CN102001683A - Process for producing potassium hydroxide by using fluorhydric acid to decompose potash feldspar at low temperature - Google Patents
Process for producing potassium hydroxide by using fluorhydric acid to decompose potash feldspar at low temperature Download PDFInfo
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Abstract
The invention discloses a process for producing potassium hydroxide by using fluorhydric acid to decompose potash feldspar at low temperature, which comprises the steps of: decomposing potash feldspar powder by using fluorhydric acid, wherein the acid material ratio is 1-5:1, the reaction time is 1-6h, and generated SiF4 gas is circularly absorbed by using water in a three-level absorption tower to obtain recycling H2SiF6 and white carbon black products; reacting slurry, and separating to obtain liquid, syrup matter and solid matters; carrying out secondary decomposition and separation on the liquid and the solid matters in an agitated reactor, decomposing the potash feldspar to finally obtain acidic liquid, syrup matters and solid matters, purifying and separating the solid matters through the fluorhydric acid to prepare a potassium fluosilicate product; recycling the acid liquid to the decomposition reaction of the potash feldspar; and after carrying out full alkaline hydrolysis reaction on K2SiF6 with KOH under the heating condition, separating to obtain a KF solution and SiO2.nH2O, after the KF solution reacts with Ca(OH)2, separating to obtain a KOH solution and a CaF2 solid, evaporating and condensing the KOH solution, and dewatering to prepare the potassium hydroxide product. The process has no three-waste during the production, and solves the technical problems of high energy consumption, low yield, low recycling rate and the like of the prior art.
Description
Technical field the invention belongs to potassium felspar sand evaluation and exploration technology field, relates to a kind of potassium felspar sand of realizing and decomposes, transforms the technology of separating the potassium composition, is specifically related to a kind of technology of utilizing the fluoric-containing acid low-temperature decomposing of potassium feldspar to produce potassium hydroxide.
The background technology potassium felspar sand is the ore that contains compositions such as potassium, aluminium, silicon with rock steady structure that nature extensively exists, the research and development history that last 100 years is abroad arranged, domestic have nearly 50 years research and development, but all be not formed with the complete skill of actual application value.Existing potassium felspar sand decompose extract that there is the energy consumption height in potassium composition technology, the potassium yield is low, utilization rate of raw materials is low, pollution is heavy, can not large-scale production etc. technical problem; the breakthrough of this technical field; can open up a production new way that contains the potassium product, promote the autonomous production capacity of China's sylvite product.Contain silicofluoric acid (H
2SiF
6), the mixing acid formed with any mol ratio of hydrofluoric acid (HF) or the two, promptly be called fluoric-containing acid, China's soluble potassium natural resources shortage, the serious dependence on import of sylvite product at present, utilizing the fluoric-containing acid low-temperature decomposing of potassium feldspar to produce potassium hydroxide is the task of top priority.
Summary of the invention the objective of the invention is to solve prior art and has technical problems such as energy consumption height, output is low, the rate of recovery is low, provides a kind of technology of utilizing the fluoric-containing acid low-temperature decomposing of potassium feldspar to produce potassium hydroxide, to overcome the deficiencies in the prior art.
