CN111606335B - Clean comprehensive utilization method of potassium salt-containing mother liquor - Google Patents
Clean comprehensive utilization method of potassium salt-containing mother liquor Download PDFInfo
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- CN111606335B CN111606335B CN202010458920.3A CN202010458920A CN111606335B CN 111606335 B CN111606335 B CN 111606335B CN 202010458920 A CN202010458920 A CN 202010458920A CN 111606335 B CN111606335 B CN 111606335B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/06—Preparation of sulfates by double decomposition
- C01D5/08—Preparation of sulfates by double decomposition with each other or with ammonium sulfate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/02—Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
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- 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 discloses a clean comprehensive utilization method of a potassium salt-containing mother solution, which comprises the steps of mixing byproduct sulfate with the potassium salt-containing mother solution in proportion, concentrating the mixture to a certain concentration, pumping the mixture into a reaction device for cyclic reaction, crystallizing, separating, washing, drying and the like the obtained final reaction liquid to prepare reagent-grade potassium sulfate, and sending the mixed mother solution obtained by separating the potassium sulfate into a spray tower for spray drying to obtain a potassium fertilizer taking the potassium sulfate as a main body. The invention uses low-value byproduct sulfate to react with the potassium salt mother liquor to prepare the potassium sulfate with higher value, and prepares the reagent-grade potassium sulfate and the potassium sulfate fertilizer respectively through fine potassium sulfate crystallization and reaction liquid spray drying, thereby further improving the economic benefit, simultaneously fully utilizing all components in the mother liquor, recycling carbon dioxide and ammonia in the reaction process, realizing clean comprehensive utilization of the potassium salt-containing mother liquor under certain economic benefit, and having simple process, low equipment investment and being beneficial to industrialized popularization.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for comprehensively utilizing clean potassium salt-containing mother liquor, and more particularly relates to a method for comprehensively utilizing clean potassium salt-containing methionine mother liquor.
Background
In the industrial chemical synthesis production process of D, L-methionine, hydantoin as an intermediate of methionine is required to be hydrolyzed in the presence of alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate to generate aqueous solution of methionine salt, and the aqueous solution of methionine salt is acidified and separated to obtain methionine product and methionine crystallization mother liquor. When the potassium salt is used as hydrolysis alkali salt, based on the process setting of physical properties, potassium ions are recycled in the hydantoin hydrolysis, methionine saponification liquid and methionine mother liquor, so that the operation of additionally separating inorganic salt is avoided, the problems that byproduct salt is difficult to separate and treat in the production process of methionine are solved, and the method has the advantages of being clean, energy-saving and the like.
However, due to the existence of side reactions in the reaction process, such as residual hydrogen cyanide is oxidized into formic acid, cyanohydrin is polymerized and decomposed into sulfur-containing impurities, hydantoin is polymerized into macromolecular pigment, methionine products are condensed into methionine dipeptide, hydantoin is incompletely hydrolyzed to obtain intermediates such as hydantoin acid, various impurities are continuously accumulated in the system along with mother liquor circulation, and finally the crystallization yield and quality of methionine are directly affected. Among the above derived impurities, other impurities are basically unidirectionally accumulated except for the part of the incomplete hydrolysis products of methionine dipeptide and hydantoin which can be regenerated and eliminated by the mother liquor under high temperature and high pressure, and the catalyst and stabilizer used in the synthesis and storage processes of 3-methylthiopropanal and cyanohydrin are also expected to be unidirectionally accumulated in the system, which is also supported by the analysis result. Therefore, in view of the process, a part of crystallization mother liquor needs to be extracted and discharged without being recycled, the potassium salt lost with the extracted mother liquor is fed into the system through fresh potassium salt, long-term stability in the process is realized by partially updating the recycling mother liquor, but more dissolved methionine and potassium salt are still unavoidable in the extracted crystallization mother liquor, and in view of economy and environmental protection, direct or indirect recovery of methionine and potassium salt is necessarily required, and the recovery cost and the benefit of the recovered product are positively or negatively beneficial in relation to the whole methionine production process.
