Ca and 0.5-1.5 percent of water, wherein the particle size distribution of the Ca is 40-60 percent of the mass proportion of the material with the particle size of 0.45-0.20 mm and 40-60 percent of the mass proportion of the material with the particle size of 0.20-0.10 mm; the granular MCP product P2O522.5-23.0 percent of Ca, 13-15 percent of Ca, 0.5-1.5 percent of ferrous iron and 0.5-1.5 percent of water, wherein the particle size of the material is distributed in the mass proportion of 50-70 percent of material with the particle size of 0.90-0.45 mm and 30-50 percent of material with the particle size of 0.45-0.20 mm.
Preferably, the calcium-containing slurry in step a is one or more of calcium carbonate, calcium bicarbonate, calcium hydrogen phosphate and calcium phosphate, and the moisture content is 30-50%.
Preferably, the calcium-containing powder in the step b is one or more of calcium carbonate, calcium bicarbonate, calcium hydrogen phosphate and calcium phosphate, and the moisture content is 0.01-3%.
Preferably, the phosphoric acid is defluorinated phosphoric acid with phosphorus pentoxide concentration of 40-50%, and the raw material proportion of step a and step b is adjusted according to Ca/P of 0.60-0.65 to obtain raw material F.
Preferably, in the step B, the raw material F and the return material C are mixed according to the dry basis mass ratio of 1: 1-3, and the material D and the return material B are mixed according to the dry basis mass ratio of 1: 0.5-5.
Preferably, the auxiliary agent comprises a granulation regulator accounting for 0.1-3% of the total weight of the material and a ferrous stabilizer accounting for 0.1-2% of the total weight of the material.
Preferably, the granulation regulator is one or more of ferrous sulfate, ferrous chloride, ferrous carbonate, ferrous fumarate and ferrous glycinate.
Preferably, the ferrous stabilizer is one or more of sodium thiosulfate, sodium metabisulfite and ascorbic acid.
Preferably, the water content of the material D in the step b is 13-25%, and the material D is obtained by reacting the raw materials at the temperature of 60-80 ℃ for 10-30 s.
Preferably, the reaction temperature in the reaction process of the material D and the return material B is 60-80 ℃, the retention time of the material is 10-30s, and the water content of the reacted material is 5-10%.
A device for producing monocalcium phosphate comprises an MCP reaction tank and a spray drying tower connected with a discharge port of the MCP reaction tank, wherein a tail gas discharge port of the spray drying tower is communicated with a dust removal chamber, and a dust outlet of the dust removal chamber and a discharge port of the spray drying tower are both connected with a secondary reactor;
the feed inlet of the secondary reactor is connected with the discharge outlet of the primary reactor, and materials discharged by the secondary reactor sequentially pass through a granulator, a drying kiln and a double-layer vibrating screen;
the discharge port corresponding to the upper screen in the double-layer vibrating mesh screen is connected to the feed port of the first-stage reactor through the crusher, and the discharge port corresponding to the lower screen in the double-layer vibrating mesh screen is directly connected with the feed port of the first-stage reactor.
The content of free phosphoric acid in the core of large-particle materials produced by a dry powder direct granulation method is higher, the content of phosphorus in fine-particle materials is lower, and the large-particle materials are irregular after being crushed and directly used as return materials to influence the appearance of the granulated materials. The invention adopts a two-stage reaction process, the dry powder with unstable product quality and irregular appearance shape is directly granulated and screened as the return material added in the first-stage reactor, and phosphoric acid and calcium carbonate/calcium hydrogen phosphate powder which are newly added in the first-stage reactor are preferentially mixed and reacted to promote the reaction homogenization of the materials, thereby better solving the problem of recycling the return material.
The invention adopts a slurry spray drying method to produce the powdery MCP product, fine dust with round and smooth appearance and part of the powdery MCP product are directly used as the return material C, so that high-quality return material with round and smooth appearance and stable quality is provided for the secondary reactor, and meanwhile, the material with better dispersity and uniformity is obtained.
The granulation regulator is added by 0.1-3%, the component is ferrous salt, the material has low viscosity, the viscosity of the MCP material can be effectively regulated and controlled, the blockage of the MCP material on equipment in the screening and crushing processes is relieved, and the operation period of the device is prolonged by more than one time; the iron ions are added, so that the strength of the material can be effectively improved, and the pulverization of the granular material in the processes of packaging, storage and transportation is avoided; ferrous salt is selected as a raw material, so that the ferrous content in the feed can be increased, and calcium and phosphorus can be supplemented while iron is supplemented.
