CN1762808A - Calcium removing and purification method of industrial potassium chloride - Google Patents
Calcium removing and purification method of industrial potassium chloride Download PDFInfo
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- CN1762808A CN1762808A CN 200510086474 CN200510086474A CN1762808A CN 1762808 A CN1762808 A CN 1762808A CN 200510086474 CN200510086474 CN 200510086474 CN 200510086474 A CN200510086474 A CN 200510086474A CN 1762808 A CN1762808 A CN 1762808A
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- potassium chloride
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Abstract
The industrial potassium chloride decalcifying process belongs to the field of inorganic chemical industrial technique, and is one stepped phase converting process to eliminate calcium sulfate impurity from industrial potassium chloride product. The decalcifying agent A is first added into the suspended solution of saturated potassium chloride with solid calcium sulfate to convert calcium sulfate calcium precipitate easy to dissolve in acid and complex and make sulfate radical ion enter to water for elimination through filtering; and the decalcifying agent B is then added to dissolve calcium precipitate selectively and make calcium enter the solution for elimination through filtering. The said process can lower the calcium content in industrial potassium chloride product from 2-15 % to below 1 %, and increase the potassium chloride content to over 99 %. The said process is also suitable for eliminating calcium sulfate from other inorganic salt system.
Description
Technical field
The present invention relates to a kind of new technology of from industrial potassium chloride, removing calcium sulfate impurity, belong to the inorganic chemical technology field.
Background technology
China is a large agricultural country, also is the country of a potash fertilizer resource famine, in order to satisfy the needs of agricultural development, country will spend a large amount of foreign exchanges from state's import potash fertilizer such as Israel (Wang Xu, the general introduction of potash fertilizer market, the world, the means of agricultural production science and technology every year, 2004,1,36-37).The potassium resource of China concentrates on the Cha Er sweat salt lake in Qinghai mostly, 1.45 hundred million tons of Repone K balance resources, account for the whole nation proven reserve 97% (Tu Huaikui, opinion western part of China potassium ore resources distribution characteristics and DEVELOPMENT PROSPECT, Gansu geology journal, 2002,1,69-75).For this reason, country drops into huge fund (25.85 hundred million yuan) and has set up the Repone K production line of producing 1000000 tons per year in the salt lake, Qinghai and gone into operation up to standardly summer in 2004, has greatly alleviated the present situation of domestic potash fertilizer shortage.
The natural bittern that the salt pan is picked up from this project utilization shines the system carnallitite, adopts reverse flotation-cold crystallization prepared Repone K again.In reverse flotation-cold crystallization technology, remove the sodium-chlor of carrying secretly in the carnallitite with flotation reagent earlier, add water selectivity dissolving magnesium chloride then, after centrifugation, drying, promptly get the Repone K product.This engineering utilization flotation technology is ingenious to have solved the separation difficult problem of sodium-chlor, Repone K, for a new way has been opened up in the extensive utilization of salt lake potassium resource.In above-mentioned technology, Repone K is in state of saturation all the time and how exists with solid form.Present problem is: the bittern that picks up from the salt lake generally all contains more calcium sulfate impurity, and calcium contents has and increases trend gradually, utilize existing technology still can't effectively remove, cause the calcium sulfate foreign matter content in the industrial potassium chloride high in 2.0～15% scopes always, the purity of Repone K product is lower than 95% mostly, and all difficult high purity product (KCE content is greater than 98%) with import is competed on quality and price.Therefore, the deliming purification problem of industrial potassium chloride has become the great technical barrier of being badly in need of solution.
In field of inorganic chemical engineering, deliming is a comparatively common technical problem from product, but calcium exists with the soluble state form mostly in the system that relates to.People generally adopt adding precipitation agent method (as vitriol, carbonate, oxalate etc. the calcium in the solution to be separated out with precipitation forms, remove (Cheng Fangqin, Li Hua, rural area spring through solid-liquid separation again, the experimental study of salt lake bittern purifying removal of impurities, University Of Shanxi's journal (natural science edition), 2004,274 (387-391)); Yuan Rongzheng, Chen Xi, Zhu Liping, Zhang Fangjun, the technology controlling and process of mixed acid process nitrophosphate fertilizer deliming process, phosphate fertilizer and multiple fertilizer, 2001,16 (6), 41-43).When if calcium is insoluble to acid with insoluble solid-state form (as calcium sulfate, lime carbonate) existence and major product, add mineral acid (hydrochloric acid, nitric acid) and also can effectively remove calcium impurities (Yin Zhong, Zhao Xiaodong, the solubleness of calcium sulfate in hydrochloric acid and sodium chloride aqueous solution, oilfield chemistry, 1994,11 (4), 345-347).But for the Repone K-calcium sulfate system that the present invention relates to, Repone K is very easily water-soluble, and the chemical property of calcium sulfate is very stable, under normal temperature condition, both be insoluble in water, solubleness in acid/alkali is also very limited, cause the deliming difficulty significantly to increase, be difficult to directly use existing deliming method.Utilize the difference of specific gravity of Repone K and calcium sulfate also can realize the roughing out of Repone K and calcium sulfate to a certain extent, but be difficult to calcium sulphate content is reduced to below 2%.Therefore, how effective elimination calcium sulfate impurity becomes still unsolved so far technical barrier both at home and abroad from Repone K, also is the key of restriction China industrial potassium chloride quality.
Summary of the invention
The purpose of this invention is to provide a kind of novel method that can from Repone K, remove calcium sulfate, under the situation that is not changing existing Production Flow Chart and processing condition, add by substep and cheap and easy to get remove calcon and can reach ideal deliming effect.Use the method for the invention that the content of calcium sulfate in the industrial potassium chloride is reduced to below 1% by 2～15%, KCE content is greater than 99%.The present invention provides a practicable novel method for the deliming of the existing industrial potassium chloride of China, and this technology also can be used for removing calcium sulfate impurity from other soluble inorganic salt system.
Technical scheme of the present invention is as follows:
A kind of calcium removing and purification method of industrial potassium chloride, it is characterized in that: described method employing thing phase inversion process removes the calcium sulfate impurity in the industrial potassium chloride step by step, at first in containing the saturated Repone K aaerosol solution of solid Repone K and solid calcium sulphate, add calcium remover A, it is lower but be soluble in the calcium deposit thing of acid or complex compound that calcium sulfate in the aaerosol solution is converted into solubleness, sulfate ion entered in the water and by filter type remove; To filter the gained solid then and add the saturated potassium chloride solution of new preparation, add calcium remover B selective dissolution calcium deposit thing, and make calcium enter solution and remove by filter, reach the deliming purpose thus;
Described calcium remover A is inorganic soluble carbon hydrochlorate or solubility oxalate, and wherein the weight ratio of calcium sulfate is 0.75～2: 1 in calcium remover A and the described aaerosol solution;
Described calcium remover B is hydrochloric acid or nitric acid, perhaps can be, quicken calcium deposit thing dissolved complexing agent with calcium generation complexing action, and wherein the weight ratio of calcium sulfate is 0.5～3: 1 in calcium remover B and the described aaerosol solution.
In the present invention, the preferred salt of wormwood of described inorganic soluble carbon hydrochlorate, yellow soda ash, volatile salt or bicarbonate of ammonia.
In the present invention, the preferred sodium oxalate of described solubility oxalate, potassium oxalate or ammonium oxalate.
In the present invention, described can be with calcium generation complexing action, quicken the preferred ammonium chloride of calcium deposit thing dissolved complexing agent, ethylenediamine tetraacetic acid (EDTA).
The calcon that removes that the deliming purification new technology that the present invention proposes is used is the chemical product that routinizes cheap and easy to get.When adopting technical finesse Repone K of the present invention, 1 percentage point of required reagent cost of the every reduction of calcium sulphate content is less than 30 yuan in the Repone K per ton, and 1 percentage point of its price of the every reduction of calcium sulphate content can increase more than 60 yuan, and economic benefit is very remarkable.The deliming method that the present invention proposes also is applicable to from other soluble inorganic salt and removes calcium sulfate.Similar work does not appear in the newspapers both at home and abroad as yet.
Embodiment
The present invention removes technical scheme by following thing inversion of phases-substep and realizes: at first utilize carbonate or oxalate to carry out the thing inversion of phases, make calcium sulfate change into lime carbonate or caoxalate, sulfate radical enters the solution after-filtration and removes, in containing the saturated KCl system of lime carbonate or caoxalate, add appropriate amount of acid or complexing agent selective dissolution calcium salt then, make calcium ion enter solution and by removing by filter.Its operation steps is undertaken by following order:
(1) the saturated Repone K aaerosol solution of getting the industrial potassium chloride production scene is as experimental raw, and the solid KCE content is 20～60% in the raw material, and the solid sulphuric acid calcium contents is 2～15%;
(2) add calcium remover A (preferred inorganic soluble carbon hydrochlorate or solubility oxalate) in above-mentioned system, wherein the weight ratio of calcium remover A and calcium sulfate is 0.75～2: 1, stirs calcium sulfate to be changed into lime carbonate or caoxalate in 1.0 hours;
(3) remove by filter sulfate radical in the solution;
(4) filter cake is scattered in the saturated potassium chloride solution of new preparation, add calcium remover B (preferred hydrochloric acid, nitric acid, ammonium chloride, ethylenediamine tetraacetic acid (EDTA)) then, the weight ratio of calcium remover B and calcium sulfate is 0.5～3: 1, and stirring at normal temperature can make calcium salt all dissolve in 0.5 hour;
(5) remove by filter calcium ion in the solution, 105 ℃ of dryings 4 hours, can obtain calcium sulphate content less than 1% then, Repone K purity is greater than 99% product.
Specific embodiment is as follows:
Embodiment 1
The saturated Repone K suspension that contains 20% solid Repone K and 2% solid calcium sulphate that adopts 100kg to take from the Repone K production scene is experimental raw, adds 0.8kg salt of wormwood in raw material, stirs (150 rev/mins) 30 minutes after-filtration; Filter cake is added 100 liters of saturated potassium chloride solution, stir (150 rev/mins) and add 1.0kg 20% hydrochloric acid after 10 minutes, continue to stir (150 rev/mins) 30 minutes, filter.Filter cake 105 ℃ of dryings 4 hours, is obtained KCE content 99.8%, the Repone K product of calcium sulphate content 0.2%.
Embodiment 2
The saturated Repone K suspension that contains 60% solid Repone K and 15% solid calcium sulphate that adopts 100kg to take from the Repone K production scene is experimental raw, adds 9kg yellow soda ash in raw material, stirs (150 rev/mins) 30 minutes after-filtration; Filter cake is added 100 liters of saturated potassium chloride solution, stir (150 rev/mins) and add 5.0kg 20% hydrochloric acid after 10 minutes, continue to stir (150 rev/mins) 30 minutes, filter.Filter cake 105 ℃ of dryings 4 hours, is obtained KCE content 99.0%, the Repone K product of calcium sulphate content 1.0%.
Embodiment 3
The saturated Repone K suspension that contains 40% solid Repone K and 5% solid calcium sulphate that adopts 100kg to take from the Repone K production scene is experimental raw, adds the 1.5kg volatile salt in raw material, stirs (150 rev/mins) 30 minutes after-filtration; Filter cake is added 100 liters of saturated potassium chloride solution, stir (150 rev/mins) and add 5kg20% nitric acid after 10 minutes, continue to stir (150 rev/mins) 30 minutes, filter.Filter cake 105 ℃ of dryings 4 hours, is obtained KCE content 99.2%, the Repone K product of calcium sulphate content 0.8%.
Embodiment 4
The saturated Repone K suspension that contains 40% solid Repone K and 10% solid calcium sulphate that adopts 100kg to take from the Repone K production scene is experimental raw, adds 3.5kg bicarbonate of ammonia in raw material, stirs (150 rev/mins) 30 minutes after-filtration; Filter cake is added 100 liters of saturated potassium chloride solution, stir (150 rev/mins) and add 6.0kg 20% hydrochloric acid after 10 minutes, continue to stir (150 rev/mins) 30 minutes, filter.Filter cake 105 ℃ of dryings 4 hours, is obtained KCE content 99.4%, the Repone K product of calcium sulphate content 0.6%.
Embodiment 5
The saturated Repone K suspension that contains 40% solid Repone K and 5% solid calcium sulphate that adopts 100kg to take from the Repone K production scene is experimental raw, adds the 2.5kg potassium oxalate in raw material, stirs (150 rev/mins) 30 minutes after-filtration; Filter cake is added 100 liters of saturated potassium chloride solution, stir (150 rev/mins) and add 5kg 20% nitric acid after 10 minutes, continue to stir (150 rev/mins) 30 minutes, filter.Filter cake 105 ℃ of dryings 4 hours, is obtained KCE content 99.5%, the Repone K product of calcium sulphate content 0.5%.
Embodiment 6
The saturated Repone K suspension that contains 40% solid Repone K and 5% solid calcium sulphate that adopts 100kg to take from the Repone K production scene is experimental raw, adds the 2.5kg sodium oxalate in raw material, stirs (150 rev/mins) 30 minutes after-filtration; Filter cake is added 100 liters of saturated potassium chloride solution, stir (150 rev/mins) and add 1kg ethylenediamine tetraacetic acid (EDTA) (EDTA) after 10 minutes, continue to stir (150 rev/mins) 30 minutes, filter.Filter cake 105 ℃ of dryings 4 hours, is obtained KCE content 99.3%, the Repone K product of calcium sulphate content 0.7%.
Embodiment 7
The saturated Repone K suspension that contains 40% solid Repone K and 5% solid calcium sulphate that adopts 100kg to take from the Repone K production scene is experimental raw, adds the 2.5kg ammonium oxalate in raw material, stirs (150 rev/mins) 30 minutes after-filtration; Filter cake is added 100 liters of saturated potassium chloride solution, stir (150 rev/mins) and add 1kg ammonium chloride after 10 minutes, continue to stir (150 rev/mins) 30 minutes, filter.Filter cake 105 ℃ of dryings 4 hours, is obtained KCE content 99.1%, the Repone K product of calcium sulphate content 0.9%.
Claims (4)
1. the calcium removing and purification method of an industrial potassium chloride, it is characterized in that: described method employing thing phase inversion process removes the calcium sulfate impurity in the industrial potassium chloride step by step, at first in containing the saturated Repone K aaerosol solution of solid Repone K and solid calcium sulphate, add calcium remover A, it is lower but be soluble in the calcium deposit thing of acid or complex compound that calcium sulfate in the aaerosol solution is converted into solubleness, sulfate ion entered in the water and by filter type remove; To filter the gained solid then and add the saturated potassium chloride solution of new preparation, add calcium remover B selective dissolution calcium deposit thing, and make calcium enter solution and remove by filter, reach the deliming purpose thus;
Described calcium remover A is inorganic soluble carbon hydrochlorate or solubility oxalate, and wherein the weight ratio of calcium sulfate is 0.75～2: 1 in calcium remover A and the described aaerosol solution;
Described calcium remover B is hydrochloric acid or nitric acid, perhaps can be, quicken calcium deposit thing dissolved complexing agent with calcium generation complexing action, and wherein the weight ratio of calcium sulfate is 0.5～3: 1 in calcium remover B and the described aaerosol solution.
2. the calcium removing and purification method of industrial potassium chloride according to claim 1, it is characterized in that: described inorganic soluble carbon hydrochlorate comprises salt of wormwood, yellow soda ash, volatile salt or bicarbonate of ammonia.
3. the calcium removing and purification method of industrial potassium chloride according to claim 1, it is characterized in that: described solubility oxalate comprises sodium oxalate, potassium oxalate or ammonium oxalate.
4. the calcium removing and purification method of industrial potassium chloride according to claim 1 is characterized in that: described can be with calcium generation complexing action, quicken calcium deposit thing dissolved complexing agent and comprise ammonium chloride, ethylenediamine tetraacetic acid (EDTA).
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| CNB2005100864743A CN100411988C (en) | 2005-09-23 | 2005-09-23 | Calcium removing and purification method of industrial potassium chloride |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476812A (en) * | 2010-11-24 | 2012-05-30 | 江苏省勤奋药业有限公司 | Production process of medicinal potassium chloride |
| CN104495878A (en) * | 2015-01-05 | 2015-04-08 | 格尔木康生钾业科技发展有限公司 | Method for preparing food-grade potassium chloride by removing calcium from high-calcium waste ore |
| CN109811371A (en) * | 2019-01-05 | 2019-05-28 | 沈阳工业大学 | A kind of method that low-grade bauxite resource prepares alusil alloy |
| CN115323199A (en) * | 2021-11-12 | 2022-11-11 | 虔东稀土集团股份有限公司 | Method for recovering rare earth elements |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304072B (en) * | 2013-07-11 | 2014-10-15 | 佛山市南海区大沥吉力达铝辅助材料厂 | Recycling method of industrial waste water |
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| GB1142901A (en) * | 1965-02-26 | 1969-02-12 | Alfred Frederick Nylander | Improved method and apparatus for separating the components in brine |
| GB1500288A (en) * | 1974-05-21 | 1978-02-08 | Canadian Ind | Purification of brine |
| US4210421A (en) * | 1978-11-13 | 1980-07-01 | Ppg Industries, Inc. | Method for reducing kcl tailings loss from evaporation |
| MXPA04007509A (en) * | 2002-01-31 | 2004-11-10 | Council Scient Ind Res | A process for recovery of low sodium salt from bittern. |
| FR2866870A1 (en) * | 2004-02-26 | 2005-09-02 | Goux Jean Yves Le | Preparation of crystallized sodium chloride (NaCl) from brines, used in conditioning salts, comprises eliminating magnesium; producing sodium carbonate; crystallizing-evaporating NaCl; precipitating sulfates; and eliminating excess calcium |
| CN100384737C (en) * | 2004-06-09 | 2008-04-30 | 华东理工大学 | Preparing method for potassium chloride with low calcium sulfate content |
-
2005
- 2005-09-23 CN CNB2005100864743A patent/CN100411988C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476812A (en) * | 2010-11-24 | 2012-05-30 | 江苏省勤奋药业有限公司 | Production process of medicinal potassium chloride |
| CN104495878A (en) * | 2015-01-05 | 2015-04-08 | 格尔木康生钾业科技发展有限公司 | Method for preparing food-grade potassium chloride by removing calcium from high-calcium waste ore |
| CN109811371A (en) * | 2019-01-05 | 2019-05-28 | 沈阳工业大学 | A kind of method that low-grade bauxite resource prepares alusil alloy |
| CN109811371B (en) * | 2019-01-05 | 2021-08-03 | 沈阳工业大学 | Method for preparing aluminum-silicon alloy from low-grade aluminum resources |
| CN115323199A (en) * | 2021-11-12 | 2022-11-11 | 虔东稀土集团股份有限公司 | Method for recovering rare earth elements |
| CN115323199B (en) * | 2021-11-12 | 2023-09-29 | 虔东稀土集团股份有限公司 | Rare earth element recovery method |
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| CN100411988C (en) | 2008-08-20 |
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