To achieve these goals, a kind of technology of utilizing the fluoric-containing acid low-temperature decomposing of potassium feldspar to produce potassium hydroxide of the present invention, its processing step is as follows:
1), batching: 150～250 purpose feldspars in powder and mass concentration are 15～30% fluoric-containing acid, prepare burden in mixing tank for coating colors by 1: 1～5 mass ratio, stir;
2), decomposition and separation: batching is joined in the reactor, stir, heat up, keep temperature in the kettle, insulation reaction 1～3 hour, the silicon tetrafluoride (SiF that reaction is produced at 60～100 ℃
4) gas introduces the three grades of water cycles in absorption tower through induced draft fan and absorb, and improves constantly the silicate fluoride solution that concentration obtains recycle, and generates slurry and white precipitate, white precipitate makes the white carbon black final product through centrifugation, washing, drying, and reaction principle is as follows:
H
2SiF
6→2HF+SiF
4↑
SiO
2+6HF→H
2SiF
6+2H
2O
3SiF
4+2H
2O→2H
2SiF
6+SiO
2↓
Slurry takes out in the reactor and separates, isolate liquid, soup compound and solid substance, liquid and solid substance return reactor and proceed decomposition reaction, when reaction was carried out 3～6 hours, the fluoric-containing acid mass concentration drops at 5～8% o'clock in the still, termination reaction, through separate acidic liquid, soup compound and solid substance, the gained acidic liquid is back to use in the decomposition reaction of potassium felspar sand after adding fluoric-containing acid adjustment concentration, gained soup compound individual curing, the gained solid substance changes purification process over to, and the conversion reaction principle of potassium is as follows:
K
2O+H
2SiF
6→K
2SiF
6↓+H
2O
3), purify: be 15～30% fluoric-containing acid with solid substance and mass concentration, mass ratio by 1: 2～3 mixes stirring in reactor, 20～40 ℃ were reacted 1 hour, remove the silicon-dioxide white precipitate, make mass content after the separation and be 95～96% potassium silicofluoride product, separating obtained liquid is back to use the decomposition reaction of potassium felspar sand, and reaction principle is:
SiO
2+6HF→H
2SiF
6+2H
2O
4), alkaline hydrolysis: the potassium silicofluoride that makes is dropped in the reactor, under the condition that stirs, heats, slowly add KOH and carry out alkaline hydrolysis, KOH add-on and K
2SiF
6Mol ratio be 4.1～4.2: 1, temperature is controlled at 60～100 ℃, alkaline hydrolysis 1～2 hour, the pH value of end reaction liquid is controlled at 6～9, termination reaction, centrifugation, the gained solid makes the white carbon black product through washing, drying, and washings and centrifugal gained liquid carry out K once more as mother liquor
2SiF
6Alkaline hydrolysis, to improve the concentration of KF solution as far as possible, contain KF in the mother liquor, its reaction principle is:
K
2SiF
6+4KOH→6KF+SiO
2↓+2H
2O
5), add the calcium reaction: after KF liquid mass concentration reaches 30～40%, under agitation condition, slowly drip excessive Ca (OH)
2Slurries fully reacted 1～2 hour, centrifugation, gained CaF
2Solid is used to prepare potassium felspar sand and decomposes required hydrofluoric acid through washing drying, and washings is used for Ca (OH)
2The preparation of slurries, centrifugal gained potassium hydroxide solution partly is back to use the K of step 4
2SiF
6The alkaline hydrolysis process, part makes the potassium hydroxide product through evaporation concentration, dehydration.Reaction principle is as follows:
2KF+Ca(OH)
2→CaF
2↓+2KOH
Described fluoric-containing acid is silicofluoric acid (H
2SiF
6), the mixing acid formed with any mol ratio of hydrofluoric acid (HF) or the two.
Whole process of production of the present invention does not have waste gas, waste residue, waste water generation, raw material cyclic utilization rate height, realize the comprehensive development and utilization of potassium felspar sand, obtained white carbon black byproduct and potassium hydroxide product, solved prior art and had technical problems such as energy consumption height, output is low, the rate of recovery is low.
