CN110316710B - Production process of high-nutrient powdery monoammonium phosphate - Google Patents
Production process of high-nutrient powdery monoammonium phosphate Download PDFInfo
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- CN110316710B CN110316710B CN201910600797.1A CN201910600797A CN110316710B CN 110316710 B CN110316710 B CN 110316710B CN 201910600797 A CN201910600797 A CN 201910600797A CN 110316710 B CN110316710 B CN 110316710B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/018—Mixtures of inorganic and organic compounds
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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
- C01B25/01—Treating phosphate ores or other raw phosphate materials to obtain phosphorus or phosphorus compounds
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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
- C01B25/28—Ammonium phosphates
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
- B03D2203/06—Phosphate ores
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a production process of high-nutrient powdery monoammonium phosphate, which specifically comprises the following steps: s1, the phosphorite blending ore comprises the following components in percentage by weight: p 2 O 5 %27.2-31.5%, mgO < 3%, K + Na < 0.5%; s2, grinding ore to prepare ore pulp; s3, extracting phosphoric acid; s4, neutralizing and concentrating to obtain a powdery monoammonium phosphate product with total nutrient content of 58-65% in mass fraction; the production process is reasonable, the product quality is high, and the stability is good; the selected flotation agent has strong collecting capability and good selectivity of flotation agent, and P obtained after flotation 2 O 5 30.9 percent of grade, 0.71 percent of MgO content and 90.15 percent of recovery rate.
Description
Technical Field
The invention belongs to the technical field of fertilizers, and particularly relates to a production process of high-nutrient powdery monoammonium phosphate.
Background
At present, domestic ammonium phosphate product market is seriously saturated, promotes product quality, realizes that the breakthrough innovation of product is the important way of promoting enterprise competitiveness, promotes the product pluralism, satisfies the demand of high-end fertile production, is that the enterprise is in fierce market competition, the important guarantee of standing on the market, reinforcing enterprise's anti-risk ability.
China is one of countries with large phosphate rock reserves, but most of the phosphate rocks are medium and low grade phosphate rocks with low phosphorus pentoxide content, and the phosphate rocks with high phosphorus pentoxide grade which can be directly exploited and utilized can only be exploited for about ten years. The development and utilization of the middle-low grade collophanite belong to a worldwide problem because various minerals are complex in inlaying relation, fine in inlaying granularity and poor in dissociation property, and silicate gangue minerals and carbonate minerals such as dolomite in the ores are high in content ratio. In phosphorite flotation, the existing collecting agent has low selectivity and poor low-temperature flotation effect.
Disclosure of Invention
The invention aims to provide a production process of high-nutrient powdery monoammonium phosphate, which is reasonable, and has high product quality and good stability.
The purpose of the invention can be realized by the following technical scheme:
a production process of high-nutrient powdery monoammonium phosphate specifically comprises the following steps:
s1, the weight ratio of each component of the phosphorite ore blending is as follows: p 2 O 5 ％27.2-31.5％、MgO＜3％、K+Na＜0.5％；
S2, grinding to prepare ore pulp: grinding the ore blending ore in the step S1 for 3-4h to form phosphorus ore pulp, and performing reverse flotation by adding a flotation agent;
s3, extraction of phosphoric acid: pumping the concentrate pulp subjected to flotation in the step S2, sulfuric acid accounting for 1/4 of the total reaction amount and return acid of a phosphoric acid settling tank into a pre-reactor, pre-reacting the concentrate pulp, the sulfuric acid and the return acid, feeding the reaction materials into a phosphoric acid extraction tank, adding sulfuric acid accounting for 3/4 of the total reaction amount, further completely decomposing the pulp and forming slurry, and filtering to obtain finished phosphoric acid; the mass fraction of the finished phosphoric acid is 33-48%;
s4, neutralizing and concentrating
(1) Introducing the phosphoric acid filtrate obtained in the step S3 into a neutralization tank, introducing ammonia gas, heating to 50-53 ℃, starting a stirring device to enable the materials to have a pre-neutralization reaction, wherein the pH is 2.4-2.7, continuing stirring and aging for 2 hours after the reaction is finished, standing and settling for 3 hours, and filtering again to obtain filter residues and filtrate containing monoammonium phosphate;
(2) And (2) introducing gas ammonia into the filtrate obtained in the step (1) again, controlling the pH value of the ammoniation process to be 4.7-5.1, and concentrating and drying the slurry after the ammoniation is finished to obtain a powdery monoammonium phosphate product with the total nutrient content of 58-65% in mass fraction.
