CN111606335A - Method for comprehensively utilizing clean potassium salt-containing mother liquor - Google Patents
Method for comprehensively utilizing clean potassium salt-containing mother liquor Download PDFInfo
- Publication number
- CN111606335A CN111606335A CN202010458920.3A CN202010458920A CN111606335A CN 111606335 A CN111606335 A CN 111606335A CN 202010458920 A CN202010458920 A CN 202010458920A CN 111606335 A CN111606335 A CN 111606335A
- Authority
- CN
- China
- Prior art keywords
- potassium
- sulfate
- mother liquor
- potassium sulfate
- methionine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a method for comprehensively utilizing clean mother liquor containing sylvite, which comprises the steps of mixing a byproduct sulfate and the mother liquor containing sylvite according to a proportion, concentrating the mixture to a certain concentration, pumping the concentrated mixture into a reaction device for circular reaction, preparing reagent-grade potassium sulfate from the obtained final reaction liquid through the steps of crystallization, separation, washing, drying and the like, and feeding the mixed mother liquor 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 method uses the low-value byproduct sulfate to react with the sylvite mother liquor to prepare the potassium sulfate with higher value, and respectively prepares the reagent-grade potassium sulfate and the potassium sulfate fertilizer by fine potassium sulfate crystallization and reaction liquid spray drying, thereby further improving the economic benefit, fully utilizing all components in the mother liquor, and recycling carbon dioxide and ammonia in the reaction process, thereby realizing the clean comprehensive utilization of the sylvite-containing mother liquor under certain economic benefit, having simple process and low equipment investment, and being beneficial to industrial popularization.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for comprehensively utilizing clean mother liquor containing sylvite, and more particularly relates to a method for comprehensively utilizing clean methionine mother liquor containing sylvite.
Background
In the industrial chemical synthesis production process of D, L-methionine, hydantoin which is an intermediate of methionine needs to be hydrolyzed in the presence of alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like to generate an aqueous solution of methionine, and the aqueous solution of methionine is acidified and separated to obtain a methionine product and a methionine crystallization mother liquor. When the potassium salt is used as the alkali hydrolysate salt, based on the process setting of physical properties, potassium ions are integrally recycled in 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 methionine production process are solved, and the process has the process advantages of cleanness, energy conservation and the like.
However, due to the existence of side reactions in the reaction process, such as the oxidation of residual hydrogen cyanide into formic acid, the polymerization and decomposition of cyanohydrin into sulfur-containing impurities, the polymerization of hydantoin into macromolecular pigments, the condensation of methionine products into methionine dipeptide, and the incomplete hydrolysis of hydantoin to obtain intermediates such as hydantoin acid, various impurities are continuously accumulated in the system along with the circulation of the mother liquor, and finally, the crystallization yield and quality of methionine are directly influenced. In addition to the methionine dipeptide and the hydantoin incomplete hydrolysis product which can be regenerated and eliminated by the mother liquor at high temperature and high pressure, other impurities are basically accumulated in a single direction, and the catalyst and the stabilizer used in the synthesis and storage process of the 3-methylthiopropanal and the cyanohydrin can be expected to be accumulated in the single direction of the system, which is supported by the analysis result. Therefore, a part of crystallization mother liquor is required to be extracted and discharged without returning to the circulation due to process consideration, potassium salt lost along with the extracted mother liquor passes through a fresh potassium salt supplementing system, long-term stability in the process is realized by partially updating the circulation mother liquor, but the inevitable extracted crystallization mother liquor still contains more dissolved methionine and potassium salt, the methionine and potassium salt are inevitably required to be directly or indirectly recovered due to economic and environmental considerations, and the recovery cost and the benefit of the recovered product determine positive or negative beneficial association to the whole methionine production process.
The patent CN1680311 discloses a method for separating crystallization mother liquor into a first circulation part and a second treatment part, heating the second part of mother liquor at a high temperature of 200-280 ℃ to hydrolyze methionine dipeptide into monomeric methionine at the high temperature, introducing carbon dioxide to precipitate methionine and potassium bicarbonate therein, separating to obtain methionine and potassium bicarbonate 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 process, in which the crystallization mother liquor is divided into a first circulation part and a second treatment part, and the second treatment part is still subjected to concentration and heat regeneration treatment, except that lower alcohol is introduced to increase the ability to recover methionine when recovering methionine in the mother liquor of the second treatment part.
