CN108946689A - A kind of production method of potassium dihydrogen phosphate - Google Patents
A kind of production method of potassium dihydrogen phosphate Download PDFInfo
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- CN108946689A CN108946689A CN201710391249.3A CN201710391249A CN108946689A CN 108946689 A CN108946689 A CN 108946689A CN 201710391249 A CN201710391249 A CN 201710391249A CN 108946689 A CN108946689 A CN 108946689A
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- acid
- phosphate
- filtrate
- potassium
- hydrochloric acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/10—Compounds containing silicon, fluorine, and other elements
- C01B33/103—Fluosilicic acid; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a kind of methods for preparing potassium dihydrogen phosphate with decomposing phosphate rock by chlorhydric acid.This method step are as follows: the first step, with hydrochloric acid and Decomposition of ammonium sulfate phosphorus ore；Second step carries out defluorinate to the filtrate in the first step with defluorinating agent, obtains fluosilicate and defluorinate filtrate；Third step neutralizes defluorinate filtrate, obtains calcium monohydrogen phosphate；4th step is reacted with the mixed solution and calcium monohydrogen phosphate of sulfuric acid and potassium acid sulfate；5th step neutralizes the filtered fluid in the 4th step with lime white；6th step obtains finished product to filtered fluid concentration, crystallization, the separation in the 5th step；Liquid part return system is evaporated to decompose for calcium monohydrogen phosphate.Process of the present invention is clear and easily controllable, product cost improves the utilization efficiency of by-product hydrochloric acid, phosphorus ore, and the product for the environment that is safe from harm much smaller than the present cost for using thermal phosphoric acid preparing potassium dihydrogen phosphate, production environment is friendly, there is good economic benefit and social benefit.
Description
Technical field
The present invention relates to a kind of production methods of potassium dihydrogen phosphate, belong to inorganic chemical production technical field.
Background technique
Potassium dihydrogen phosphate is important inorganic compound, is widely used in modern chemical industry, medicine, food, papermaking, detergent
Etc. industries；It is called " chemical fertilizer precise " in farming and animal husbandry, is a kind of excellent fertilizer of efficient rapid available phosphorus, potassium for water-saving agriculture；?
It is used as buffer and casate in Chemical Manufacture；The conventional production methods of potassium dihydrogen phosphate are with potassium hydroxide and thermal method
Phosphatase reaction, but this method higher cost.
Chinese patent literature CN1412107A(application number: CN01128971.6) disclose a kind of potassium dihydrogen phosphate that produces
Preparation method, this method be with potassium acid sulfate and sulfuric acid mixed solution directly and phosphorus ore reaction, then with separating methanol phosphoric acid with
Potassium dihydrogen phosphate, but this method during can generate potassium fluosilicate, utilization rate of raw materials is not high, the later period with separating methanol cost compared with
Height, obtained potassium dihydrogen phosphate impurity are more；Chinese patent literature CN105480959A(application number: CN201210046088.X)
A kind of method with fluoride salt method of purification production potassium dihydrogen phosphate is disclosed, this method is to use ammonia with after fluoride salt purifying phosphoric acid
After neutralising phosphoric acid and potassium chloride is by metathesis reaction preparing potassium dihydrogen phosphate and ammonium chloride, phosphoric acid purification need to be concentrated, technique
Process is more difficult to control.
The metal ion of phosphorus ore is an important factor for influencing potassium dihydrogen phosphate quality.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of production method of potassium dihydrogen phosphate.
Technical scheme is as follows.
A kind of production method of potassium dihydrogen phosphate, the method steps are as follows.
(1) phosphate ore pulp and ammonium sulfate, the hydrochloric acid that mass concentration is 15 ~ 30% for being 0 ~ 30% by water content, 60 ~ 90 DEG C of reactions
1.5 ~ 4h filters ardealite, obtain comprising hydrochloric acid, phosphoric acid, ammonium chloride, monoammonium phosphate, calcium chloride mixed solution, in filtrate
CaO and P2O5Molar ratio is 1.5 ~ 2.3:1.
(2) mixed solution in step (1) is taken, defluorinating agent, 30 ~ 60 DEG C of 1 ~ 2h of reaction is added, filtering obtains defluorinate filtrate
And fluosilicate.
(3) with the defluorinate filtrate in ammonia neutralization procedure (2), ph value 5 ~ 8 is adjusted, is filtered, washed, obtains filter cake and ammonium chloride
Solution；Filter cake and water are configured to slurry: mass concentration is 20 ~ 40%, and ammonium chloride solution concentration, crystallization, isolated ammonium chloride are brilliant
Body.
Potassium chloride and excess sulfuric acid reaction, obtain the mixed solution of sulfuric acid and potassium acid sulfate: potassium acid sulfate mass content is
30% ~ 65%, it is mixed with the filter cake slurry in step (3), reaction temperature is 70 ~ 90 DEG C, the reaction time is 2.5 ~ 4.5h, crosses and filters out
Ardealite obtains the mixed solution of phosphoric acid and potassium dihydrogen phosphate.