According to the invention, 0.1-2% of ferrous stabilizer is added, and the component is a reducing substance, so that the additive can effectively inhibit the added ferrous auxiliary agent from being oxidized, and can also effectively reduce ferric ions carried in phosphoric acid to be converted into ferrous ions, thereby realizing the high-efficiency utilization of iron in MCP and improving the added value of products.
The granular MCP product obtained by the invention has uniform and round granules, good fluidity and excellent anti-caking performance, and at the same time, more than 80% of iron element carried in the product is ferrous, so that the granular MCP product can be efficiently absorbed by animals, the nutritional value of the product is improved, and the granular MCP product has obvious market competitiveness.
Compared with the prior art, the invention has the beneficial effects of at least one of the following:
the single set of system can simultaneously produce powdery and granular feed-grade monocalcium phosphate products with stable quality and excellent fluidity and anti-caking performance.
And the dust material is recycled and used for producing granular MCP products, and the anti-caking performance of the powdery products is improved.
By adopting a two-stage reaction homogenization technology, the returned materials with larger product stability difference are utilized in a grading way, and the uniformity and stability of the product are improved.
And a granulation regulator and a ferrous stabilizer are added, so that the equipment blockage in the processes of material screening and crushing is effectively relieved, the particle strength is improved, the particle pulverization is avoided, the ferrous content of the product is improved, and the granular MCP product capable of supplementing phosphorus, calcium and iron is obtained.
Drawings
FIG. 1 is a flow chart of the process of calcium dihydrogen phosphate according to 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:
by P2O5Defluorinated phosphoric acid with the concentration of 40 percent and calcium carbonate slurry with the water content of 50 percent are prepared into MCP slurry in an MCP reaction tank 1, and are atomized and dried by a spray drying tower 2 to obtain a powdery MCP product, and the dried tail gas is dedusted by a dedusting chamber 3 to obtain a dust material which is mixed with the powdery MCP product according to the dry basis mass ratio of 1:10 to be used as a return material B; calcium carbonate powder containing 0.01% of water and P2O5The dosage of the defluorinated phosphoric acid with the concentration of 40 percent is adjusted according to the Ca/P ratio of 0.60, 0.1 percent of ferrous fumarate and ferrous glycinate and 0.1 percent of sodium metabisulfite are added, the mixture and the return material C enter a primary reactor 4 according to the dry basis mass ratio of 1:3, the temperature of the reactant is 60 ℃, the residence time is 10s, the moisture content of the material D is 13%, the mixture D and the return material B enter a secondary reactor 5 according to the dry basis mass ratio of 1:0.5, the temperature of the reactant is 60 ℃, the residence time is 10s, the moisture content of the material E is 10%, the mixture E enters a granulator 6 for granulation, the granulated material is dried by a drying kiln 7, the material with qualified particle size is sieved by a double-layer vibrating screen 8, the oversize material of the upper layer screen is crushed by a crusher 9 until the particle size is smaller than 40 meshes and the proportion is larger than 80%, and mixing the MCP powder with undersize materials of the lower-layer screen mesh to obtain a return material C, wherein the material obtained between the two layers of screen meshes is a granular MCP product.
TABLE 1-1 Return index and particle size distribution
Figure GDA0002372300030000041
TABLE 1-2 index and particle size distribution of powdery and granular MCP product
Figure GDA0002372300030000042
Figure GDA0002372300030000051
Example 2:
by P2O5Defluorinated phosphoric acid with the concentration of 45 percent and calcium hydrophosphate slurry with the water content of 40 percent are prepared into MCP slurry in an MCP reaction tank 1, a powdery MCP product is obtained after atomization drying in a spray drying tower 2, a dust material is obtained after drying tail gas is dedusted in a dedusting chamber 3, and the powdery MCP product and the dust material are mixed according to the ratio of 1:5 to be used as a return material B; calcium hydrogen phosphate powder with water content of 3.0% and P2O5The dosage of the defluorinated phosphoric acid with the concentration of 45 percent is adjusted according to the Ca/P ratio of 0.61, 0.5 percent of ferrous carbonate and 0.5 percent of sodium metabisulfite are added, feeding the material D and the return material C into a primary reactor 4 according to the dry basis mass ratio of 1:2, keeping the temperature of the reactant at 70 ℃ for 15s to obtain the moisture content of the material D of 20%, feeding the material D and the return material B into a secondary reactor 5 according to the dry basis mass ratio of 1:2, keeping the temperature of the reactant at 70 ℃ for 15s to obtain the moisture content of the material E of 7%, feeding the material E into a granulator 6 for granulation, drying the granulated material by using a drying kiln 7, sieving the material with qualified particle size by using a double-layer vibrating screen 8, crushing the oversize material of the upper-layer screen by using a crusher 9 until the particle size is smaller than 40 meshes and is larger than 80%, and mixing the MCP powder with undersize materials of the lower-layer screen mesh to obtain a return material C, wherein the material obtained between the two layers of screen meshes is a granular MCP product.
