CN1413961A - Method for preparing chemical fertilizer from salt-making mother liquor (bittern) or salt water - Google Patents
Method for preparing chemical fertilizer from salt-making mother liquor (bittern) or salt water Download PDFInfo
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- CN1413961A CN1413961A CN 02135647 CN02135647A CN1413961A CN 1413961 A CN1413961 A CN 1413961A CN 02135647 CN02135647 CN 02135647 CN 02135647 A CN02135647 A CN 02135647A CN 1413961 A CN1413961 A CN 1413961A
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- mother liquor
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- bittern
- glaserite
- ammonia
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Abstract
A process for preparing chemical fertilizer from the bitter halogen or saline features that the magnesium ammonium phosphate, potassium sulfate and ammonium (or calcium) chloride are deposited and separated step by step according to their solubilities. Its advantages are high extracting rate up to more than 98% for Mg2+, K+ and SO42-, and low cost.
Description
One, the technical field
The invention belongs to the field of inorganic chemical industry, in particular to a method for utilizing Mg-containing2+、K+、SO4 2-The new comprehensive utilization process of extracting chemical fertilizer such as ammonium magnesium phosphate, potassium sulfate, ammonium chloride, etc. from salt-making mother liquor (bittern) or salt water.
Second, background Art
The yield of raw salt in China is squashed to lead the front of the world, the annual yield is about 2000 more than ten thousand tons, and the discharged salt making mother liquor (bittern) is nearly 2000 ten thousand tons, wherein the salt making mother liquor contains Mg2+50 to 70g/L of K+10 to 15g/L of SO4 2-60-80 g/L. Since the end of the fifties of the last century, China began to research and develop the utilization of salt-making mother liquor, and KCl and Br were basically formed in the seventies2And halogen block (MgCl)2·6H2O) is the production process of the product by the halogen adding method. However, the total utilization rate of bittern is less than 10 percent due to laggard process, high energy consumption, low product added value and low extraction rate of the bittern-exchange method, and a large amount of bittern is still discharged into sea polluted areas; in recent years, although a good comprehensive bittern utilization process is available, no method capable of changing waste into valuable and fundamentally solving the harm of bittern exists before the invention. China is a big agricultural country and a country short of potassium resources, and the chemical fertilizer market demand is huge, if bitter bittern and Mg in salt water are used2+、K+And SO4 2-The conversion of the bittern into chemical fertilizer not only radically treats bittern pollution, changes waste into valuable, but also is a fundamental way for improving resource utilization rate.
Third, the invention
The invention aims to provide a method for preparing salt from Mg by aiming at the current situation that the prior salt-making mother liquor (bittern) is not fully utilized and the demand of chemical fertilizers is large2+、K+And SO4 2-To make saltMother liquor (bittern)Or the process scheme of preparing chemical fertilizers such as ammonium magnesium phosphate, potassium sulfate, ammonium chloride and the like from salt water.
The invention is realized by the following technical measures:
a process for preparing chemical fertilizer from the mother liquid of salt production (bittern) or salt water features that the mother liquid of salt production (bittern) or natural salt water is prepared through fractional precipitation and separation according to the solubility of substance to be prepared. The method is characterized by comprising the following steps:
(1) according to Mg in salt mother liquor (bittern) or salt water prepared from raw materials2+In terms of magnesium ammonium phosphate (NH)4MgPO4) Adding phosphoric acid (industrial phosphoric acid or wet-process phosphoric acid) in an equivalent amount, and neutralizing with ammonia to pH 4 or more under stirring, namely the following reaction occurs:
(2) K in the magnesium ammonium phosphate mother liquor obtained according to the step (1)+And SO4 2-In terms of glaserite (NaK)3(SO4)2) Adjusting the ratio of potassium ions to sulfate ions; introducing ammonia gas while continuously stirring, wherein the ammonia concentration of a liquid phase is kept between 1 and 30mol/l when the reaction is ended, and the following reactions are carried out:
(3) Glaserite (NaK) in the step (2)3(SO4)2) Carrying out double decomposition reaction with KCl to obtain K2SO4The product, the reaction is as follows:
(4) NH is contained in the glaserite mother liquor obtained in the step (2)4Cl and NaClby evaporationNH is converted by using the relation of solubility and phase equilibrium4Cl and NaCl were separated.
(5) NH is contained in the glaserite mother liquor obtained in the step (2)4Cl and NaCl, or by adding alkaline substances (such as lime and the like) to convert ammonium chloride into free ammonia and recovering the ammonia by distillation.