Further, in step S2, the adding amount of the flotation agent is 0.6-0.8% of the weight of the phosphorite pulp in step S2.
Further, in step S2, the flotation agent comprises the following raw materials in parts by weight: 0.5-0.8 part of flotation reagent, 10-15 parts of sulfuric acid and 1 part of citric acid.
Further, the preparation method of the flotation reagent comprises the following steps: adding 1mol of allyl polyoxyethylene glycidyl ether, a platinum catalyst and 2L of a toluene solvent into a reaction kettle, uniformly stirring, heating to 55-60 ℃, dropwise adding 1.1-1.2mol of hydrogen-containing silicone oil, finishing dropwise adding within 1h, continuously heating to 130-140 ℃, carrying out reflux reaction for 6-8h, cooling to 85-100 ℃ after the reaction is finished, adding 1.1-1.2mol of stearic acid and 10mmol of cesium carbonate, continuously stirring for reaction for 5-7h, cooling to room temperature, filtering, carrying out rotary evaporation to remove toluene, washing a concentrate with 300ml of water and 300ml of ethanol for 3 times, and drying to obtain the flotation reagent.
Further, the platinum catalyst is H 2 PtCl 6 ·6H 2 O, the adding amount of the platinum catalyst is 3-5mmol.
The synthesis principle of the flotation reagent is as follows: the flotation reagent of the invention firstly takes allyl polyoxyethylene glycidyl ether and hydrogen-containing silicone oil as starting materials, generates hydrosilylation reaction under the action of a platinum catalyst, then stearic acid is added, carboxyl oxygen anions are formed by stearic acid under alkaline conditions to attack carbon (primary carbon) with small steric hindrance on epoxy groups, the epoxy groups open rings to form ester alcohol oxygen anions, then hydrogen of another molecule of carboxylic acid is captured to obtain an electric neutral product, and carboxyl oxygen anions are generated to continue the reaction.
The flotation principle of the flotation reagent is as follows: the flotation reagent is physically adsorbed to the surface of phosphorite, the hydration is weakened by reducing the electrokinetic potential of the mineral, so that the floatability of the mineral is improved, and the surface tension of a flotation solution system is reduced by a silicone bond, a hydrophobic aliphatic carbon chain and polyoxyethylene ether in the flotation reagent, so that the surface of the mineral is floated in a hydrophobic manner; in addition, the functional groups in the flotation reagent comprise hydroxyl and ester groups, the water solubility of the flotation reagent is increased by the hydrophilic groups of the hydroxyl and the ester groups, the hydrophobicity of the reagent is increased by the carbon chain growth and the introduction of the organic silicone grease, and the collecting capacity and the selectivity of the reagent are enhanced.
Further, in the step S3, in the extraction process, the extraction temperature is controlled to 85-90 ℃, and the vacuum cooling vacuum degree is controlled to-0.030-0.045 MPa.
