CN103539163A - Technology for preparing potassium sulfate by use of potassium feldspar - Google Patents
Technology for preparing potassium sulfate by use of potassium feldspar Download PDFInfo
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- CN103539163A CN103539163A CN201310527135.9A CN201310527135A CN103539163A CN 103539163 A CN103539163 A CN 103539163A CN 201310527135 A CN201310527135 A CN 201310527135A CN 103539163 A CN103539163 A CN 103539163A
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Abstract
The invention provides a technology for preparing potassium sulfate by use of potassium feldspar, which comprises the following steps: (1) reaction, namely sufficiently mixing potassium feldspar, fluorite, ammonium fluoride and 98% sulfuric acid and then reacting; (2) gas absorption, namely introducing the gas generated by the reaction into a dust removal filter to remove dust, and after dust removal filtration, sequentially introducing the gas into first-level and second-level absorption towers, and absorbing through absorption liquid; (3) leaching of the reaction residue, namely transferring the solid residue into a leaching tank through a discharge helix, and leaching with a dilute sulfuric acid solution; (4) preparation of potassium fluosilicate, namely adding a fluosilicic acid solution into the leaching liquid to prepare potassium fluosilicate powder; and (5) preparation of potassium sulfate, namely feeding the potassium fluosilicate powder and concentrated sulfuric acid into a calcinator, and after reaction, dissolving the residue by use of clear water, filtering and recrystallizing the filtrate to obtain the potassium sulfate product. By adopting the technology provided by the invention, conversion from slightly-soluble sylvite into soluble sylvite is realized, the high-purity potassium sulfate is prepared, and the problem of insufficient soluble potassium resource in China is solved.
Description
Technical field
The present invention relates to potassium felspar sand Decomposition-Synthesis and utilize technology, be specifically related to a kind of technique of utilizing potassium felspar sand preparing potassium sulfate.
Background technology
Using fertilizer is step indispensable in modern agricultural production, and in existing fertilizer, potassium nutrition element has occupied very important position.China Shi Ge large agricultural country, because China's soluble potassium resource is extremely poor, is difficult to meet domestic needs, and China's proportion of N and K fertilizer on agricultural fertilizer is seriously lacked of proper care.But China's insoluble potassium resource is a lot, especially potash feldspar ore reserves are extremely abundant, mainly be distributed in 19 provinces and regions such as Yunnan, Guizhou, Sichuan, Hunan, Hubei, Henan, Anhui, Jiangxi, Shandong and Xinjiang, therefore, how utilizing potassium felspar sand to manufacture potash fertilizer is problem demanding prompt solution.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, thereby the technique of utilizing potassium felspar sand preparing potassium sulfate is provided.
To achieve these goals, the technical solution adopted in the present invention is: utilize the technique of potassium felspar sand preparing potassium sulfate, comprise the following steps:
(1) reaction: after potassium felspar sand, fluorite, Neutral ammonium fluoride, the vitriol oil are fully mixed, join in converter reactor, react under 180～250 ℃ and autogenous pressure, reaction principle is:
CaF
2?+?H
2SO
4?=?2HF?+?CaSO
4
2K[AlSi
3O
8]?+?24HF?+?4H
2SO
4?=?K
2SO
4?+?Al
2(SO
4)
3?+?6SiF
4↑+?16H
2O
Wherein, the sulfuric acid that the vitriol oil is 98%, potassium felspar sand, fluorite, Neutral ammonium fluoride, 98% sulfuric acid mass ratio are 1:0.3～0.5:1.12～1.73:1.6～1.8;
(2) gas absorption: the gas that reaction is produced is introduced dedusting in dust removal filter, after dust removal and filtration, pass into successively in I and II absorption tower and by absorption liquid and absorb, generate white precipitate and silicate fluoride solution, through centrifugation, washing and dryly make white carbon black product, gained filtrate is silicate fluoride solution; The aqueous ethanolic solution that wherein absorption liquid is 10～30%; Reaction principle is: 3SiF
4+ 2H
2o=2H
2siF
6+ SiO
2↓;
(3) leaching of reaction residues: reacted solid residue in described converter reactor is proceeded to leaching groove by discharging spiral, at 90～110 ℃, the dilution heat of sulfuric acid that is 8～10% by volume fraction leaching, then filters and obtains leaching liquid the solution after leaching;
(4) preparation of potassium silicofluoride: leaching liquid is got in potassium silicofluoride reactor and regulated temperature at 55～65 ℃ through pump, according to stoichiometric relation, add the silicate fluoride solution making in step (2) to generate potassium silicofluoride precipitation, silicofluoric acid excessive 20～100%, through ageing, then through Filter Press, washing the dry potassium silicofluoride powder that makes;
(5) preparation of vitriolate of tartar: the potassium silicofluoride powder making in step (4) and the vitriol oil are dropped in calcining furnace, potassium silicofluoride and sulfuric acid mole ratio be 1:1.05～1.1, at 150～300 ℃, react 0.5～1h, the gas producing passes into successively I and II absorption tower and absorbs, after reaction, the main component of residue is vitriolate of tartar and contains a small amount of silicon-dioxide, with clear water, residue is dissolved, then filter and filtrate recrystallization is obtained to potassium product.