Patent CN109485589 discloses a method for preparing zinc methionine chelate from methionine mother liquor containing potassium carbonate or potassium bicarbonate, which comprises the steps of treating the concentrated methionine mother liquor by bipolar membrane electrodialysis until the molar ratio of methionine to potassium ions is 1:0.8-1.1, reacting the methionine desalted mother liquor obtained in an acid chamber with 0.5 methionine molar equivalent of zinc salt at 70-90 ℃ for 30-90min, cooling and separating to prepare zinc methionine chelate, and recycling the recovered potassium hydroxide diluted alkali obtained in an alkali chamber to produce methionine.
Patent CN106748932 discloses a mother liquor post-treatment method comprising the steps of filtration, acidification, gas-liquid separation, methionine separation, saturated acidification column regeneration and the like. The method comprises the steps of filtering methionine and macromolecular polymers of intermediates in extracted mother liquor through a microporous membrane, acidifying filtrate through acidic resin to adsorb metal cations, carrying out steam stripping separation on carbon dioxide to obtain a mixed solution with main components of methionine and potassium formate, and carrying out electrodialysis separation to obtain methionine concentrated solution and potassium formate concentrated solution which are respectively recycled and subjected to biochemical treatment. Finally, the ion exchange resin is acidified and regenerated to obtain the potassium sulfate byproduct.
In summary, the problems of the prior art are: mainly focuses on recovering beneficial methionine from the extracted mother liquor, and the recovery measures for more and higher sylvite are less; in the process of recycling methionine, new reagents such as organic solvents, metal salts and the like are introduced, extra separation or treatment is needed, and the subsequent environment-friendly treatment pressure is increased; the extracted mother liquor has limited economic value, and expensive equipment (such as a chromatograph, an ion separation column, polymer membrane separation, electrodialysis equipment and the like) is introduced to be not beneficial to long-term treatment and industrial popularization; a systematic and low-cost comprehensive utilization scheme is lacked.
Disclosure of Invention
In view of the above, the present invention provides a composition for preparing a potassium fertilizer mainly containing potassium sulfate.
Further, the composition comprises a potassium salt-containing mother liquor and a sulfate salt.
Further, the potassium salt-containing mother liquor is a residual liquor of a crystal substance with potassium hydroxide, potassium carbonate and potassium bicarbonate as main bodies, 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 liquor is 0.5-0.6: 1.
further, the ammonium sulfate is commercial ammonium sulfate or byproduct ammonium sulfate.
Preferably, the ammonium sulfate is a liquid methionine production by-product ammonium sulfate, and the liquid methionine MHA content is less than 2%, preferably less than 1%.
Preferably, the mother liquor containing potassium salt is a mother liquor containing potassium hydroxide, potassium carbonate and potassium bicarbonate as main potassium salts in the pharmaceutical and chemical production process.
Preferably, the potassium salt-containing mother liquor is any one of residual mother liquor of one or more than one crystallization of methionine and high potassium salt mother liquor, wherein potassium carbonate and potassium bicarbonate are used as main potassium salts, the high potassium salt mother liquor is residual potassium salt-containing mother liquor obtained after zinc sulfate and/or copper sulfate and/or manganese sulfate inorganic salt is added into the residual mother liquor of one or more than one crystallization of methionine to generate methionine metal chelate, and the molar ratio of potassium ions in the potassium salt-containing mother liquor to the methionine is more than 1.7, and more preferably more than 2.0.
The invention aims to provide a method for preparing a potash fertilizer mainly containing potassium sulfate by using the composition.
The method specifically comprises the steps of fully reacting the mother liquor containing potassium salt with sulfate to obtain a potassium sulfate solution, then crystallizing and separating the potassium sulfate solution to obtain a potassium sulfate crystal and a potassium sulfate crystal mother liquor, and then spray drying the potassium sulfate crystal mother liquor to obtain the potassium fertilizer taking potassium sulfate as a main body.
Further, the reaction temperature of the reaction is 100-200 ℃.
And further washing and drying the potassium sulfate crystal to obtain reagent-grade potassium sulfate.
And further, mixing the washing solution obtained by washing the potassium sulfate crystal with the potassium sulfate crystal mother liquor, and performing spray drying to obtain the potassium fertilizer taking potassium sulfate as a main body.