Embodiment the present invention utilizes the fluoric-containing acid low-temperature decomposing of potassium feldspar to produce the technology of potassium hydroxide, and specific embodiment is as follows:
Embodiment 1:
1), batching: 200 purpose feldspars in powder and mass concentration are 30% silicofluoric acid, prepare burden in mixing tank for coating colors by 1: 4 mass ratio, stir;
2), decomposition and separation: batching is joined in the reactor, stir, heat up, keep temperature in the kettle at 60 ℃, insulation reaction 1 hour, the silicon tetrafluoride gas that reaction is produced is introduced the three grades of water cycles in absorption tower through induced draft fan and is absorbed, improve constantly concentration and obtain the silicate fluoride solution of recycle, and generation slurry and white precipitate, white precipitate is through centrifugation, washing, drying makes the white carbon black final product, slurry takes out in the reactor and separates, isolate liquid, soup compound and solid substance, liquid and solid substance return reactor and proceed decomposition reaction, when reaction was carried out 3 hours, the fluoric-containing acid mass concentration drops at 5% o'clock, termination reaction in the still, through separate acidic liquid, soup compound and solid substance, the gained acidic liquid is back to use in the decomposition reaction of potassium felspar sand after adding fluoric-containing acid adjustment concentration, gained soup compound individual curing, and the gained solid substance changes purification process over to;
3), purify: be 30% silicofluoric acid with solid substance and mass concentration, mass ratio by 1: 3 mixes stirring in reactor, 20 ℃ were reacted 1 hour, remove the silicon-dioxide white precipitate, make mass content after the separation and be 96% potassium silicofluoride product, separating obtained liquid is back to use the decomposition reaction of potassium felspar sand;
4), alkaline hydrolysis: the potassium silicofluoride that makes is dropped in the reactor, under the condition that stirs, heats, slowly add KOH and carry out alkaline hydrolysis, KOH add-on and K
2SiF
6Mol ratio be 4.1: 1, temperature is controlled at 60 ℃, alkaline hydrolysis 1 hour, the pH value of end reaction liquid is controlled at 7, termination reaction, centrifugation, the gained solid is SiO
2.nH
2O makes the white carbon black product through washing, drying, and washings and centrifugal gained liquid are that KF solution carries out K once more as mother liquor
2SiF
6Alkaline hydrolysis, to improve the concentration of KF solution as far as possible, contain KF in the mother liquor;
5), add calcium: after KF liquid mass concentration reaches 40%, under agitation condition, slowly drip excessive Ca (OH)
2Slurries fully reacted 1 hour, centrifugation, gained CaF
2Solid is used to prepare potassium felspar sand and decomposes required hydrofluoric acid through washing drying, and washings is used for Ca (OH)
2The preparation of slurries, centrifugal gained potassium hydroxide solution partly is back to use the K of step 4
2SiF
6The alkaline hydrolysis process, part makes the potassium hydroxide product through evaporation concentration, dehydration.
Embodiment 2: according to embodiment 1, with hydrofluoric acid (HF) replacement fluorine silicic acid (H
2SiF
6).
Embodiment 3: according to embodiment 1, with silicofluoric acid (H
2SiF
6) and hydrofluoric acid (HF) form mixing acid, replacement fluorine silicic acid (H by 1: 2 mol ratio
2SiF
6).
Embodiment 4: according to embodiment 1, with silicofluoric acid (H
2SiF
6) and hydrofluoric acid (HF) form mixing acid, replacement fluorine silicic acid (H by 5: 5 mol ratio
2SiF
6).