Patent CN1680311 discloses a method of separating a crystallization mother liquor into a first circulation portion and a second treatment portion, heating the second portion of mother liquor at a high temperature of 200-280 ℃ to hydrolyze methionine dipeptide into monomer methionine at a high temperature, introducing carbon dioxide to precipitate methionine and potassium bicarbonate therein, separating to obtain methionine and potassium hydrogen carbonate precipitate and a second crystallization mother liquor, and continuously circulating or extracting the second crystallization mother liquor according to the state.
Patent CN1017351125 discloses a similar method, in which the crystallization mother liquor is divided into a first circulation portion and a second treatment portion, and the second treatment portion is still subjected to concentration and thermal regeneration treatment, except that a lower alcohol is introduced to increase the ability to recover methionine when recovering methionine in the mother liquor of the second treatment portion.
Patent CN109485589 discloses a method for preparing methionine zinc chelate by methionine mother liquor containing potassium carbonate or potassium bicarbonate, wherein the molar ratio of methionine mother liquor to methionine to potassium ions after concentration is 1:0.8-1.1 by bipolar membrane electrodialysis treatment, the methionine desalination mother liquor and zinc salt with 0.5 molar equivalent of methionine are obtained in an acid chamber to react for 30-90min at 70-90 ℃, then the temperature is reduced and separated to prepare the methionine zinc chelate, and the recovered potassium hydroxide dilute alkali is recycled in an alkali chamber to be used for methionine production.
Patent CN106748932 discloses a method for post-treatment of mother liquor comprising the steps of filtration, acidification, gas-liquid separation, methionine separation, regeneration of saturated acidification column and the like. Filtering the extracted mother liquor through a microporous membrane to remove methionine and macromolecular polymers of intermediate, acidifying the filtrate through acidic resin, adsorbing metal cations in the filtrate, stripping and separating carbon dioxide to obtain a mixed solution with main components of methionine and potassium formate, and carrying out electrodialysis separation to obtain methionine concentrate and potassium formate concentrate, wherein the methionine concentrate and the potassium formate concentrate enter recycling and biochemical treatment respectively. And finally, acidifying and regenerating the ion exchange resin to obtain a potassium sulfate byproduct.
In summary, the current technology has the following general problems: mainly focuses on the recovery of beneficial methionine from the extracted mother liquor, while less recovery measures are taken for still more higher potassium salts; the new reagents such as organic solvent, metal salt and the like are introduced in the methionine recovery process, and additional separation or treatment is needed, so that the subsequent environment-friendly treatment pressure is increased; the economic value of the treatment of the extracted mother liquor is limited, and the introduction of expensive equipment (such as chromatography, ion separation columns, polymer membrane separation, electrodialysis equipment and the like) is not beneficial to long-term treatment and industrial popularization; and a comprehensive utilization scheme with low cost and system is lacked.
Disclosure of Invention
In view of the above, the present invention aims to provide a composition for preparing a potassium fertilizer mainly comprising potassium sulfate.
Further, the composition includes a potassium salt-containing mother liquor and a sulfate salt.
The potassium salt-containing mother liquor is the remainder of the crystal mainly comprising potassium hydroxide, potassium carbonate and potassium bicarbonate, and the sulfate is ammonium sulfate or ammonium bisulfate.
Further, the mass concentration ratio of the sulfate to potassium ions in the potassium salt-containing mother solution is 0.5-0.6:1.
further, the ammonium sulfate is commercial ammonium sulfate or by-product ammonium sulfate.
Preferably, the ammonium sulfate is a by-product of liquid methionine production, and the liquid methionine MHA content is less than 2%, preferably less than 1%.
Preferably, the mother liquor containing potassium salt is the mother liquor with potassium hydroxide, potassium carbonate and potassium bicarbonate as main potassium salt in the pharmaceutical and chemical production process.
Preferably, the potassium salt-containing mother liquor is any one of potassium carbonate, remaining mother liquor of methionine with potassium bicarbonate as main potassium salt and high potassium salt mother liquor, the Gao Jiayan mother liquor is remaining mother liquor of methionine with potassium salt obtained after the remaining mother liquor of methionine with one or more crystallization generates methionine metal chelate by adding zinc sulfate and/or copper sulfate and/or manganese sulfate inorganic salt, and the molar ratio of potassium ions in the potassium salt-containing mother liquor to the methionine is more than 1.7, more preferably more than 2.0.