Further, before the reaction, the potassium salt-containing mother liquor 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 2.5-7.5 mol/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 atmospheric or reduced pressure distillation, membrane concentration, and the like.
Further, the crystallization comprises one or more of the combination operations of concentration, temperature reduction, ammonia water addition and potassium sulfate seed crystal addition, and the crystallization temperature is 20-80 ℃, preferably 30-60 ℃; the washing liquid selected for washing is deionized water or a 30% ammonia water solution, and the washing liquid can be used for washing the potassium sulfate crystal as a reagent in the next batch or returned to a mixed liquid mixing or concentrating step.
Further, the potash fertilizer taking the potassium sulfate obtained by spray drying as a main body is yellowish or white-like powder and particles, and mainly comprises the following components: potassium sulfate, ammonium sulfate, potassium formate, methionine (small amount of liquid methionine), wherein the content of potassium sulfate 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 prepared by the method and mainly using the potassium sulfate.
The invention aims to provide a production system for producing a potash fertilizer taking potassium sulfate as a main body.
Production system connects gradually enrichment facility, reaction unit, crystallization device and spray drying device, the enrichment facility contains the concentrated mixed liquid discharge gate of sylvite mother liquor feed inlet and sulfate feed inlet, bottom at top, reaction unit contains the circulating pump and connects the reaction unit bottom is equipped with the gas outlet with the material passageway at top, top and concentrated mixed liquid feed inlet, bottom are equipped with the discharge gate.
Further, the other end of the feed inlet of the potassium salt-containing mother liquor is connected with a methionine production system.
Further, the crystallization device is connected with a drying device.
Further, the reaction device is a stripping tower or an evaporator.
Further, the concentration device is a normal pressure or reduced pressure distillation device or a membrane concentration device.
The invention aims to provide a method for producing a potash fertilizer mainly containing potassium sulfate by using the production system.
Introducing a potassium salt-containing mother liquor and sulfate into the concentration device, mixing and concentrating to obtain a concentrated mixed liquor, introducing the concentrated mixed liquor into a reaction device, reacting to obtain a potassium sulfate solution, crystallizing and separating the potassium sulfate solution to obtain a potassium sulfate crystallized mother liquor, and spray-drying the potassium sulfate crystallized mother liquor to obtain the potassium fertilizer taking potassium sulfate as a main body.
Further, crystallizing and separating the potassium sulfate solution in a crystallizing device to obtain a potassium sulfate crystal, washing and drying the potassium sulfate crystal to obtain the reagent-grade potassium sulfate.
And further, spraying and drying the washing liquid obtained by washing the potassium sulfate crystal and/or the potassium sulfate crystal mother liquor in a spray drying device to obtain the potassium fertilizer of the potassium sulfate main body.
Further, the mass concentration of salt ions in the sulfate in the concentrated mixed solution is 2.5-7.5 mol/L.
Further, the crystallization comprises one or more of the combination operations of concentration, temperature reduction, ammonia water addition and potassium sulfate seed crystal addition, and the crystallization temperature is 20-80 ℃, preferably 30-60 ℃; the washing liquid selected for washing is deionized water or a 30% ammonia water solution, and the washing liquid can be used for washing the potassium sulfate crystal as a reagent in the next batch or returned to a mixed liquid mixing or concentrating step.
Further, the potash fertilizer taking the potassium sulfate obtained by spray drying as a main body is yellowish or white-like powder and particles, and mainly comprises the following components: potassium sulfate, ammonium sulfate, potassium formate, methionine (small amount of liquid methionine), wherein the content of potassium sulfate 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.
Further, the potassium salt-containing mother liquor is a residual liquor of a crystal substance with potassium hydroxide, potassium carbonate and potassium bicarbonate as main bodies, and the sulfate is ammonium sulfate or ammonium bisulfate.
Further, the ammonium sulfate is commercial ammonium sulfate or byproduct ammonium sulfate.
Preferably, the ammonium sulfate is a liquid methionine production by-product ammonium sulfate, 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 liquor is 0.5-0.6: 1.
preferably, the mother liquor containing potassium salt is a mother liquor containing potassium hydroxide, potassium carbonate and potassium bicarbonate as main potassium salts in the pharmaceutical and chemical production process.