The mother liquor after ammonia distillation contains CaCl2And NaCl, the CaCl is obtained by evaporating and separating NaCl by utilizing the solubility and phase equilibrium relation of the NaCl2。
The number m of crystal water of the magnesium ammonium phosphate in the step (1) is 1 or 6; the salt-making mother liquor or salt water used in the step (1) refers to that the system contains Mg2+Or containing Mg2+、K+、SO4 2-(ii) a The phosphoric acid used in step (1) may also be replaced by an equivalent amount of soluble phosphate, and the other operating steps are unchanged.
It is obvious from the above reactions that the present invention can prepare three kinds of chemical fertilizer from salt-making mother liquor (bittern). Especially, the best is the magnesium ammonium phosphate which is a multi-element, high-concentration and slow-release compound fertilizer which is popular in agriculture; potassium sulfate is also a chlorine-free potassium fertilizer widely applicable to commercial crops; ammonium chloride is a versatile nitrogen fertilizer. Compared with the prior art, the invention has the advantages that the magnesium, potassium and sulfate radicals in the salt-making mother liquor (bittern) or the salt water are fully extracted and utilized, and nearly 100 percent of magnesium in thesystem is separated out in the form of ammonium magnesium phosphate; the primary conversion rate of potassium ions and sulfate ions can reach 90-98%, so that energy is greatly saved, and cost is reduced.
The process makes salt-making mother liquor (bittern) and Mg-contained2+、K+、SO4 2-The salt water is fully utilized, the problem of the outlet of bittern and the like is effectively solved, waste is changed into valuable, and high-quality fertilizer is provided for agriculture.
Example 1
Taking out Mg2+63.0g/L、K+8.1g/L、Na+32.1g/L、SO4 2-55.0g/L、Cl-202.5g/L of mother liquor (bittern) for salt production 10L, based on Mg contained in raw material liquid2+In the amount of magnesium ammonium phosphate (NH)4MgPO4)Ratio of (1), equivalent weight (in terms of P)2O5Meter) was added 3.76L of wet-process phosphoric acid at 48.9% concentration. Then ammonia gas is introduced at room temperature while stirring continuously, ammonia introduction is stopped when the pH value of the system reaches 7, and then 6.31Kg of magnesium ammonium phosphate hexahydrate is obtained after clarification, filtration, washing and drying, wherein the precipitation rate of magnesium is 99.45%.
According to K contained in the magnesium ammonium phosphate mother liquor+And SO4 2-In number of K3Na(SO4)2The chemical composition proportioning of the method is measured, 96 percent of potassium chloride is added into the magnesium ammonium phosphate mother liquor, then ammonia gas is introduced at room temperature while continuously stirring, when the content of free ammonia in the system reaches 11.5mol/L, the ammonia introduction is stopped, and then the glaserite is clarified, filtered, washed and dried to obtain 0.955 Kg. The precipitation rate of potassium and sulfur is more than 98 percent. The glaserite is reacted with potassium chloride to obtain potassium sulfate 0.98Kg (K)2O content 50.1%, Cl-Content of 0.9%), and most of sodium chloride can be recovered by evaporation.
After the glaserite mother liquor is distilled to recover ammonia, most of sodium chloride (0.54Kg) and ammonium chloride (2.21Kg) are separated by evaporation and crystallization processes, and the mother liquor can be returned to the system for recycling.
Example 2
Taking out Mg2+63.0g/L、K+8.1g/L、Na+32.1g/L、SO4 2-55.0g/L、Cl-202.5g/L of mother liquor (bittern) for salt production 10L, based on Mg contained in raw material liquid2+In the amount of magnesium ammonium phosphate (NH)4MgPO4) Chemical composition ratio of (1), equivalent weight (in terms of P)2O5Meter) was added 3.12L of wet-process phosphoric acid having a concentration of 58.9%. Then ammonia gas is introduced at 340 plus or minus 3 ℃ K while continuously stirring, when the pH value of the system reaches 7.5, the ammonia introduction is stopped, and then the mixture is clarified, filtered, washed and dried to obtain 4.0Kg of monohydrate magnesium ammonium phosphate, wherein the precipitation rate of magnesium is 99.8 percent.
Phosphoric acidK contained in magnesium ammonium mother liquor+And SO4 2-In number of K3Na(SO4)2The chemical composition proportioning of the method is measured, 96 percent of potassium chloride is added into the magnesium ammonium phosphate mother liquor, then ammonia gas is introduced at room temperature while continuously stirring, when the content of free ammonia in the system reaches 12mol/L, the ammonia introduction is stopped, and then the glaserite is clarified, filtered, washed and dried to obtain 0.952 Kg. The precipitation rate of potassium and sulfur is 98.1%. Remixing of glaseritePotassium chloride reacts to produce potassium sulfate 0.97Kg (K)2O content 50.6%, Cl-Content of 0.83%), and most of sodium chloride can be recovered by evaporation.