Claims (1)
1. technology of utilizing the fluoric-containing acid low-temperature decomposing of potassium feldspar to produce potassium hydroxide is characterized in that processing step is as follows:
1), batching: 150～250 purpose feldspars in powder and mass concentration are 15～30% fluoric-containing acid, prepare burden in mixing tank for coating colors by 1: 1～5 mass ratio, stir;
2), decomposition and separation: batching is joined in the reactor, stir, heat up, keep temperature in the kettle at 60～100 ℃, insulation reaction 1～3 hour, the silicon tetrafluoride gas that reaction is produced is introduced the three grades of water cycles in absorption tower through induced draft fan and is absorbed, improve constantly concentration and obtain the silicate fluoride solution of recycle, and generation slurry and white precipitate, white precipitate is through centrifugation, washing, drying makes the white carbon black final product, slurry takes out in the reactor and separates, isolate liquid, soup compound and solid substance, liquid and solid substance return reactor and proceed decomposition reaction, when reaction was carried out 3～6 hours, the fluoric-containing acid mass concentration drops at 5～8% o'clock, termination reaction in the still, through separate acidic liquid, soup compound and solid substance, the gained acidic liquid is back to use in the decomposition reaction of potassium felspar sand after adding fluoric-containing acid adjustment concentration, gained soup compound individual curing, and the gained solid substance changes purification process over to;
3), purify: be 15～30% fluoric-containing acid with solid substance and mass concentration, mass ratio by 1: 2～3 mixes stirring in reactor, 20～40 ℃ were reacted 1 hour, remove the silicon-dioxide white precipitate, make mass content after the separation and be 95～96% potassium silicofluoride product, separating obtained liquid is back to use the decomposition reaction of potassium felspar sand;
4), alkaline hydrolysis: the potassium silicofluoride that makes is dropped in the reactor, under the condition that stirs, heats, slowly add KOH and carry out alkaline hydrolysis, KOH add-on and K
2SiF
6Mol ratio be 4.1～4.2: 1, temperature is controlled at 60～100 ℃, alkaline hydrolysis 1～2 hour, the pH value of end reaction liquid is controlled at 6～9, termination reaction, centrifugation, the gained solid makes the white carbon black product through washing, drying, and washings and centrifugal gained liquid carry out K once more as mother liquor
2SiF
6Alkaline hydrolysis;
5), add the calcium reaction: after KF liquid mass concentration reaches 30～40%, under agitation condition, slowly drip excessive Ca (OH)
2Slurries fully reacted 1～2 hour, centrifugation, gained CaF
2Solid is used to prepare potassium felspar sand and decomposes required hydrofluoric acid through washing drying, and washings is used for Ca (OH)
2The preparation of slurries, centrifugal gained potassium hydroxide solution partly is back to use the K of step 4
2SiF
6The alkaline hydrolysis process, part makes the potassium hydroxide product through evaporation concentration, dehydration.
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|---|---|---|---|
| CN2010105863038A CN102001683B (en) | 2010-12-01 | 2010-12-01 | Process for producing potassium hydroxide by using fluorhydric acid to decompose potash feldspar at low temperature |
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|---|---|---|---|
| CN2010105863038A CN102001683B (en) | 2010-12-01 | 2010-12-01 | Process for producing potassium hydroxide by using fluorhydric acid to decompose potash feldspar at low temperature |
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| CN102001683A true CN102001683A (en) | 2011-04-06 |
| CN102001683B CN102001683B (en) | 2012-07-18 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4268492A (en) * | 1979-08-06 | 1981-05-19 | Pennzoil Company | Process for production of potassium sulfate and hydrochloric acid |
| CN1138567A (en) * | 1996-03-19 | 1996-12-25 | 化学工业部长沙化学矿山设计研究院 | Wetting decomposition process of potash feldspar ore |
| CN101559959A (en) * | 2009-05-23 | 2009-10-21 | 陈锋 | Process for producing potassium sulfate and ammonia sulfate by wet decomposing potassium feldspar |
| CN101704687A (en) * | 2009-09-28 | 2010-05-12 | 陈锋 | Method for producing potassium sulphate by decomposing potassium feldspar at low temperature |
-
2010
- 2010-12-01 CN CN2010105863038A patent/CN102001683B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4268492A (en) * | 1979-08-06 | 1981-05-19 | Pennzoil Company | Process for production of potassium sulfate and hydrochloric acid |
| CN1138567A (en) * | 1996-03-19 | 1996-12-25 | 化学工业部长沙化学矿山设计研究院 | Wetting decomposition process of potash feldspar ore |
| CN101559959A (en) * | 2009-05-23 | 2009-10-21 | 陈锋 | Process for producing potassium sulfate and ammonia sulfate by wet decomposing potassium feldspar |
| CN101704687A (en) * | 2009-09-28 | 2010-05-12 | 陈锋 | Method for producing potassium sulphate by decomposing potassium feldspar at low temperature |
Non-Patent Citations (1)
| Title |
|---|
| 《化肥工业》 20061231 陈定盛等 焙烧钾长石制硫酸钾的实验研究 20-23 1 第33卷, 第6期 2 * |
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