Preferably, the potassium salt-containing mother liquor is any one of residual mother liquor of one or more than one crystallization of methionine and high potassium salt mother liquor, wherein potassium carbonate and potassium bicarbonate are used as main potassium salts, the high potassium salt mother liquor is residual potassium salt-containing mother liquor obtained after zinc sulfate and/or copper sulfate and/or manganese sulfate inorganic salt is added into the residual mother liquor of one or more than one crystallization of methionine to generate methionine metal chelate, and the molar ratio of potassium ions in the potassium salt-containing mother liquor to the methionine is more than 1.7, and more preferably more than 2.0.
Specifically, the operation temperature in the reaction device is 100-200 ℃, the cyclic operation is performed for 1-6 times, preferably 2-5 times, carbon dioxide, ammonia and water vapor are obtained from 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 from the bottom of the reaction device, the final reaction liquid is extracted from a bottom extraction valve and enters a crystallization device, the final reaction liquid is crystallized in the crystallization device at the crystallization temperature of 20-80 ℃, preferably 30-60 ℃, then the final reaction liquid is washed, and the washed washing liquid and the crystallized mother liquid enter spray drying equipment to be dried to obtain the potassium fertilizer taking potassium sulfate as a main body.
The invention has the beneficial effects that:
the method uses the by-product ammonium sulfate or the ammonium sulfate mother liquor as the treating agent, so that the cost is low;
the method obtains a potassium sulfate solution after reaction and conversion, wherein one part of the potassium sulfate solution is crystallized and refined into a reagent potassium sulfate with higher added value, and the rest part of the potassium sulfate solution is used as a potash fertilizer taking the 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 fertilize soil to provide nutrition for plants;
the carbon dioxide and ammonia gas obtained in the reaction process are collected and recycled to the methionine production, the whole potassium-containing mother liquor is comprehensively utilized, three wastes are not generated, and the method is clean and sustainable.
Drawings
FIG. 1 is a flow chart of a potassium fertilizer production process.
FIG. 2 is a diagram of a potassium fertilizer production system.
FIG. 3 is a diagram of a potassium fertilizer production system (the potassium-containing mother liquor is methionine mother liquor).
Detailed Description
The examples are given for the purpose of better illustration of the invention, but the invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
The embodiment of the invention comprises the following steps: methionine crystallization mother liquor containing potassium carbonate and/or potassium bicarbonate and ammonium sulfate (solid or solution) according to K+:(NH4)2SO4 -Uniformly mixing and concentrating the mixture until the concentration of ammonium ions is 2.5-7.5mol/L according to the molar ratio of 2:1-1.2, pumping the concentrated mixed solution into a stripping tower to remove carbon dioxide and ammonia (the mixed solution can be circularly operated for 1-5 times), obtaining a solution containing potassium sulfate at the bottom of the stripping tower, and collecting and recovering ammonia and carbon dioxide at the top of the stripping tower to be used for preparing methionine. Cooling, crystallizing (naturally, adding ammonia water and/or seed crystal) and washing the solution containing potassium sulfate at the bottom of the stripping tower to obtain a reagent potassium sulfate, and separating to obtain a crystallization mother liquor, and recycling the crystallization mother liquor to next crystallization or spray drying to prepare the potassium fertilizer taking potassium sulfate as a main body.
In the examples of the present invention, the by-produced ammonium sulfate is obtained from the by-produced ammonium sulfate in the production of liquid Methionine (MHA) and carries a small amount of MHA, unless otherwise specified.
In the embodiment of the invention, referring to fig. 2,1a is a potassium-containing mother liquor feeding port, 1b is a sulfate feeding port, 1c is a concentrated mixed liquor discharging port, and 1 is a concentrating device; 2a is a concentrated mixed liquid feeding port, 2b is an air outlet, 2c is a potassium sulfate discharging port, and 2 is a reaction device; 3 is a crystallizing device, 3a is a potassium sulfate feeding port, and 3b is a discharging port; 4 is a spray drying device, 4a is a feeding hole of the crystallization mother liquor and/or the washing liquor, and 4b is a discharging hole.
In the embodiment of the invention, referring to fig. 3,5a is a discharge port of potassium-containing mother liquor, 5 is a methionine production system, and the others refer to fig. 2.