Based on above-mentioned, in step (2), it is that circulation absorption process object is the concentration that improves constantly silicate fluoride solution that gas leads to the process absorbing in I and II absorption tower successively.
Based on above-mentioned, with the solids manufacture aerated bricks filtering out in step (3).
The present invention utilizes the technique of potassium felspar sand preparing potassium sulfate, compared with prior art has advantages of following main:
1. the present invention adopts the technique of low temperature semidrying decomposing of potassium feldspar, and temperature of reaction, at 180～250 ℃, is compared with pyroprocess decomposing of potassium feldspar, and reaction conditions is gentle, lower to the requirement of equipment.
2. the present invention is directed to the problem that potassium element that potassium felspar sand contains belongs to insoluble potassium resource, the fluorine-containing auxiliary agent low-temperature decomposing of potassium feldspar of a kind of use is proposed, by dissolving and adding the method for silicate fluoride solution that sylvite is extracted separately, further reaction at 150～300 ℃, passing into afterwards the vitriol oil makes vitriolate of tartar and makes solid sulphuric acid potassium by crystallization, realized the transformation of insoluble sylvite to soluble potassium salt, prepared highly purified vitriolate of tartar, a kind of new approaches are provided, have solved the problem of China's soluble potassium inadequate resource.Production process produces without the three wastes, and energy consumption is low, output is high, the rate of recovery is high, has realized production serialization, and the effective constituent of potassium felspar sand is also fully utilized.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that the present invention utilizes potassium felspar sand preparing potassium sulfate.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Utilize the embodiment of the technique of potassium felspar sand preparing potassium sulfate
Embodiment 1
As shown in Figure 1, comprise the following steps:
(1) reaction: after potassium felspar sand, fluorite, Neutral ammonium fluoride, 98% sulfuric acid are fully mixed, join in converter reactor, react under 180～250 ℃ and autogenous pressure; Reaction principle is:
CaF
2?+?H
2SO
4?=?2HF?+?CaSO
4
2K[AlSi
3O
8]?+?24HF?+?4H
2SO
4?=?K
2SO
4?+?Al
2(SO
4)
3?+?6SiF
4↑+?16H
2O
Wherein, potassium felspar sand, fluorite, Neutral ammonium fluoride, 98% sulfuric acid mass ratio are 1:0.3～0.5:1.12～1.73:1.6～1.8;
(2) gas absorption: the gas that reaction is produced is introduced dedusting in dust removal filter, after dust removal and filtration, pass into successively in I and II absorption tower and by absorption liquid and absorb, generate white precipitate and silicate fluoride solution, through centrifugation, washing and dryly make white carbon black product, gained filtrate is silicate fluoride solution; The aqueous ethanolic solution that wherein absorption liquid is 10～30%; Reaction principle is: 3SiF
4+ 2H
2o=2H
2siF
6+ SiO
2↓;
(3) leaching of reaction residues: reacted solid residue in described converter reactor is proceeded to leaching groove by discharging spiral, and at 100 ℃, the dilution heat of sulfuric acid that is 10% by volume fraction leaching, then filters and obtain leaching liquid the solution after leaching;
(4) preparation of potassium silicofluoride: leaching liquid is got in potassium silicofluoride reactor and regulated temperature at 60 ℃ through pump, according to stoichiometric relation, add the silicate fluoride solution making in step (2) to generate potassium silicofluoride precipitation, silicofluoric acid excessive 20～100%, through ageing, then through Filter Press, washing the dry potassium silicofluoride powder that makes;
(5) preparation of vitriolate of tartar: the potassium silicofluoride powder making in step (4) and the vitriol oil are dropped in calcining furnace, potassium silicofluoride and sulfuric acid mole ratio be 1:1.1, at 150～300 ℃, react 0.5～1h, the gas producing passes into successively I and II absorption tower and absorbs, after reaction, the main component of residue is vitriolate of tartar and contains a small amount of silicon-dioxide, with clear water, residue is dissolved, then filter and filtrate recrystallization is obtained to potassium product.