The invention aims to provide a method for preparing a potash fertilizer taking potassium sulfate as a main body by using the composition.
The method comprises the steps of fully reacting the potassium salt-containing mother liquor with sulfate to obtain potassium sulfate solution, crystallizing and separating the potassium sulfate solution to obtain potassium sulfate crystals and potassium sulfate crystallization mother liquor, and spray-drying the potassium sulfate crystallization mother liquor to obtain the potassium fertilizer taking potassium sulfate as a main body.
Further, the reaction temperature of the reaction is 100-200 ℃.
Further, washing and drying the potassium sulfate crystal to obtain the reagent-grade potassium sulfate.
And further, mixing the washing solution obtained after washing the potassium sulfate crystals with the potassium sulfate crystallization mother liquor, and spray-drying the potassium fertilizer taking potassium sulfate as a main body.
Further, before the reaction, the potassium salt-containing mother solution and the sulfate are concentrated to obtain a concentrated mixed solution, wherein the mass concentration of salt ions in the sulfate in the concentrated mixed solution is 2.5-7.5mol/L.
Further, the reaction also produces carbon dioxide, ammonia and water vapor.
Further, the reaction is circulated 1 to 6 times, more preferably 2 to 5 times.
Further, the concentration is a concentration operation such as distillation under normal pressure or reduced pressure, membrane concentration, or the like.
Further, the crystallization includes, but is not limited to, one or more of concentration, cooling, addition of ammonia water, addition of potassium sulfate seed crystal, crystallization temperature of 20-80 ℃, preferably 30-60 ℃; the washing liquid used for washing is deionized water or 30% ammonia water solution, and the washing liquid can be used for washing the next batch of reagent potassium sulfate crystals or returned to the mixed liquid mixing or concentrating step.
Further, the potassium fertilizer with potassium sulfate as a main body obtained by spray drying is yellowish or white-like powder and particles, and comprises the following main components: potassium sulfate, ammonium sulfate, potassium formate, methionine (small amount of liquid methionine), wherein the potassium sulfate content should be more than 50%, preferably more than 70%.
Further, the reaction also generates carbon dioxide, ammonia and water vapor, and the generated carbon dioxide, ammonia and water vapor can be used for synthesizing methionine.
The invention also aims to provide a potash fertilizer and/or reagent-grade potassium sulfate which are prepared by the method and take potassium sulfate as a main body.
The invention aims to provide a production system for producing potash fertilizer taking potassium sulfate as a main body.
The production system is connected with a concentration device, a reaction device, a crystallization device and a spray drying device in sequence, wherein the concentration device comprises a potassium salt mother liquor feed inlet and a sulfate feed inlet at the top and a concentrated mixed liquor discharge outlet at the bottom, the reaction device comprises a circulating pump and is connected with a material channel at the bottom and the top of the reaction device, an air outlet is formed in the top, and a discharge outlet is formed in the bottom.
Further, the other end of the potassium salt-containing mother liquor feed inlet is connected with a methionine production system.
Further, the crystallization device is connected with the drying device.
Further, the reaction device is a stripper or an evaporator.
Further, the concentration device is an atmospheric or reduced pressure distillation device or a membrane concentration device.
The invention aims to provide a method for producing potash fertilizer mainly comprising potassium sulfate by using the production system.
The method comprises the steps of introducing potassium salt-containing mother liquor and sulfate into a concentrating device for mixing and concentrating to obtain concentrated mixed liquor, introducing the concentrated mixed liquor into a reaction device for reacting to obtain potassium sulfate solution, crystallizing and separating the potassium sulfate solution to obtain potassium sulfate crystallization mother liquor, and spray-drying the potassium sulfate crystallization mother liquor to obtain the potassium fertilizer taking potassium sulfate as a main body.