Example 1
955.5kg of methionine crystallization mother liquor (MET: 5.93%, K)+9.91%, potassium formate: 3.75%) and 195.4kg of by-product ammonium sulfate (82% ammonium sulfate, 17.5% moisture, 0.64% MHA) are uniformly mixed and concentrated to 800L (ammonium ion concentration 3.03mol/L), mixed heat after concentration is pumped from the top of a stripping tower, the circulating stripping is carried out for 2 times at 80-200 ℃, ammonia gas and carbon dioxide are recovered from the top of the stripping tower, 680L of stripped feed liquid is obtained from the bottom of the stripping tower, and ammonium ions are detected: 1.01 mol/L. Cooling the feed liquid to 20-25 ℃, precipitating a large amount of crystals, washing the separated solids for 2 times by using deionized water, and drying to obtain 55.8kg of colorless transparent potassium sulfate crystals with analytical purity: 99.5 percent.
And combining the crystal washing liquid and the stripping crystallization mother liquid, conveying the mixture into a spray drying tower, and spray drying at the temperature of 80-150 ℃ to obtain 230.2kg of light yellow powder solid, wherein analytical components are as follows: 41.9 percent of potassium sulfate, 19.5 percent of ammonium sulfate, 24.2 percent of methionine (liquid egg MHA) and 14.9 percent of potassium formate.
Example 2
955.5kg of methionine crystallization mother liquor (MET: 5.93%, K +: 9.91%, potassium formate: 3.75%) and 195.4kg of by-product ammonium sulfate (82% ammonium sulfate, 17.5% moisture, 0.64% MHA) are uniformly mixed and concentrated to 800L (ammonium ion concentration: 3.03mol/L), the concentrated mixed heat is pumped from the top of a stripping tower, the circulating stripping is carried out for 2 times at 80-200 ℃, ammonia and carbon dioxide are recovered from the top of the stripping tower, 680L of stripped feed liquid is obtained at the bottom of the stripping tower, and ammonium ion detection is carried out: 1.01 mol/L. Feeding the final gas feed liquid into a spray drying tower, and spray drying at 80-150 ℃ to obtain 290.2kg of yellowish powder solid, wherein the final gas feed liquid comprises the following analytical components: 55.2% potassium sulfate, 15.5% ammonium sulfate, 19.0% methionine (liquid egg MHA), 11.7% potassium formate.
Example 3
701.5kg of methionine secondary crystallization mother liquor (MET: 6.53%, K)+15.91 percent, 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 4.4mol/L), mixed heat after concentration was pumped from the top of the stripping column, and cyclic stripping was performed at 80-200 ℃ for 2 times, ammonia gas and carbon dioxide were recovered from the top of the stripping column, 570L of stripped feed liquid was obtained from the bottom of the stripping column, and ammonium ion detection was performed: 0.56 mol/L. Cooling the feed liquid to 25-40 ℃, separating out a large amount of crystals, washing the separated solids for 2 times by using deionized water, and drying to obtain 73.5kg of colorless transparent potassium sulfate crystals with analytical purity: 99.5 percent.
The crystal washing liquid and the stripping crystallization mother liquid are merged and sent into a spray drying tower, and spray drying is carried out at the temperature of 80-150 ℃ to obtain 234.2kg of light yellow powder solid, and the analytical components are as follows: 56.0 percent of potassium sulfate, 9.9 percent of ammonium sulfate, 21.1 percent of methionine (liquid egg MHA) and 12.2 percent of potassium formate.
Example 4
645.2kg of methionine high potassium salt crystallization mother liquor (MET: 0.93%, K)+17.75%, 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) are uniformly mixed and concentrated to 650L (ammonium ion concentration 4.51mol/L), 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 gas and carbon dioxide are recovered from the top of the stripping tower, stripped feed liquid 602L is obtained from the bottom of the stripping tower, and ammonium ions are detected: 0.49 mol/L. Cooling the feed liquid to 25-40 ℃, separating out 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 with analytical purity: 99.5 percent.
And combining the crystal washing liquid and the stripping crystallization mother liquid, conveying the mixture into a spray drying tower, and performing spray drying to obtain 182.7kg of white-like powder solid, wherein the analytical components are as follows: 68.7 percent of potassium sulfate, 11.5 percent of ammonium sulfate, 3.5 percent of methionine (liquid egg MHA) and 16.4 percent of potassium formate.