Adding a proper amount of lime into the glaserite mother liquor, distilling to recover ammonia, evaporating and crystallizing to obtain most of sodium chloride (0.65Kg), and continuously evaporating to obtain calcium chloride (5.20 Kg).
Example 3
Taking out Mg2+63.0g/L、K+8.1g/L、Na+32.1g/L、SO4 2-55.0g/L、Cl-202.5g/L of mother liquor (bittern) for salt production 10L, based on Mg contained in raw material liquid2+In the amount of magnesium ammonium phosphate (NH)4MgPO4) Stoichiometric ratio of (in P), equivalent weight2O5Metered in) ammonium salt of phosphoric acid. Then slowly introducing ammonia gas at room temperature while continuously stirring, stopping introducing ammonia gas when the pH value of the system reaches 7, and then clarifying, filtering, washing and drying to obtain 6.31Kg of magnesium ammonium phosphate hexahydrate, wherein the precipitation rate of magnesium is 99.67%.
According to K contained in the magnesium ammonium phosphate mother liquor+And SO4 2-In number of K3Na(SO4)2The chemical composition proportioning of the method is measured, 96 percent of potassium chloride is added into the magnesium ammonium phosphate mother liquor, then ammonia gas is introduced at room temperature while continuously stirring, when the content of free ammonia in the system reaches 10.65mol/L, the ammonia introduction is stopped, and then the glaserite is clarified, filtered, washed and dried to obtain 0.952 Kg. The precipitation rate of potassium and sulfur is more than 98 percent. The glaserite is reacted with potassium chloride to obtain potassium sulfate 0.983Kg (K)2O content 50.2%, Cl-Content 0.89%), mother liquor was separated by evaporationMost of the sodium chloride can be recycled.
After ammonia is recovered from the glaserite mother liquor by distillation, most of sodium chloride (0.54Kg) and ammonium chloride (2.21Kg) are separated by evaporation and crystallization processes, and the mother liquor can be returned to the system for recycling.
Claims (4)
1. A process for preparing chemical fertilizer from the mother liquid of salt production (bittern) or salt water features that the mother liquid of salt production (bittern) or natural salt water is prepared through fractional precipitation and separation according to the solubility of substance to be prepared. The method is characterized by comprising the following steps:
(1) according to Mg in salt mother liquor (bittern) or salt water prepared from raw materials2+In terms of magnesium ammonium phosphate (NH)4MgPO4) Adding phosphoric acid (industrial phosphoric acid or wet-process phosphoric acid) in an equivalent amount, and neutralizing with ammonia to pH 4 or more under stirring, namely the following reaction occurs:
(2) K in the magnesium ammonium phosphate mother liquor obtained according to the step (1)+And SO4 2-In terms of glaserite (NaK)3(SO4)2) Adjusting the ratio of potassium ions to sulfate ions; introducing ammonia gas while continuously stirring, wherein the ammonia concentration of a liquid phase is kept between 1 and 30mol/l when the reaction is ended, and the following reactions are carried out:
(3) Glaserite (NaK) in the step (2)3(SO4)2) Carrying out double decomposition reaction with KCl to obtain K2SO4The product, the reaction is as follows:
(4) NH is contained in the glaserite mother liquor obtained in the step (2)4Cl and NaCl, NH by evaporation, exploiting their solubility and phase equilibrium relationship4Cl and NaCl were separated.
(5) NH is contained in the glaserite mother liquor obtained in the step (2)4Cl and NaCl, or by adding alkaline substances (such as lime and the like) to convert ammonium chloride into free ammonia and recovering the ammonia by distillation.
The mother liquor after ammonia distillation contains CaCl2And NaCl, the CaCl is obtained by evaporating and separating NaCl by utilizing the solubility and phase equilibrium relation of the NaCl2。
2. The method for producing chemical fertilizer from salt-making mother liquor (bittern) or brine according to claim 1, wherein number m of crystal water of magnesium ammonium phosphate in step (1) is 1 or 6.