And further, crystallizing and separating the potassium sulfate solution in a crystallization device to obtain potassium sulfate crystals, washing and drying the potassium sulfate crystals to obtain the reagent-grade potassium sulfate.
And further, spray-drying the washing solution after washing the potassium sulfate crystals and/or the potassium sulfate crystallization mother liquor in a spray-drying device to obtain the potassium fertilizer with the potassium sulfate as the main body.
Further, the mass concentration of salt ions in the sulfate in the concentrated mixed solution is 2.5-7.5mol/L.
Further, the crystallization includes, but is not limited to, one or more of concentration, cooling, addition of ammonia water, addition of potassium sulfate seed crystal, crystallization temperature of 20-80 ℃, preferably 30-60 ℃; the washing liquid used for washing is deionized water or 30% ammonia water solution, and the washing liquid can be used for washing the next batch of reagent potassium sulfate crystals or returned to the mixed liquid mixing or concentrating step.
Further, the potassium fertilizer with potassium sulfate as a main body obtained by spray drying is yellowish or white-like powder and particles, and comprises the following main components: potassium sulfate, ammonium sulfate, potassium formate, methionine (small amount of liquid methionine), wherein the potassium sulfate content should be more than 50%, preferably more than 70%.
Further, the reaction also generates carbon dioxide, ammonia and water vapor, and the generated carbon dioxide, ammonia and water vapor can be used for synthesizing methionine.
The potassium salt-containing mother liquor is the remainder of the crystal mainly comprising potassium hydroxide, potassium carbonate and potassium bicarbonate, and the sulfate is ammonium sulfate or ammonium bisulfate.
Further, the ammonium sulfate is commercial ammonium sulfate or by-product ammonium sulfate.
Preferably, the ammonium sulfate is a by-product of liquid methionine production, and the liquid methionine MHA content is less than 2%, preferably less than 1%.
The sulfate is ammonium sulfate or ammonium bisulfate, and the mass concentration ratio of the sulfate to potassium ions in the potassium-containing mother solution is 0.5-0.6:1.
preferably, the mother liquor containing potassium salt is the mother liquor with potassium hydroxide, potassium carbonate and potassium bicarbonate as main potassium salt in the pharmaceutical and chemical production process.
Preferably, the potassium salt-containing mother liquor is any one of potassium carbonate, remaining mother liquor of methionine with potassium bicarbonate as main potassium salt and high potassium salt mother liquor, the Gao Jiayan mother liquor is remaining mother liquor of methionine with potassium salt obtained after the remaining mother liquor of methionine with one or more crystallization generates methionine metal chelate by adding zinc sulfate and/or copper sulfate and/or manganese sulfate inorganic salt, and the molar ratio of potassium ions in the potassium salt-containing mother liquor to the methionine is more than 1.7, more preferably more than 2.0.
Specifically, the operation temperature in the reaction device is 100-200 ℃, the cyclic operation is carried out for 1-6 times, preferably 2-5 times, carbon dioxide, ammonia and water vapor are obtained at the top of the reaction device in the reaction process, the cyclic reaction is finished, the final reaction liquid mainly containing potassium sulfate is obtained at the bottom of the reaction device, the final reaction liquid is extracted by a bottom extraction valve and enters a crystallization device, crystallization is carried out in the crystallization device at the crystallization temperature of 20-80 ℃, preferably 30-60 ℃, then washing is carried out, and the washing liquid and the crystallization mother liquid after washing enter spray drying equipment for drying the potash fertilizer taking potassium sulfate as a main body.
The invention has the beneficial effects that:
the invention uses the byproduct ammonium sulfate or ammonium sulfate mother liquor as the treating agent, and has low cost;
according to the invention, a potassium sulfate solution is obtained after reaction and conversion, a part of crystals are refined into reagent potassium sulfate with higher added value, and the rest is used as potash fertilizer taking potassium sulfate as a main body;
the potassium sulfate fertilizer produced by the invention contains a small amount of methionine, ammonium sulfate and potassium formate, and can also enrich soil and provide nutrition for plants;
the carbon dioxide and the ammonia gas obtained in the reaction process are collected and recycled into methionine production, the whole potassium-containing mother liquor is comprehensively utilized, three wastes are not harmful, and the method is clean and sustainable.