TABLE 2-1 Return index and particle size distribution
Figure GDA0002372300030000052
TABLE 2-2 index and particle size distribution of powdery and granular MCP product
Figure GDA0002372300030000053
Example 3:
by P2O5Defluorinated phosphoric acid with the concentration of 45 percent and calcium bicarbonate slurry with the water content of 40 percent are prepared into MCP slurry in an MCP reaction tank 1, a powdery MCP product is obtained after atomization drying in a spray drying tower 2, a dust material is obtained after drying tail gas is dedusted in a dedusting chamber 3, and the powdery MCP product and the dust material are mixed according to the ratio of 1:1 to serve as a return material B; calcium bicarbonate powder with water content of 1% and P2O5The dosage of the defluorinated phosphoric acid with the concentration of 45 percent is adjusted according to the Ca/P ratio of 0.63, 1.5 percent of ferrous chloride and 1.0 percent of sodium thiosulfate are added, feeding the material D and the return material C into a primary reactor 4 according to the dry basis mass ratio of 1:2, keeping the temperature of the reactant at 70 ℃ for 25s to obtain the moisture content of the material D of 20%, feeding the material D and the return material B into a secondary reactor 5 according to the dry basis mass ratio of 1:3, keeping the temperature of the reactant at 70 ℃ for 15s to obtain the moisture content of the material E of 7%, feeding the material E into a granulator 6 for granulation, drying the granulated material by using a drying kiln 7, sieving the material with qualified particle size by using a double-layer vibrating screen 8, crushing the oversize material of the upper-layer screen by using a crusher 9 until the particle size is smaller than 40 meshes and is larger than 80%, and mixing the MCP powder with undersize materials of the lower-layer screen mesh to obtain a return material C, wherein the material obtained between the two layers of screen meshes is a granular MCP product.
TABLE 3-1 Return index and particle size distribution
Figure GDA0002372300030000061
TABLE 3-2 index and particle size distribution of powdery and granular MCP products
Figure GDA0002372300030000062
Example 4:
by P2O5Defluorinated phosphoric acid with concentration of 50% and water content of 30%Preparing the calcium phosphate slurry in an MCP reaction tank 1 to obtain MCP slurry, performing atomization drying in a spray drying tower 2 to obtain a powdery MCP product, removing dust from dried tail gas in a dust removal chamber 3 to obtain a dust material, and mixing the dust material with the powdery MCP product according to a ratio of 1:0 to obtain a return material B; calcium phosphate powder containing 2% of water and P2O5The dosage of the defluorinated phosphoric acid with the concentration of 50 percent is adjusted according to the Ca/P ratio of 0.65, 3 percent of ferrous sulfate and 2 percent of ascorbic acid are added, feeding the material D and the return material C into a primary reactor 4 according to the dry basis mass ratio of 1:2, keeping the temperature of the reactant at 80 ℃ for 30s to obtain the moisture content of the material D at 25%, feeding the material D and the return material B into a secondary reactor 5 according to the dry basis mass ratio of 1:5, keeping the temperature of the reactant at 80 ℃ for 30s to obtain the moisture content of the material E at 5%, feeding the material E into a granulator 6 for granulation, drying the granulated material by using a drying kiln 7, sieving the material with qualified particle size by using a double-layer vibrating screen 8, crushing the oversize material of the upper-layer screen by using a crusher 9 until the particle size is smaller than 40 meshes and is larger than 80%, and mixing the MCP powder with undersize materials of the lower-layer screen mesh to obtain a return material C, wherein the material obtained between the two layers of screen meshes is a granular MCP product.