Example 5
645.2kg of methionine high potassium salt crystallization mother liquor (MET: 0.93%, K)+17.75%, 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) are uniformly mixed and concentrated to 650L (ammonium ion concentration 4.51mol/L), mixed heat after concentration is pumped from the top of a stripping tower, the mixture is circularly stripped for 3 times at 90-190 ℃, ammonia gas and carbon dioxide are recovered from the top of the stripping tower, stripped feed liquid 592L is obtained from the bottom of the stripping tower, and ammonium ions are detected: 0.46 mol/L. Cooling the feed liquid to 40-60 ℃, separating out 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 with analytical purity: 99.9 percent.
Feeding the stripping crystallization mother liquor into a spray drying tower, and spray drying to obtain 197.1kg of white powder solid, wherein the analytical components are as follows: 70.8% potassium sulfate, 10.9% ammonium sulfate, 3.3% methionine (liquid egg MHA), 15.6% potassium formate.
Example 6
685.6kg of methionine high potassium salt mother liquor (MET: 1.33%, K)+16.96 percent, potassium formate: 4.88%, zinc ion: 0.01%) and 236.4kg of by-product ammonium sulfate (98.5% ammonium sulfate, 1.1% moisture, 0.54% MHA) are uniformly mixed and concentrated to 650L (ammonium ion concentration 5.43mol/L), mixed heat after concentration is pumped from the top of a stripping tower, the circulating stripping is carried out for 2 times at 80-200 ℃, ammonia gas and carbon dioxide are recovered from the top of the stripping tower, 600L of feed liquid after stripping is obtained at the bottom of the stripping tower, and ammonium ions are detected: 0.43 mol/L. Cooling the feed liquid to 40-65 ℃, precipitating a large amount of crystals, washing the separated solids for 2 times by using deionized water, and drying to obtain 112.1kg of colorless transparent potassium sulfate crystals with analytical purity: 99.9 percent.
And combining the crystal washing liquid and the stripping crystallization mother liquid, conveying the mixture into a spray drying tower, and performing spray drying to obtain light yellow powder solid 231.2kg, wherein the analytical components are as follows: 73.6 percent of potassium sulfate, 8.0 percent of ammonium sulfate, 3.9 percent of methionine (liquid egg MHA) and 14.5 percent of potassium formate.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, 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 or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (17)
1. Composition for the preparation of a potash fertilizer based on potassium sulfate, characterized in that it comprises a mother liquor containing potassium salts and sulfate salts.
2. The composition of claim 1, wherein the potassium salt-containing mother liquor is a raffinate of a crystal comprising potassium hydroxide, potassium carbonate, and potassium bicarbonate as a main component, and the sulfate is ammonium sulfate or ammonium bisulfate.
3. The composition as claimed in claim 2, wherein the molar number ratio of the sulfate salt to the potassium ion in the potassium salt-containing mother liquor is 0.5-0.6: 1.
4. the composition as claimed in claim 1, wherein the mother liquor containing potassium salt is any one of potassium carbonate, residual mother liquor of methionine once or more than once crystallized with potassium bicarbonate as main potassium salt, and high potassium salt mother liquor, the high potassium salt mother liquor is residual mother liquor containing potassium salt obtained after adding zinc sulfate and/or copper sulfate and/or manganese sulfate inorganic salt into residual mother liquor of methionine once or more than once crystallized to generate methionine metal chelate, and the molar ratio of potassium ion in the mother liquor containing potassium salt to methionine is more than 1.7.
5. The method for preparing a potash fertilizer mainly containing potassium sulfate by using the composition of claim 1, wherein the method specifically comprises: and fully reacting the potassium salt-containing mother liquor with sulfate to obtain a potassium sulfate solution, crystallizing and separating the potassium sulfate solution to obtain a potassium sulfate crystal and a potassium sulfate crystal mother liquor, and spray-drying the potassium sulfate crystal mother liquor to obtain the potassium fertilizer taking potassium sulfate as a main body.
6. The method as claimed in claim 5, wherein the reaction temperature is 100-200 ℃.
7. The method as claimed in claim 5, wherein the potassium sulfate crystal is washed and dried to obtain reagent-grade potassium sulfate.
8. The method as claimed in claim 7, wherein the washing solution obtained by washing the potassium sulfate crystals is mixed with the mother solution of potassium sulfate crystals and then spray-dried to obtain the potassium fertilizer mainly containing potassium sulfate.