Drawings
Fig. 1 is a flow chart of a potash fertilizer production process.
Fig. 2 is a diagram of a potash fertilizer production system.
FIG. 3 is a diagram of a potash fertilizer production system (the potassium-containing mother liquor is methionine mother liquor).
Detailed Description
The examples are presented for better illustration of the invention, but the invention is not limited to the examples. Those skilled in the art will appreciate that various modifications and adaptations of the embodiments described above are possible in light of the above teachings and are intended to be within the scope of the invention.
The embodiment of the invention comprises the following steps: the methionine crystallization mother liquor containing potassium carbonate and/or potassium bicarbonate and ammonium sulfate (solid or solution) are mixed according to K + :(NH 4 ) 2 SO 4 - The molar ratio is 2:1-1.2, the mixture is uniformly mixed and concentrated until the concentration of ammonium ions is 2.5-7.5mol/L, the concentrated mixture is pumped into a stripping tower to remove carbon dioxide and ammonia (can be circularly operated for 1-5 times), a solution containing potassium sulfate is obtained at the bottom of the stripping tower, and ammonia and carbon dioxide are collected and recovered at the top of the stripping tower and can be used for methionine preparation. The solution containing potassium sulfate at the bottom of the stripping tower is cooled, (natural, ammonia water and/or seed crystal are added) and crystallized and washed to obtain reagent potassium sulfate, and the separated crystallization mother liquor is recycled to the next batch of crystallization or spray drying to prepare the potassium fertilizer taking potassium sulfate as the main body.
In the embodiment of the invention, if not specified, the byproduct ammonium sulfate is from the byproduct ammonium sulfate in the production process of liquid Methionine (MHA), and a small amount of MHA is entrained.
In the embodiment of the invention, referring to fig. 2,1a is a potassium-containing mother liquor feed inlet, 1b is a sulfate feed inlet, 1c is a concentrated mixed liquor discharge outlet, and 1 is a concentrating device; 2a is a concentrated mixed solution feed inlet, 2b is an air outlet, 2c is a potassium sulfate discharge outlet, and 2 is a reaction device; 3 is a crystallization device, 3a is a potassium sulfate feed inlet, and 3b is a discharge outlet; 4 is a spray drying device, 4a is a crystallization mother liquor and/or washing liquid feed port, and 4b is a discharge port.
In the embodiment of the invention, referring to fig. 3,5a is a discharge port of the mother liquor containing potassium, 5 is a methionine production system, and other reference is made to fig. 2.
Example 1
955.5kg of methionine crystallization mother liquor (MET: 5.93%, K) + 9.91 percent of potassium formate: 3.75%) and 195.4kg of byproduct ammonium sulfate (82% ammonium sulfate, 17.5% moisture, 0.64% MHA) were uniformly mixed and concentrated to 800L (ammonium ion concentration 3.03 mol/L), the mixed heat after concentration was pumped from the top of the stripping tower, the circulating stripping was carried out 2 times at 80-200 ℃, ammonia and carbon dioxide were recovered from the top of the stripping tower, 680L of stripped feed liquid was obtained from the bottom of the stripping tower, and ammonium ions were detected: 1.01mol/L. Cooling the above solution to 20-25deg.C to precipitate a large amount of crystals, and separating solid to remove ionsWashing with water for 2 times, and drying to obtain 55.8kg of colorless transparent potassium sulfate crystals, wherein the analytical purity is as follows: 99.5%.
Mixing the crystal washing liquid and the stripping crystallization mother liquid, sending into a spray drying tower, spray drying at 80-150 ℃ to obtain 230.2kg of light yellow powder solid, and analyzing the components to obtain the product: 41.9% of potassium sulfate, 19.5% of ammonium sulfate, 24.2% of methionine (egg-containing MHA) and 14.9% of potassium formate.