TABLE 4-1 Return index and particle size distribution
Figure GDA0002372300030000063
Figure GDA0002372300030000071
TABLE 4-2 index and particle size distribution of powdery and granular MCP products
Figure GDA0002372300030000072
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 (6)

1. A processing method of monocalcium phosphate is characterized in that: the method comprises the following steps:
step a: taking phosphoric acid and calcium-containing slurry as raw materials, obtaining a powdery MCP product by adopting a spray drying method, recovering a dust material A in dried tail gas, and mixing the dust material A and the powdery MCP product to obtain a return material B;
step b: taking phosphoric acid, calcium-containing powder, an auxiliary agent and a return material C as raw materials, carrying out reaction to obtain a material D, mixing the material D with the return material B, carrying out reaction to obtain a material E, sequentially carrying out granulation, drying and screening on the material E to obtain a granular MCP product meeting the requirement of a specified particle size, and mixing the crushed material with the particle size smaller than the specified particle size to obtain the return material C; the material D in the step b is obtained by reacting the raw materials for 10-30s at the temperature of 60-80 ℃; the reaction temperature in the reaction process of the material D and the return material B is 60-80 ℃, and the retention time of the material is 10-30 s;
the auxiliary agent comprises a granulation regulator accounting for 0.1-3% of the total weight of the materials and a ferrous stabilizer accounting for 0.1-2% of the total weight of the materials;
the granulation regulator is one or more of ferrous sulfate, ferrous chloride, ferrous carbonate, ferrous fumarate and ferrous glycinate; the ferrous stabilizer is one or more of sodium thiosulfate, sodium metabisulfite and ascorbic acid.
2. The method for processing monocalcium phosphate according to claim 1, wherein the calcium-containing slurry in step a is one or more of calcium carbonate, calcium bicarbonate, calcium hydrogen phosphate and calcium phosphate, and the water content is 30-50%.
3. The method for processing monocalcium phosphate according to claim 1, wherein the calcium-containing powder in step b is one or more of calcium carbonate, calcium bicarbonate, calcium hydrogen phosphate and calcium phosphate, and the moisture content is 0.01-3%.
4. The method for processing monocalcium phosphate according to claim 1, wherein the phosphoric acid is defluorinated phosphoric acid with a phosphorus pentoxide concentration of 40-50%, and the raw material ratio in each of step a and step b is adjusted to 0.60-0.65 in terms of a Ca/P ratio to obtain a raw material F.
5. The method for processing monocalcium phosphate according to claim 4, wherein in step B, a raw material F and a return material C are mixed in a dry-basis mass ratio of 1: 1-3, a material D and a return material B are mixed in a dry-basis mass ratio of 1: 0.5-5, and the raw material F is a mixture of phosphoric acid, calcium-containing powder and an auxiliary agent.
6. The device for producing monocalcium phosphate is characterized by comprising an MCP reaction tank (1) and a spray drying tower (2) connected with a discharge port of the MCP reaction tank, wherein the MCP reaction tank and the spray drying tower are sequentially connected, a tail gas discharge port of the spray drying tower (2) is communicated with a dust removal chamber (3), and a dust outlet of the dust removal chamber (3) and the discharge port of the spray drying tower (2) are both connected with a secondary reactor (5); a feed inlet of the secondary reactor (5) is connected with a discharge outlet of the primary reactor (4), and materials discharged by the secondary reactor (5) sequentially pass through a granulator (6), a drying kiln (7) and a double-layer vibrating screen (8);
the discharge port corresponding to the upper layer screen mesh in the double-layer vibrating mesh screen (8) is connected to the feed port of the first-stage reactor (4) through a crusher (9), and the discharge port corresponding to the lower layer screen mesh in the double-layer vibrating mesh screen (8) is directly connected with the feed port of the first-stage reactor (4).
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WO1999002455A1 (en) * 1997-07-08 1999-01-21 S A Feed Phosphates (Proprietary) Limited A method for the production of a mono-calcium phosphate product
CN102515127A (en) * 2011-11-16 2012-06-27 贵州川恒化工有限责任公司 Method for preparing fodder-grade calcium hydrogen phosphate or fodder-grade calcium hydrogen phosphate type III
CN102701171B (en) * 2012-06-21 2014-03-19 中化云龙有限公司 Production method of feed-grade granular calcium hydrogen phosphate III-type product
CN105217592A (en) * 2015-09-17 2016-01-06 中化云龙有限公司 The production method of the granular monocalcium phosphate of feed grade
CN205367732U (en) * 2015-12-18 2016-07-06 瓮福(集团)有限责任公司 Fodder level calcium dihydrogen phosphate apparatus for producing

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