The present invention utilizes the technique of the process using low temperature semidrying decomposing of potassium feldspar of potassium felspar sand preparing potassium sulfate, compares with pyroprocess decomposing of potassium feldspar, and reaction conditions is gentle, lower to the requirement of equipment; The potassium element that potassium felspar sand is contained belongs to the problem of insoluble potassium resource, the fluorine-containing auxiliary agent low-temperature decomposing of potassium feldspar of a kind of use is proposed, by dissolving and adding the method for silicate fluoride solution that sylvite is extracted separately, further reaction at 150～300 ℃, passing into afterwards dilute sulphuric acid makes vitriolate of tartar and makes solid sulphuric acid potassium by crystallization, realized the transformation of insoluble sylvite to soluble potassium salt, prepared highly purified vitriolate of tartar, a kind of new approaches are provided, have solved the problem of China's soluble potassium inadequate resource.Production process produces without the three wastes, and energy consumption is low, output is high, the rate of recovery is high, has realized production serialization, and the effective constituent of potassium felspar sand is also fully utilized.
Embodiment 2
As different from Example 1, in step (2), it is that circulation absorption process object is the concentration that improves constantly silicate fluoride solution that gas leads to the process absorbing in I and II absorption tower successively.
Embodiment 3
Different from above-described embodiment, with the solids manufacture aerated bricks filtering out in step (3).
In other embodiments of the invention, different from above-described embodiment is, in step (1), (1) temperature of reaction can be chosen 180 ℃, 200 ℃ or 250 ℃ as required, potassium felspar sand, fluorite, Neutral ammonium fluoride, 98% sulfuric acid mass ratio can be chosen for 1:0.3:1.12:1.6,1:0.4:1.4:1.7 or 1:0.5:1.73:1.8 as required; In step (2), absorption liquid can be chosen 10% aqueous ethanolic solution as required, 20% aqueous ethanolic solution or 30% aqueous ethanolic solution; In step (3), temperature can also be as required at 90 ℃ or 110 ℃ etc., the volume fraction of dilution heat of sulfuric acid can also choose 8% or 9% etc. as required, in step (4), can adjust the temperature to as required 55 ℃ or 65 ℃ etc., silicofluoric acid can be as required excessive 20%, 50% even 100%; In step 5, temperature of reaction can be 150 ℃, 250 ℃ or 300 ℃, and the reaction times can be selected 0.50 h, 7 h or 1h, potassium silicofluoride and sulfuric acid mole ratio can choose as required 1:1.05 or 1:1.08 etc.
Finally should be noted that: above embodiment is only in order to illustrate that technical scheme of the present invention is not intended to limit; Although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the field are to be understood that: still can modify or part technical characterictic is equal to replacement the specific embodiment of the present invention; And not departing from the spirit of technical solution of the present invention, it all should be encompassed in the middle of the technical scheme scope that the present invention asks for protection.
Claims (3)
1. utilize the technique of potassium felspar sand preparing potassium sulfate, it is characterized in that comprising the following steps:
(1) reaction: after potassium felspar sand, fluorite, Neutral ammonium fluoride, 98% sulfuric acid are fully mixed, join in converter reactor, react under 180～250 ℃ and autogenous pressure, reaction principle is:
CaF
2?+?H
2SO
4?=?2HF?+?CaSO
4
2K[AlSi
3O
8]?+?24HF?+?4H
2SO
4?=?K
2SO
4?+?Al
2(SO
4)
3?+?6SiF
4↑+?16H
2O
Wherein, potassium felspar sand, fluorite, Neutral ammonium fluoride, 98% sulfuric acid mass ratio are 1:0.3～0.5:1.12～1.73:1.6～1.8;
(2) gas absorption: the gas that reaction is produced is introduced dedusting in dust removal filter, after dust removal and filtration, pass into successively in I and II absorption tower and by absorption liquid and absorb, generate white precipitate and silicate fluoride solution, through centrifugation, washing and dryly make white carbon black product, gained filtrate is silicate fluoride solution; The aqueous ethanolic solution that wherein absorption liquid is 10～30%; Reaction principle is: 3SiF
4+ 2H
2o=2H
2siF
6+ SiO
2↓;
(3) leaching of reaction residues: reacted solid residue in described converter reactor is proceeded to leaching groove by discharging spiral, at 90～110 ℃, the dilution heat of sulfuric acid that is 8～10% by volume fraction leaching, then filters and obtains leaching liquid the solution after leaching;
(4) preparation of potassium silicofluoride: leaching liquid is got in potassium silicofluoride reactor and regulated temperature at 55～65 ℃ through pump, according to stoichiometric relation, add the silicate fluoride solution making in step (2) to generate potassium silicofluoride precipitation, silicofluoric acid excessive 20～100%, through ageing, then through Filter Press, washing the dry potassium silicofluoride powder that makes;
(5) preparation of vitriolate of tartar: the potassium silicofluoride powder making in step (4) and the vitriol oil are dropped in calcining furnace, potassium silicofluoride and sulfuric acid mole ratio be 1:1.05～1.1, at 150～300 ℃, react 0.5～1h, the gas producing passes into successively I and II absorption tower and absorbs, after reaction, the main component of residue is vitriolate of tartar and contains a small amount of silicon-dioxide, with clear water, residue is dissolved, then filter and filtrate recrystallization is obtained to potassium product.