Example 2
955.5kg of methionine crystallization mother liquor (MET: 5.93%, K+:9.91%, potassium formate: 3.75%) was uniformly mixed with 195.4kg of by-product ammonium sulfate (82% ammonium sulfate, 17.5% moisture, 0.64% MHA) and concentrated to 800L (ammonium ion concentration 3.03 mol/L), the mixed heat after concentration was pumped from the stripping column top, and was circularly stripped 2 times at 80-200 ℃, ammonia gas and carbon dioxide were recovered from the column top, 680L of stripped feed liquid was obtained from the bottom of the stripping column, and ammonium ions were detected: 1.01mol/L. Feeding the gas final feed liquid into a spray drying tower, spray drying at 80-150 ℃ to obtain 290.2kg of yellowish powder solid, and analyzing components to obtain the following components: 55.2% of potassium sulfate, 15.5% of ammonium sulfate, 19.0% of methionine (egg-containing MHA) and 11.7% of potassium formate.
Example 3
701.5kg of methionine secondary crystallization mother liquor (MET: 6.53%, K) + 15.91 percent of potassium formate: 3.92%) and 230.3kg of by-product ammonium sulfate (82% ammonium sulfate, 17.5% moisture, 0.64% mha) were uniformly mixed and concentrated to 650L (ammonium ion concentration 4.4 mol/L), the mixed heat after concentration was pumped from the top of the stripping tower, circulated stripping was performed 2 times at 80-200 ℃, ammonia and carbon dioxide were recovered from the top of the stripping tower, 570L of stripped feed liquid was obtained from the bottom of the stripping tower, and ammonium ions were detected: 0.56mol/L. Cooling the feed liquid to 25-40 ℃, precipitating a large amount of crystals, washing the separated solids with deionized water for 2 times, drying to obtain 73.5kg of colorless transparent potassium sulfate crystals, and analyzing the purity: 99.5%.
Mixing the crystal washing liquid and the stripping crystallization mother liquid, sending into a spray drying tower, spray drying at 80-150 ℃ to obtain 234.2kg of light yellow powder solid, and analyzing the components to obtain the product: 56.0% potassium sulfate, 9.9% ammonium sulfate, 21.1% methionine (egg-in-liquid MHA), 12.2% potassium formate.
Example 4
645.2kg of methionine high potassium salt crystallization mother liquor (MET: 0.93%, K) + 17.75 percent of potassium formate: 4.75%, zinc ion: 0.02%) and 236.4kg of byproduct ammonium sulfate (82% ammonium sulfate, 17.5% moisture, 0.64% MHA) are uniformly mixed and concentrated to 650L (ammonium ion concentration 4.51 mol/L), the mixed heat after concentration is pumped from the top of a stripping tower, the circulating stripping is carried out for 2 times at 90-190 ℃, ammonia and carbon dioxide are recovered from the top of the stripping tower, 602L of stripped feed liquid is obtained from the bottom of the stripping tower, and ammonium ions are detected: 0.49mol/L. Cooling the feed liquid to 25-40 ℃, precipitating a large amount of crystals, washing the separated solids with deionized water for 2 times, and drying to obtain 96.2kg of colorless transparent potassium sulfate crystals, wherein the analytical purity is as follows: 99.5%.
Mixing the crystal washing liquid and the stripping crystallization mother liquid, sending into a spray drying tower, spray drying to obtain 182.7kg of off-white powder solid, and analyzing the components to obtain the following components: 68.7% potassium sulfate, 11.5% ammonium sulfate, 3.5% methionine (egg-in-liquid MHA), 16.4% potassium formate.
Example 5
645.2kg of methionine high potassium salt crystallization mother liquor (MET: 0.93%, K) + 17.75 percent of potassium formate: 4.75%, zinc ion: 0.02%) and 236.4kg of by-product ammonium sulfate (82% ammonium sulfate, 17.5% moisture, 0.64% MHA) were uniformly mixed and concentrated to 650L (ammonium ion concentration 4.51 mol/L), the mixed heat after concentration was pumped from the top of the stripping tower, circulated stripping was carried out 3 times at 90-190 ℃, ammonia and carbon dioxide were recovered from the top of the stripping tower, a stripped feed liquid 592L was obtained from the bottom of the stripping tower, and ammonium ions were detected: 0.46mol/L. Cooling the feed liquid to 40-60 ℃, precipitating a large amount of crystals, washing the separated solids with deionized water for 2 times, and drying to obtain 86.2kg of colorless transparent potassium sulfate crystals, wherein the analytical purity is as follows: 99.9%.