9. The method as claimed in claim 5, wherein before the reaction, the potassium salt-containing mother liquor and the sulfate are concentrated to obtain a concentrated mixed solution, and the mass concentration of salt ions in the sulfate in the concentrated mixed solution is 2.5-7.5 mol/L.
10. The method according to claim 5, wherein the potassium salt-containing mother liquor is fully reacted with sulfate to further generate carbon dioxide, ammonia and water vapor, and the carbon dioxide, ammonia and water vapor are recovered to prepare methionine.
11. Potash fertilizer and/or reagent grade potassium sulfate mainly based on potassium sulfate prepared by the method of any one of claims 5 to 10.
12. Production uses potash fertilizer's of potassium sulphate as main part production system, a serial communication port, production system connects gradually enrichment facility, reaction unit, crystallization device and spray drying device, the enrichment facility contains the concentrated mixed liquid discharge gate of sylvite mother liquor feed inlet and sulfate feed inlet, bottom at top, reaction unit contains the circulating pump and connects the material passageway at reaction unit bottom and top, top are equipped with the gas outlet and the concentrated mixed liquid feed inlet, bottom are equipped with the discharge gate.
13. The production system of claim 12, wherein the feed inlet of the mother liquor containing potassium salt is connected with the methionine production system at the other end.
14. The production system of claim 12, wherein the crystallization device is connected to a drying device.
15. The method for producing the potash fertilizer mainly containing potassium sulfate by using the production system as claimed in any one of claims 12 to 14, wherein the method specifically comprises introducing a mother liquor containing potassium salt and sulfate into the concentration device to be mixed and concentrated to obtain a concentrated mixed liquor, then introducing the concentrated mixed liquor into a reaction device to react to obtain a potassium sulfate solution, then crystallizing and separating the potassium sulfate solution to obtain a potassium sulfate crystallized mother liquor, and then spray-drying the potassium sulfate crystallized mother liquor to obtain the potash fertilizer mainly containing potassium sulfate.
16. The method as recited in claim 16 wherein the potassium sulfate solution is crystallized and separated in the crystallization device to obtain potassium sulfate crystals, and the potassium sulfate crystals are washed and dried to obtain reagent grade potassium sulfate.
17. The method as claimed in claim 17, wherein the washing liquid obtained by washing the potassium sulfate crystal and/or the mother solution of potassium sulfate crystal is spray-dried in a spray-drying apparatus to obtain a potassium fertilizer containing potassium sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010458920.3A CN111606335B (en) | 2020-05-27 | 2020-05-27 | Clean comprehensive utilization method of potassium salt-containing mother liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010458920.3A CN111606335B (en) | 2020-05-27 | 2020-05-27 | Clean comprehensive utilization method of potassium salt-containing mother liquor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111606335A true CN111606335A (en) | 2020-09-01 |
| CN111606335B CN111606335B (en) | 2023-06-23 |
Family
ID=72196053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010458920.3A Active CN111606335B (en) | 2020-05-27 | 2020-05-27 | Clean comprehensive utilization method of potassium salt-containing mother liquor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111606335B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113860331A (en) * | 2021-11-02 | 2021-12-31 | 浙江大洋生物科技集团股份有限公司 | Method for synthesizing high-activity potassium fluoride and co-producing sodium fluoride by using waste liquid as raw material |
| CN114249352A (en) * | 2020-09-25 | 2022-03-29 | 沈阳化工研究院有限公司 | Method for treating wastewater generated in production of 6-methoxy tetralone |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585548A (en) * | 2009-07-06 | 2009-11-25 | 华南理工大学 | Method for preparing inorganic sylvine crystal and feed additive by using molasses fermented waste liquid |
| CN105130549A (en) * | 2015-07-14 | 2015-12-09 | 湖北三宁化工股份有限公司 | Method of producing macro-element water-soluble fertilizer from industrial-grade monoammonium phosphate mother liquid |
| CN106315627A (en) * | 2016-08-12 | 2017-01-11 | 宜昌富升化工有限公司 | Production technology of potassium sulfate |