The invention has the beneficial effects that:
the invention provides a production process of high-nutrient powdery monoammonium phosphate, which is used for producing the monoammonium phosphate by taking middle-low grade phosphate ore as a raw material, and has the advantages of reasonable production process, high product quality and good stability; the selected flotation agent has strong collecting capability and good selectivity of flotation agent, and P obtained after flotation 2 O 5 The grade is 30.9 percent, the MgO content is 0.71 percent, and the recovery rate reaches 90.15 percent; the flotation reagent is physically adsorbed to the surface of phosphorite, the hydration is weakened by reducing the electrokinetic potential of the mineral, so that the floatability of the mineral is improved, and the surface tension of a flotation solution system is reduced by a silicone bond, a hydrophobic aliphatic carbon chain and polyoxyethylene ether in the flotation reagent, so that the surface of the mineral is floated in a hydrophobic manner; in addition, functional groups in the flotation reagent comprise hydroxyl and ester groups, the water solubility of the flotation reagent is improved by the hydrophilic groups of the hydroxyl and the ester groups, the hydrophobicity of the reagent is improved by the increase of the carbon chain and the introduction of the organic silicone grease, and the collecting capacity and the selectivity of the reagent are enhanced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A production process of high-nutrient powdery monoammonium phosphate specifically comprises the following steps:
s1, the phosphorite blending ore comprises the following components in percentage by weight: p is 2 O 5 ％27.2-31.5％、MgO＜3％、K+Na＜0.5％；
S2, grinding the ore to prepare ore pulp: 1t of ore blending ore in the step S1 is ground for 4h to form phosphorus ore pulp, and reverse flotation is carried out by adding 7kg of flotation agent; the flotation results were: p is 2 O 5 The grade is 30.9 percent, the MgO content is 0.71 percent, and the recovery rate reaches 90.15 percent;
s3, extraction of phosphoric acid: pumping the concentrate pulp subjected to flotation in the step S2, sulfuric acid accounting for 1/4 of the total consumption of the reaction and return acid of a phosphoric acid settling tank into a pre-reactor, pre-reacting the concentrate pulp, the sulfuric acid and the return acid, feeding the reaction materials into a phosphoric acid extraction tank, adding sulfuric acid accounting for 3/4 of the total consumption of the reaction, further completely decomposing the pulp to form slurry, and filtering to obtain finished phosphoric acid; in the process, the extraction temperature is controlled to 85 ℃, and the vacuum degree of vacuum cooling is controlled to-0.030-0.045 MPa; the mass fraction of the finished phosphoric acid is 36%;
s4, neutralizing and concentrating
(1) Introducing the phosphoric acid filtrate obtained in the step S3 into a neutralization tank, introducing ammonia gas, heating to 50-53 ℃, starting a stirring device to enable the materials to have a pre-neutralization reaction, wherein the pH is 2.6, continuing stirring and aging for 2 hours after the reaction is finished, standing and settling for 3 hours, and filtering again to obtain filter residues and filtrate containing monoammonium phosphate;
(2) Introducing gas ammonia into the filtrate obtained in the step (1) again, controlling the pH value in the ammoniation process to be 4.8, and concentrating and drying the slurry after the ammoniation is finished to obtain a powdery monoammonium phosphate product with the total nutrient content of 60% in mass fraction; the product has effective P in mass fraction 2 O 5 47.8 percent of N, 10.5 percent of N, 58.3 percent of total nutrient and H 2 O is less than 3 percent, and water-soluble phosphorus is 84.6 percent.
The flotation agent comprises the following raw materials in parts by weight: 0.7 part of flotation reagent, 10 parts of sulfuric acid and 1 part of citric acid;
the preparation method of the flotation reagent comprises the following steps: 1mol of allyl polyoxyethylene glycidyl ether and 5mmol of platinum catalyst H 2 PtCl 6 ·6H 2 Adding O and 2L of toluene solvent into a reaction kettle, uniformly stirring, heating to 55 ℃, dropwise adding 1.1mol of hydrogen-containing silicone oil, after finishing dropwise adding within 1h, continuously heating to 135 ℃, performing reflux reaction for 7h, after finishing the reaction, cooling to 92 ℃, adding 1.1mol of stearic acid and 10mmol of cesium carbonate, continuously stirring to react for 6h, reducing to room temperature, filtering, performing rotary evaporation to remove toluene, alternately washing the concentrate with 300ml of water and 300ml of ethanol for 3 times, and drying to obtain a flotation reagent;