Sending the stripping crystallization mother liquor into a spray drying tower, spray drying to obtain 197.1kg of white-like powder solid, and analyzing components to obtain the following components: 70.8% of potassium sulfate, 10.9% of ammonium sulfate, 3.3% of methionine (egg-containing MHA) and 15.6% of potassium formate.
Example 6
685.6kg of methionine high potassium salt mother liquor (MET: 1.33%, K) + 16.96 percent of potassium formate: 4.88%, zinc ion: 0.01%) with 236.4kg of by-product ammonium sulfate (98.5% ammonium sulfate, 1.1% moisture, 0.54% MHA) andconcentrating to 650L (ammonium ion concentration is 5.43 mol/L), pumping mixed heat after concentration from the top of a stripping tower, circularly stripping for 2 times at 80-200 ℃, recovering ammonia gas and carbon dioxide from the top of the stripping tower, obtaining 600L of stripped feed liquid at the bottom of the stripping tower, and detecting ammonium ions: 0.43mol/L. Cooling the feed liquid to 40-65 ℃, precipitating a large amount of crystals, washing the separated solids with deionized water for 2 times, and drying to obtain 112.1kg of colorless transparent potassium sulfate crystals, wherein the analytical purity is as follows: 99.9%.
The crystal washing liquid and the stripping crystallization mother liquid are combined and sent into a spray drying tower, 231.2kg of light yellow powder solid is obtained by spray drying, and analytical components are obtained: 73.6% potassium sulfate, 8.0% ammonium sulfate, 3.9% methionine (egg-in-liquid MHA), 14.5% potassium formate.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (4)
1. A method for preparing reagent-grade potassium sulfate and potash fertilizer taking potassium sulfate as main body by using a composition, which is characterized in that the composition comprises potassium salt-containing mother liquor and sulfate; the sulfate is a byproduct ammonium sulfate or ammonium sulfate mother liquor produced by liquid methionine production; the method specifically comprises the following steps: fully reacting the potassium salt-containing mother solution with sulfate to obtain potassium sulfate solution, crystallizing and separating the potassium sulfate solution to obtain potassium sulfate crystals and potassium sulfate crystallization mother solution, spray-drying the potassium sulfate crystallization mother solution to obtain potassium fertilizer taking potassium sulfate as a main body, and washing and drying the potassium sulfate crystals to obtain reagent-grade potassium sulfate; the reaction temperature of the reaction is 100-200 ℃; the potassium salt-containing mother liquor fully reacts with sulfate to generate carbon dioxide, ammonia and water vapor, and the carbon dioxide, the ammonia and the water vapor are recovered to prepare methionine; the potassium salt-containing mother solution is any one of the residual mother solution of more than one crystallization of methionine and the high potassium salt mother solution of which the potassium carbonate and the potassium bicarbonate are main potassium salts, the Gao Jiayan mother solution is the residual mother solution of more than one crystallization of methionine, which is obtained after the residual mother solution of more than one crystallization of methionine is added with zinc sulfate, copper sulfate and/or manganese sulfate to generate methionine metal chelate, and the molar ratio of potassium ions to methionine in the potassium salt-containing mother solution is more than 1.7.
2. The method according to claim 1, wherein the molar quantity ratio of sulfate to potassium ions in the potassium salt-containing mother liquor is 0.5 to 0.6:1.
3. the method according to claim 1, wherein the potassium sulfate-based potash fertilizer is spray-dried by mixing the washed solution of the potassium sulfate crystals with the mother liquor of potassium sulfate crystallization.
4. The method according to claim 1, wherein the potassium salt-containing mother liquor and the sulfate are concentrated to obtain a concentrated mixed solution before the reaction, and the mass concentration of salt ions in the sulfate in the concentrated mixed solution is 2.5-7.5mol/L.
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