3. The method for preparing chemical fertilizer from salt-making mother liquor (bittern) or salt water according to claim 1, wherein the salt-making mother liquor or salt water used in step (1) is Mg-containing system2+Or containing Mg2+、K+、SO4 2-。
4. A process for the preparation of a chemical fertilizer from a salt-making mother liquor (bittern) or brackish water according to claim 1, characterized in that the phosphoric acid used in step (1) can also be replaced by an equivalent amount of soluble phosphate, without changing the other operating steps.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02135647 CN1238308C (en) | 2002-10-21 | 2002-10-21 | Method for preparing chemical fertilizer from salt-making mother liquor (bittern) or salt water |
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| CN1238308C CN1238308C (en) | 2006-01-25 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093104A (en) * | 2010-12-02 | 2011-06-15 | 广东海洋大学 | Preparation method of ecological foliar fertilizer for plant |
| CN102503619A (en) * | 2011-09-02 | 2012-06-20 | 天津科技大学 | Method for preparing compound fertilizer from salt manufacturing mother liquor |
| CN102701809A (en) * | 2012-06-07 | 2012-10-03 | 湖南润亿农生态有机肥科技发展有限公司 | Novel microbial organic fertilizer and preparation method thereof |
| CN108483710A (en) * | 2018-04-04 | 2018-09-04 | 连云港职业技术学院 | A kind of seawater comprehensive utilizing method and system |
| CN108569684A (en) * | 2018-03-05 | 2018-09-25 | 山东和生海洋科技有限公司 | The method for producing ammonium magnesium phosphate using seawater or bittern water |
| CN108996791A (en) * | 2018-08-03 | 2018-12-14 | 山东和生海洋科技有限公司 | A kind of sea water desalination and comprehensive utilization new process |
| CN109020630A (en) * | 2018-08-24 | 2018-12-18 | 澔海科技(杭州)有限公司 | Struvite and extraction method thereof |
| CN109265242A (en) * | 2018-10-18 | 2019-01-25 | 白玉梅 | A kind of composite microbiological fertilizer and preparation method thereof |
| CN111453746A (en) * | 2020-04-01 | 2020-07-28 | 蔡梅初 | Preparation and application method of bittern preparation for salt pan capable of improving quality and yield of agricultural products |
| CN112408429A (en) * | 2020-11-25 | 2021-02-26 | 华融化学股份有限公司 | Process for refining primary saline water and preparing by-product slow-release compound fertilizer |
-
2002
- 2002-10-21 CN CN 02135647 patent/CN1238308C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093104A (en) * | 2010-12-02 | 2011-06-15 | 广东海洋大学 | Preparation method of ecological foliar fertilizer for plant |
| CN102503619A (en) * | 2011-09-02 | 2012-06-20 | 天津科技大学 | Method for preparing compound fertilizer from salt manufacturing mother liquor |
| CN102503619B (en) * | 2011-09-02 | 2013-11-06 | 天津科技大学 | Method for preparing compound fertilizer from salt manufacturing mother liquor |
| CN102701809A (en) * | 2012-06-07 | 2012-10-03 | 湖南润亿农生态有机肥科技发展有限公司 | Novel microbial organic fertilizer and preparation method thereof |
| CN108569684A (en) * | 2018-03-05 | 2018-09-25 | 山东和生海洋科技有限公司 | The method for producing ammonium magnesium phosphate using seawater or bittern water |
| CN108483710A (en) * | 2018-04-04 | 2018-09-04 | 连云港职业技术学院 | A kind of seawater comprehensive utilizing method and system |
| CN108483710B (en) * | 2018-04-04 | 2022-03-25 | 连云港职业技术学院 | Comprehensive seawater utilization method and system |
| CN108996791B (en) * | 2018-08-03 | 2021-02-12 | 山东和生海洋科技有限公司 | Novel process for seawater desalination and comprehensive utilization |
| CN108996791A (en) * | 2018-08-03 | 2018-12-14 | 山东和生海洋科技有限公司 | A kind of sea water desalination and comprehensive utilization new process |
| CN109020630B (en) * | 2018-08-24 | 2019-09-13 | 澔海科技(杭州)有限公司 | struvite and extraction method thereof |
| WO2020037872A1 (en) * | 2018-08-24 | 2020-02-27 | 澔海科技(杭州)有限公司 | Struvite and extraction method therefor |
| CN109020630A (en) * | 2018-08-24 | 2018-12-18 | 澔海科技(杭州)有限公司 | Struvite and extraction method thereof |
| US11220431B2 (en) | 2018-08-24 | 2022-01-11 | Howhigh Science & Technology (Hangzhou) Co., Ltd. | Struvite and extracting method therefor |
| CN109265242A (en) * | 2018-10-18 | 2019-01-25 | 白玉梅 | A kind of composite microbiological fertilizer and preparation method thereof |
| CN111453746A (en) * | 2020-04-01 | 2020-07-28 | 蔡梅初 | Preparation and application method of bittern preparation for salt pan capable of improving quality and yield of agricultural products |
| CN112408429A (en) * | 2020-11-25 | 2021-02-26 | 华融化学股份有限公司 | Process for refining primary saline water and preparing by-product slow-release compound fertilizer |
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| CN1238308C (en) | 2006-01-25 |
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