the infrared characterization of flotation reagent B is as follows:IR(KBr):
2943、2932(-CH 2 -/-CH 3 ),1759(-COO-),1180(-O-Si-C-)cm- 1 ；
the reaction process is as follows:
the flotation reagent is physically adsorbed to the surface of phosphorite, the hydration is weakened by reducing the electrokinetic potential of the mineral, so that the floatability of the mineral is improved, and the surface tension of a flotation solution system is reduced by silicon-fat bonds, hydrophobic aliphatic carbon chains and polyoxyethylene ether in the flotation reagent, so that the surface of the mineral is floated in a hydrophobic manner; in addition, the functional groups in the flotation reagent comprise hydroxyl and ester groups, the water solubility of the flotation reagent is increased by the hydrophilic groups of the hydroxyl and the ester groups, the hydrophobicity of the reagent is increased by the carbon chain growth and the introduction of the organic silicone grease, and the collecting capacity and the selectivity of the reagent are enhanced.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (3)
1. A production process of high-nutrient powdery monoammonium phosphate is characterized by comprising the following steps: the method specifically comprises the following steps:
s1, the phosphorite blending ore comprises the following components in percentage by weight: p 2 O 5 27.2-31.5％、MgO＜3％、K+Na＜0.5％；
S2, grinding the ore to prepare ore pulp: grinding the ore blending ore in the step S1 for 3-4h to form phosphorus ore pulp, and performing reverse flotation by adding a flotation agent;
s3, extraction of phosphoric acid: pumping the concentrate pulp subjected to flotation in the step S2, sulfuric acid accounting for 1/4 of the total reaction amount and return acid of a phosphoric acid settling tank into a pre-reactor, pre-reacting the concentrate pulp, the sulfuric acid and the return acid, feeding the reaction materials into a phosphoric acid extraction tank, adding sulfuric acid accounting for 3/4 of the total reaction amount, further completely decomposing the pulp and forming slurry, and filtering to obtain finished phosphoric acid;
s4, neutralizing and concentrating
(1) Introducing the phosphoric acid filtrate obtained in the step S3 into a neutralization tank, introducing ammonia gas, heating to 50-53 ℃, starting a stirring device to enable the materials to have a pre-neutralization reaction, wherein the pH is 2.4-2.7, continuing stirring and aging for 2 hours after the reaction is finished, standing and settling for 3 hours, and filtering again to obtain filter residues and filtrate containing monoammonium phosphate;
(2) Introducing gas ammonia into the filtrate obtained in the step (1) again, controlling the pH value in the ammoniation process to be 4.7-5.1, and concentrating and drying the slurry after ammoniation is finished to obtain a powdery monoammonium phosphate product with the total nutrient content of 58-65% by mass fraction;
in the step S2, the flotation agent comprises the following raw materials in parts by weight: 0.5-0.8 part of flotation reagent, 10-15 parts of sulfuric acid and 1 part of citric acid;
the preparation method of the flotation reagent comprises the following steps: adding 1mol of allyl polyoxyethylene glycidyl ether, a platinum catalyst and 2L of a toluene solvent into a reaction kettle, uniformly stirring, heating to 55-60 ℃, dropwise adding 1.1-1.2mol of hydrogen-containing silicone oil, finishing dropwise adding within 1h, continuously heating to 130-140 ℃, carrying out reflux reaction for 6-8h, cooling to 85-100 ℃ after the reaction is finished, adding 1.1-1.2mol of stearic acid and 10mmol of cesium carbonate, continuously stirring for reaction for 5-7h, cooling to room temperature, filtering, carrying out rotary evaporation to remove toluene, washing a concentrate with 300ml of water and 300ml of ethanol for 3 times, and drying to obtain a flotation reagent;
the platinum catalyst is H 2 PtCl 6 ·6H 2 O, the adding amount of the platinum catalyst is 3-5mmol.
2. The process for producing high-nutrient powdery monoammonium phosphate according to claim 1, wherein the process comprises the following steps: in step S2, the adding amount of the flotation agent is 0.6-0.8% of the weight of the phosphorite pulp in step S2.
3. The process for producing high-nutrient powdery monoammonium phosphate according to claim 1, wherein the process comprises the following steps: in the step S3, in the extraction process, the extraction temperature is controlled to 85-90 ℃, and the vacuum degree of vacuum cooling is controlled to-0.030-0.045 MPa.
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