2. the technique of utilizing potassium felspar sand preparing potassium sulfate according to claim 1, it is characterized in that: in step (2), it is that circulation absorption process object is the concentration that improves constantly silicate fluoride solution that gas leads to the process absorbing in I and II absorption tower successively.
3. the technique of utilizing potassium felspar sand preparing potassium sulfate according to claim 1 and 2, is characterized in that: with the solids manufacture aerated bricks filtering out in step (3).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439160A (en) * | 2015-11-29 | 2016-03-30 | 洛阳绿仁环保设备有限公司 | Method for preparing potassium silicate from potassium feldspar |
| CN105439167A (en) * | 2015-11-29 | 2016-03-30 | 洛阳绿仁环保设备有限公司 | Method for preparing 3A molecular sieve from potassium feldspar |
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| CN1118333A (en) * | 1994-09-09 | 1996-03-13 | 林延芳 | Process for extracting soluble non-sulfur potassium salt from feldspar |
| CN1146982A (en) * | 1995-05-04 | 1997-04-09 | 贺觉德 | Process for producing potassium sulfate and its by-product using potassium ore |
| CN1259487A (en) * | 1998-11-09 | 2000-07-12 | 裴敬 | Technology of preparing potassium sulfate using leopoldite |
| CN101704687A (en) * | 2009-09-28 | 2010-05-12 | 陈锋 | Method for producing potassium sulphate by decomposing potassium feldspar at low temperature |
| CN103172074A (en) * | 2013-01-17 | 2013-06-26 | 洛阳氟钾科技有限公司 | Process for decomposing potassium feldspar by adopting low-temperature semidry method for comprehensive utilization |
-
2013
- 2013-10-31 CN CN201310527135.9A patent/CN103539163B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB135545A (en) * | ||||
| CN1118333A (en) * | 1994-09-09 | 1996-03-13 | 林延芳 | Process for extracting soluble non-sulfur potassium salt from feldspar |
| CN1146982A (en) * | 1995-05-04 | 1997-04-09 | 贺觉德 | Process for producing potassium sulfate and its by-product using potassium ore |
| CN1259487A (en) * | 1998-11-09 | 2000-07-12 | 裴敬 | Technology of preparing potassium sulfate using leopoldite |
| CN101704687A (en) * | 2009-09-28 | 2010-05-12 | 陈锋 | Method for producing potassium sulphate by decomposing potassium feldspar at low temperature |
| CN103172074A (en) * | 2013-01-17 | 2013-06-26 | 洛阳氟钾科技有限公司 | Process for decomposing potassium feldspar by adopting low-temperature semidry method for comprehensive utilization |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439160A (en) * | 2015-11-29 | 2016-03-30 | 洛阳绿仁环保设备有限公司 | Method for preparing potassium silicate from potassium feldspar |
| CN105439167A (en) * | 2015-11-29 | 2016-03-30 | 洛阳绿仁环保设备有限公司 | Method for preparing 3A molecular sieve from potassium feldspar |
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Address after: 471400, Luoyang, Henan, Songxian province township industrial agglomeration area Luoyang potassium fluoride technology joint-stock company Applicant after: LUOYANG POTASSIUM FLUORIDE TECHNOLOGY CO.,LTD. Address before: 471400, Henan, Luoyang province Songxian meal slope Township Industrial Agglomeration Applicant before: Luoyang Fluorine and Potassium Technology Co.,Ltd. Address after: 471400, Henan, Luoyang province Songxian meal slope Township Industrial Agglomeration Applicant after: Luoyang Fluorine and Potassium Technology Co.,Ltd. Address before: 471400, Luoyang, Songxian, Henan province Township Po Industrial Agglomeration Area Luoyang fluorine potassium Technology Co., Ltd. Applicant before: Luoyang Fluoride & Potassium Technology Co.,Ltd. |
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