| CN107032834A (en) * | 2017-06-15 | 2017-08-11 | 开封大学 | The technique that liquid phase mortar gunite method produces potassium sulfate |
| CN109678769A (en) * | 2019-02-14 | 2019-04-26 | 禄丰天宝磷化工有限公司 | A method of comprehensive utilization methionine crystalline mother solution produces methionine metal chelate |
-
2020
- 2020-05-27 CN CN202010458920.3A patent/CN111606335B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585548A (en) * | 2009-07-06 | 2009-11-25 | 华南理工大学 | Method for preparing inorganic sylvine crystal and feed additive by using molasses fermented waste liquid |
| CN105130549A (en) * | 2015-07-14 | 2015-12-09 | 湖北三宁化工股份有限公司 | Method of producing macro-element water-soluble fertilizer from industrial-grade monoammonium phosphate mother liquid |
| CN106315627A (en) * | 2016-08-12 | 2017-01-11 | 宜昌富升化工有限公司 | Production technology of potassium sulfate |
| CN107032834A (en) * | 2017-06-15 | 2017-08-11 | 开封大学 | The technique that liquid phase mortar gunite method produces potassium sulfate |
| CN109678769A (en) * | 2019-02-14 | 2019-04-26 | 禄丰天宝磷化工有限公司 | A method of comprehensive utilization methionine crystalline mother solution produces methionine metal chelate |
Non-Patent Citations (1)
| Title |
|---|
| 荣维华: ""谷氨酸母液综合治理方案探讨"", 《发酵科技通讯》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114249352A (en) * | 2020-09-25 | 2022-03-29 | 沈阳化工研究院有限公司 | Method for treating wastewater generated in production of 6-methoxy tetralone |
| CN114249352B (en) * | 2020-09-25 | 2023-07-28 | 沈阳化工研究院有限公司 | Method for treating wastewater generated in production of 6-methoxy tetralone |
| CN113860331A (en) * | 2021-11-02 | 2021-12-31 | 浙江大洋生物科技集团股份有限公司 | Method for synthesizing high-activity potassium fluoride and co-producing sodium fluoride by using waste liquid as raw material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111606335B (en) | 2023-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111606335B (en) | Clean comprehensive utilization method of potassium salt-containing mother liquor | |
| CN108658821B (en) | Clean production method of D, L-methionine and product thereof | |
| CN115947486B (en) | Desulfurization waste liquid recycling treatment process and system | |
| CN109734637B (en) | Methionine crystallization mother liquor treatment method | |
| US20220081394A1 (en) | Method for preparing sodium taurate as taurine intermediate, and method for preparing taurine | |
| CN101993384B (en) | Deamination new process by alkaline hydrolysis of nitrile compounds | |
| CN104628012A (en) | Production method for preparing ammonium sulfate by alkylating waste acid | |
| CN102659650B (en) | Device and method for preparing DL-methionine salt | |
| CN114149351A (en) | Methionine optimized preparation method based on sulfuric acid direct acidification method and sodium sulfate washing equipment | |
| CN109485589B (en) | Method for preparing zinc methionine chelate from methionine mother liquor containing potassium carbonate or potassium bicarbonate | |
| CN116535338B (en) | Potassium salt recycling process in production process of D, L-methionine | |
| CN105130861A (en) | Separation and purification method for methionine hydroxy analogue synthesized through hydrolysis of cyanohydrins | |
| CN101549898A (en) | Resource recycling technique of low-concentration formaldehyde wastewater and formaldehyde tail gas | |
| CN112707850B (en) | Preparation method of oligomer hydroxy methionine metal chelate | |
| CN111592473B (en) | Method and system for circularly preparing taurine | |
| CN106586990B (en) | With the method for Wet-process Phosphoric Acid Production potassium dihydrogen phosphate | |
| CN106748839B (en) | A kind of clean preparation method of glycine and iminodiacetic acid coproduction | |
| CN104529801A (en) | Synthetic method for p-hydroxyphenyl glycine | |
| CN111393323A (en) | Environment-friendly clean production method of high-purity cyanoacetic acid, cyanoacetic ester and malonic ester | |
| CN109232338A (en) | A kind of isolation and purification method of methionine hydroxy analog | |
| CN111892222B (en) | Ammonium sulfate wastewater recycling method | |
| CN101544574A (en) | Environment-friendly clean process method for continuously synthesizing iminodiacetic acid (salt) | |
| CN114539082A (en) | Environment-friendly preparation and purification method of betaine hydrochloride | |
| CN109651072B (en) | Method for preparing chloroethane from hydrochloric acid containing sulfur dioxide | |
| CN105949097B (en) | A method of reducing impurity in the exhaust of methionine ion-exchange and methionine crystalline mother solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |