CN103539165B - Method for producing potassium sulfate by utilizing insoluble rocks containing potassium - Google Patents
Method for producing potassium sulfate by utilizing insoluble rocks containing potassium Download PDFInfo
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- CN103539165B CN103539165B CN201310509851.4A CN201310509851A CN103539165B CN 103539165 B CN103539165 B CN 103539165B CN 201310509851 A CN201310509851 A CN 201310509851A CN 103539165 B CN103539165 B CN 103539165B
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- potassium
- ammonium fluoride
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Abstract
The invention relates to a method for producing potassium sulfate by utilizing insoluble rocks containing potassium. The technological process comprises the following steps: (1) pretreating the insoluble rocks containing potassium; (2) treating the insoluble rocks containing potassium by use of ammonium fluoride; (3) filtering a product treated with the ammonium fluoride; (4) performing acidolysis on the product obtained after treatment based on ammonium fluoride; (5) dissolving the product obtained after treatment based on sulfuric acid in water; (6) performing fractional precipitation by regulating the pH (Potential Of Hydrogen) so as to obtain a potassium sulfate solution; (7) regenerating and recycling an ammonium fluoride solution. Potash feldspars K(AlSi3O8) are mainly taken as the rocks containing potassium. Rubidium feldspars and cesium feldspars, which are utilized to replace the potash feldspars, are used for producing rubidium sulfate and cesium sulfate by utilizing the process and the process condition which are provided by the invention. The insoluble rocks containing potassium are converted into acid-soluble solids by use of ammonium fluoride, so that the potassium sulfate is obtained after the acid-soluble solids are acidified by the sulfuric acid; meanwhile, other elements in the rocks are effectively utilized. The ammonium fluoride is recycled in the whole technological process. The technological process is low in temperature, easy to control and high in reaction yield.
Description
Technical field
The invention belongs to insoluble potassium bearing rock evaluation and exploration technology field.In particular to a kind of method of utilizing insoluble potassium bearing rock to produce potassium sulfate.
Background technology
Potassium is one of essential macronutrient of crop growth, can strengthen the degeneration-resistant border of crop ability, and therefore the promoter action that is formed with to crop better quality is counted as " Quality Element ".Because Potassium in Soils in many situations can not meet crop requirement, need application of potash fertilizer, so potassium is called as one of " major fertilizer elements ".China's severe potassium deficiency, the arable land that need to mend potassium accounts for more than 70%, approximately needs every year 8000000 tons of left and right of the pure amount of potash fertilizer, is converted to potassium sulfate quantity of goods produced 1,500 ten thousand tons of left and right.China's soluble potassium ore resources ratio is lower, and insoluble potassium potassium bearing rock resource reserve is larger, needs every year a large amount of potash fertilizer of import.Therefore, utilize insoluble potassium potassium bearing rock to produce potash fertilizer, be conducive to alleviate the domestic demand to potassium.
Insoluble potassium bearing rock main component is potassium felspar sand, and potash feldspar ore is that potassium content is higher, distribute the widest, the maximum water-insoluble potassium resource of reserves, and its main chemical compositions is SiO
2, Al
2o
3, K
2o etc.China from the beginning of the research that just starts to utilize producing potassium fertilizer from potash feldspar, has successively carried out tens of kinds of technical studies from twentieth century sixties, mainly contains sintering process, high-temperature melting method, low-temperature decomposition method.Sintering process utilizes Wingdale and coal to make raw material, through pulverizing, after balling-up, in shaft kiln calcination, makes potassium oxide wherein change into water-soluble.This kind of method production cost is low, but in production process, energy consumption is large, and the potassium transformation efficiency in potassium felspar sand lower (60%～90%), and product potassium content is low, and its popularization is hindered.High-temperature melting method is being produced on the basis of fused(calcium magnesium)phosphate, the potassium felspar sand of proportioning 25%～30%, and high-temperature fusion (1200～1300 ℃) makes calcium magnesium phosphorus potassium complex fertilizer, and its product is containing available phosphorus (P
2o
5) 10%～14%, soluble potassium (K
2o) 4%～5%, the method production cost is low.Low-temperature decomposition method potassium felspar sand raw material is crushed to below 6mm through volume formula crusher, Raymond mill is crushed to mineral below 100 meshes, by adhesive tape conveyor, mineral are transported in pond and CaO water soaking 20min, then through pump, hit the person and heat in plus-pressure furnace, in stove, temperature is controlled at 100～200 ℃, after certain hour, from stove, flow out and enter in pond and Na
2sO
4mix and soak, by techniques such as crystallization, solid-liquid separation, obtain K
2sO
4, NaOH industrial raw material.In sum, in having technology now, from insoluble potassium bearing rock, extract potassium, exist that temperature is high, energy consumption is large, potassium content is low, the problem such as complex process, the rate of recovery are low.
Therefore, researching and developing feasible Technology, by the industrialization of insoluble potassium bearing rock production high density potash fertilizer, is the needs of China's economic society and agricultural development.
Summary of the invention
The object of this invention is to provide a kind of method of utilizing insoluble potassium bearing rock to produce potassium sulfate, for utilizing insoluble potassium bearing rock to produce potassium sulfate, simultaneously for the aluminium in comprehensive utilization potassium bearing rock, silicon are produced aluminum oxide, silicon-dioxide provides basic condition.
A kind of method of utilizing insoluble potassium bearing rock to produce potassium sulfate of the present invention, its technical process and processing step are:
(1) pre-treatment: insoluble potassium bearing rock is pulverized, processed and remove wherein carbonate with dilute hydrochloric acid, the not carbonato insoluble potassium bearing rock powder that dewaters to obtain, is called for short potassium rock dust;
(2) Neutral ammonium fluoride is processed: the reacting by heating in reactor by potassium rock dust and ammonium fluoride aqueous solution, obtains potassium silicofluoride, aluminum fluosilicate, aluminum fluoride, its reaction principle:
Collect ammonia;
(3) filter: the product after Neutral ammonium fluoride is processed filters, and filtrate-main component is the complete ammonium fluoride solution of unreacted, returns to step (2), and filter residue enters next step processing;
(4) acidolysis: step (3) filter residue is obtained to potassium sulfate through vitriol oil reacting by heating, its reaction principle:
Collect SiF
4and HF;
(5) water-soluble: the product after vitriolization is added to water, potassium sulfate is dissolved, filter, wash, filtrate is for the production of potassium sulfate;
(6) adjust pH: the filtrate of step (5) adjusts pH to equal 4 with alkaline solution, separated ironic hydroxide, adjusts pH to equal 11, and separated aluminium hydroxide, obtains potassium sulfate solution;
(7) reclaim: the SiF that the ammonia that step (2) is collected and step (4) are collected
4in aminating reaction still, react to obtain Neutral ammonium fluoride and silicon-dioxide with HF, Neutral ammonium fluoride returns to step (2), and silicon-dioxide is byproduct, reaction principle:
The processing condition of each processing step of the present invention are:
(1) pre-treatment: insoluble potassium bearing rock is levigate to 100～300 orders, with the dilute hydrochloric acid of 1%w/w, process to not emitting CO
2till, obtain potassium rock dust;
(2) Neutral ammonium fluoride is processed: the ammonium fluoride aqueous solution stirring heating in reactor that is 10%～45%w/w with concentration by potassium rock dust is reacted, 80 ℃～110 ℃ of temperature of reaction, reaction times 1～3h, the water-soluble weight ratio of potassium rock dust and Neutral ammonium fluoride is 1: 10～20, collects ammonia;
(3) filter: step (2) reactant is filtered, and filtrate is returned to step (2), and filter residue enters next step processing;
(4) acidolysis: step (3) filter residue is carried out to acidolysis processing through 98% vitriol oil at 140 ℃～210 ℃, and vitriol oil consumption is raw material weight 60%～100%, collects SiF
4and HF;
(5) water-soluble: the product after vitriolization is added to water treatment, and the weight ratio of product and water is 1: 3～5, and potassium sulfate is fully dissolved, after filtration, washing, filtrate and washings merge and enter lower step and process, and filter residue is made byproduct;
(6) adjust pH: the solution that step (5) obtains equals 4 with adjusting PH with base, separated ironic hydroxide, adjusts pH to equal 11, and separated aluminium hydroxide, obtains potassium sulfate solution;
(7) reclaim: the SiF that the ammonia that step (2) is collected and step (4) are collected
4in aminating reaction still, react to obtain Neutral ammonium fluoride and silicon-dioxide with HF, Neutral ammonium fluoride returns to step (2), and silicon-dioxide is byproduct.
It is a kind of in ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, volatile salt that above-mentioned steps (6) is adjusted alkali that pH uses.
The insoluble potassium bearing rock of indication of the present invention mainly refers to potassium felspar sand
.
With rubidium feldspar and caesium feldspar, replace potassium felspar sand, by the above-mentioned technique of the present invention and processing condition, produce rubidiurn sulfate and cesium sulfate.
The present invention adopts Neutral ammonium fluoride that insoluble potassium bearing rock is converted to solubility in acid solid, obtains potassium sulfate after sulfuric acid acidation, and other elements in ore have also obtained effective utilization simultaneously.Haveing suffered technological process Neutral ammonium fluoride recycles.The technological process temperature relating in the present invention is low, is easy to control, and reaction yield is high.This invention technology has realized effective utilization of insoluble potassium bearing rock.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the inventive method.
Embodiment
Embodiment 1
(1) by 200 object potassium bearing rock powder 50g, the dilute hydrochloric acid 200ml with 1% processes, and filters, dewaters;
(2) step (1) potassium bearing rock powder is added to 500ml concentration is housed is 20% NH
4in the reactor of F solution, stirring heating is reacted under the temperature condition of 95 ℃～105 ℃, collects ammonia and the water vapour evaporating with absorption bottle;
(3) after reaction 2h, reactant filters, and filtrate is returned to step (2) and recycled, and solid drying is standby;
(4) solid step (3) being obtained and the 40g98% vitriol oil carry out acidolysis reaction under the condition of 190 ℃～200 ℃, pass in the ammoniacal liquor of step (2) collection after the fluoro-gas foam removal volatilizing;
(5) acidolysis solid product 200g water dissolution step (4) being obtained, filters, washs;
(6) filtrate step (5) being obtained is used ammoniacal liquor regulator solution pH value, sediment separate out during pH value 4, and sediment separate out when filtrate continuation regulates pH value 11, obtains potassium sulfate and ammonium sulfate mixture 57.4g altogether after filtrate is concentrated.
Embodiment 2
(1) by 200 object potassium bearing rock powder 50g, the dilute hydrochloric acid 200ml with 1% processes, and filters, dewaters;
(2) step (1) potassium bearing rock powder is added to 500ml concentration is housed is 20% NH
4in the reactor of F solution, stirring heating is reacted under the temperature condition of 95 ℃～105 ℃, collects ammonia and the water vapour evaporating with absorption bottle;
(3) after reaction 1h, reactant filters, and filtrate is returned to step (2) and recycled, and solid drying is standby;
(4) solid step (3) being obtained and 40g 98% vitriol oil carry out acidolysis reaction under the condition of 175 ℃～190 ℃, pass in the ammoniacal liquor of step (2) collection after the fluoro-gas foam removal volatilizing;
(5) acidolysis solid product 200g water dissolution step (4) being obtained, filters, washs;
(6) filtrate step (5) being obtained is used ammoniacal liquor regulator solution pH value, sediment separate out during pH value 4, and sediment separate out when filtrate continuation regulates pH value 11, obtains potassium sulfate and ammonium sulfate mixture 54.6g altogether after filtrate is concentrated.
Any technical solution of the present invention content that do not depart from, any simple modification of above embodiment being done according to the present invention program's essence, equivalent variations or modification, all belong to the scope of technical solution of the present invention.
Claims (5)
1. utilize insoluble potassium bearing rock to produce a method for potassium sulfate, it is characterized in that technical process and processing step are:
(1) pre-treatment: insoluble potassium bearing rock is pulverized, processed and remove wherein carbonate with dilute hydrochloric acid, the not carbonato insoluble potassium bearing rock powder that dewaters to obtain, is called for short potassium rock dust;
(2) Neutral ammonium fluoride is processed: the reacting by heating in reactor by potassium rock dust and ammonium fluoride aqueous solution, obtains potassium silicofluoride, aluminum fluosilicate, aluminum fluoride, its reaction principle:
Collect ammonia;
(3) filter: the product after Neutral ammonium fluoride is processed filters, and filtrate-main component is the complete ammonium fluoride solution of unreacted, returns to step (2), and filter residue enters next step processing;
(4) acidolysis: step (3) filter residue is obtained to potassium sulfate through vitriol oil reacting by heating, its reaction principle:
Collect SiF
4and HF;
(5) water-soluble: the product after vitriolization is added to water, potassium sulfate is dissolved, filter, wash, filtrate is for the production of potassium sulfate;
(6) adjust pH: the filtrate of step (5) adjusts pH to equal 4 with alkaline solution, separated ironic hydroxide, adjusts pH to equal 11, and separated aluminium hydroxide, obtains potassium sulfate solution;
(7) reclaim: the SiF that the ammonia that step (2) is collected and step (4) are collected
4in aminating reaction still, react to obtain Neutral ammonium fluoride and silicon-dioxide with HF, Neutral ammonium fluoride returns to step (2), and silicon-dioxide is byproduct.
2. a kind of method of utilizing insoluble potassium bearing rock to produce potassium sulfate according to claim 1, is characterized in that the processing condition of each processing step are:
(1) pre-treatment: insoluble potassium bearing rock is levigate to 100～300 orders, with the dilute hydrochloric acid of 1%w/w, process to not emitting CO
2till, obtain potassium rock dust;
(2) Neutral ammonium fluoride is processed: the ammonium fluoride aqueous solution stirring heating in reactor that is 10%～45%w/w with concentration by potassium rock dust is reacted, 80 ℃～110 ℃ of temperature of reaction, reaction times 1～3h, the weight ratio of potassium rock dust and ammonium fluoride aqueous solution is 1: 10～20, collects ammonia;
(3) filter: step (2) reactant is filtered, and filtrate is returned to step (2), and filter residue enters next step processing;
(4) acidolysis: step (3) filter residue is carried out to acidolysis processing through 98% vitriol oil at 140 ℃～210 ℃, and vitriol oil consumption is raw material weight 60%～100%, collects SiF
4and HF;
(5) water-soluble: the product after vitriolization is added to water treatment, and the weight ratio of product and water is 1: 3～5, and potassium sulfate is fully dissolved, after filtration, washing, filtrate and washings merge and enter lower step and process, and filter residue is made byproduct;
(6) adjust pH: the solution that step (5) obtains equals 4 with adjusting PH with base, separated ironic hydroxide, adjusts pH to equal 11, and separated aluminium hydroxide, obtains potassium sulfate solution;
(7) reclaim: the SiF that the ammonia that step (2) is collected and step (4) are collected
4in aminating reaction still, react to obtain Neutral ammonium fluoride and silicon-dioxide with HF, Neutral ammonium fluoride returns to step (2), and silicon-dioxide is byproduct.
3. a kind of method of utilizing insoluble potassium bearing rock to produce potassium sulfate according to claim 1 and 2, is characterized in that: the alkali that step (6) adjusts pH to use is a kind of in ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, volatile salt.
4. a kind of method of utilizing insoluble potassium bearing rock to produce potassium sulfate according to claim 1 and 2, is characterized in that: the insoluble potassium bearing rock of indication refers to potassium felspar sand
.
5. according to a kind of application that utilizes insoluble potassium bearing rock to produce the method for potassium sulfate described in claim 1 or 2, it is characterized in that: with rubidium feldspar and caesium feldspar, replace potassium felspar sand, by above-mentioned technique and processing condition, produce rubidiurn sulfate and cesium sulfate.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864496B (en) * | 2014-02-26 | 2016-03-09 | 化工部长沙设计研究院 | The technique of potash fertilizer prepared by a kind of potassium felspar sand |
| CN103951472B (en) * | 2014-04-16 | 2016-06-15 | 贵州远盛钾业科技有限公司 | A kind of potash fertilizer production unit and the application in silicofluoric acid and potassium bearing rock production potash fertilizer thereof |
| CN104370307B (en) * | 2014-10-23 | 2016-09-21 | 贵州省化工研究院 | A kind of method of potassium-bearing shale comprehensive utilization |
| CN105060350A (en) * | 2015-08-04 | 2015-11-18 | 贵州远盛钾业科技有限公司 | Production method of iron oxide by utilizing potassium-bearing rock |
| CN105439177A (en) * | 2015-11-30 | 2016-03-30 | 洛阳绿仁环保设备有限公司 | Method for preparing lithium carbonate/white carbon black composite material from potassium feldspar |
| CN108610098A (en) * | 2016-12-12 | 2018-10-02 | 贵州远盛钾业科技有限公司 | A kind of production method of water-soluble silicon-potassium fertilizer material |
| CN106631269A (en) * | 2016-12-12 | 2017-05-10 | 贵州远盛钾业科技有限公司 | Method for producing medium element fertilizer at low cost |
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| GB135545A (en) * | ||||
| CN1118333A (en) * | 1994-09-09 | 1996-03-13 | 林延芳 | Process for extracting soluble non-sulfur potassium salt from feldspar |
| CN1062844C (en) * | 1995-05-04 | 2001-03-07 | 贺觉德 | Process for producing potassium sulfate and its by-product using potassium ore |
| CN1078564C (en) * | 1998-11-09 | 2002-01-30 | 裴敬 | Technology of preparing potassium sulfate using leopoldite |
| CN1314628C (en) * | 2004-02-04 | 2007-05-09 | 薛彦辉 | Low temperature decomposition method for potassium feldspar |
| CN101704687B (en) * | 2009-09-28 | 2011-12-21 | 陈锋 | Method for producing potassium sulphate by decomposing potassium feldspar at low temperature |
| CN102491342B (en) * | 2011-11-14 | 2014-07-09 | 贵州瓮福蓝天氟化工股份有限公司 | Method for preparing white carbon black by using fluosilicic acid gas ammonification process |
| CN103172074B (en) * | 2013-01-17 | 2014-11-26 | 洛阳氟钾科技有限公司 | Process for decomposing potassium feldspar by adopting low-temperature semidry method for comprehensive utilization |
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Owner name: GUIZHOU YUANSHENG POTASSIUM TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: TIAN JUAN Effective date: 20140828 Free format text: FORMER OWNER: CHEN WENXING Effective date: 20140828 |
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Inventor after: Tian Juan Inventor after: Chen Wenxing Inventor after: Chen Shili Inventor after: Ren Wei Inventor after: Zhou Changping Inventor after: Jiang Renbo Inventor before: Tian Juan Inventor before: Chen Wenxing Inventor before: Zhou Changping Inventor before: Jiang Renbo |
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