With the mixed solution in lime white neutralization procedure (4), adjusting ph value is 5 ~ 8, and calcium monohydrogen phosphate and phosphoric acid is obtained by filtration
Potassium dihydrogen filtrate.
By filtrate concentration, the crystallization in process (5), crystallization is filtered, washed, obtains potassium dihydrogen phosphate crystal after dry.
It is preferred according to the present invention, phosphate ore pulp in the step (1), hydrochloric acid, ammonium sulfate hybrid mode be phosphorus ore and sulphur
Sour ammonium is co-grinded into after mixed ore pulp and hydrochloric acid reaction.
Preferred according to the present invention, CaO the and P2O5 molar ratio of filtrate is 1.5 ~ 2.3:1 in the step (1).
Preferred according to the present invention, the defluorinating agent in the step (2) is sodium chloride and silica mixture.
It is preferred according to the present invention, it is 5 ~ 8 after slurry ph value adjusts in the step (3)；Mode of washing is classification washing 3
~ 4 times, particularly preferred mode of washing is to be washed 3 ~ 4 times with higher than 80 DEG C of clear water.
Preferred according to the present invention, the content of chloride ion is less than in the nitration mixture of potassium acid sulfate and sulfuric acid in the step (4)
0.15%；
Preferred according to the present invention, mode of washing is classification washing 3 ~ 4 times in the step (4), and particularly preferred mode of washing is
It is washed 3 ~ 4 times with 80 DEG C of clear water are higher than.
It is preferred according to the present invention, it is 5 ~ 8 after slurry ph value adjusts in the step (5).
It is preferred according to the present invention, when potassium dihydrogen phosphate is second-rate in the step (6), it need to be recrystallized.
Filtrate in step (3) return step (1) before unsaturation prepares phosphorus ore slurry；Washing lotion conduct in step (4)
Acid reflux return step (3)；Filtrate in step (6) is used as other purposes such as fertilizer production, no longer returns when foreign ion is excessive
Step (4) are gone back to use.
Reaction equation of the present invention are as follows:
Ca5F(PO4)3+10HCl=5CaCl2+3H3PO4+HF↑
6HF+SiO2=H2SiF6+2H2O
H2SiF6+2NaCl=Na2SiF6↓+2HCl
CaCl2+H3PO4+2NH3=CaHPO4↓+NH4Cl
H2SO4+KCl=KHSO4+HCl
2CaHPO4+H2SO4+KHSO4=2CaSO4↓+H3PO4+KH2PO4
Ca(OH)2+H3PO4=CaHPO4•2H2O↓。
The present invention is using potassium chloride, sulfuric acid, phosphorus ore as raw material, with the decomposing phosphate rock by chlorhydric acid that potassium chloride and sulfuric acid reaction are produced,
Ammonia preparing phosphoric acid hydrogen calcium is added after defluorinate, then reacts preparing potassium dihydrogen phosphate and phosphoric acid with sulfuric acid and potassium acid sulfate, is eventually adding
Lime white separation, lower production costs, utilization rate of raw materials are high, product quality is good, and can by-product fluosilicic acid sodium.With existing skill
Art, which is compared, following beneficial effect.
Using potassium chloride, sulfuric acid, phosphorus ore as raw material, compared with tradition using potassium hydroxide with thermal phosphoric acid as feedstock production process
Significantly reduce production cost.
The present invention produces that react the potassium dihydrogen phosphate purity produced again after calcium monohydrogen phosphate excellent first with acidolysis phosphoric acid defluorinate
It is good, meet the requirement of national standard.
Fluorine is the harmful element in fertilizer, and directly application has damage to soil environment, and the present invention efficiently solves in phosphorus ore
The recycling and utilization of fluorine resource have good economic benefit and social benefit.
In preparation process of the present invention, phosphor resource recycles in process of production, and utilization rate of raw materials is higher.
Present invention process process is clear, easily controllable, and application is good, the product for the environment that is safe from harm, production environment friend
It is good.
Claims (3)
1. a kind of production method of potassium dihydrogen phosphate, which is characterized in that the method steps are as follows:
(1) phosphate ore pulp and ammonium sulfate, the hydrochloric acid that mass concentration is 15 ~ 30% for being 0 ~ 30% by water content: CaO, SO3, HCl 1:
The molar ratio of 0.4 ~ 0.7:1 mixes, 60 ~ 90 DEG C of 1.5 ~ 4h of reaction, filters ardealite, obtain include hydrochloric acid, phosphoric acid, ammonium chloride,
The mixed solution of monoammonium phosphate, CaO, P in filtrate2O5For molar ratio 1:0.5 ~ 1；
(2) mixed solution in step (1) is taken, defluorinating agent is added, reaction temperature is 30 ~ 60 DEG C, and the reaction time is 1 ~ 2h, mistake
Filter, obtains defluorinate filtrate and fluosilicate；
(3) it is filtered, washed with defluorinate filtrate, adjustment ph value 5 ~ 8 in ammonia, obtains filter cake and ammonium chloride solution；Filter cake and water are matched
Slurry is made: mass concentration is 20 ~ 40%, and ammonium chloride solution concentration, crystallization, centrifugation obtain ammonia chloride crystal；
(4) potassium chloride and excess sulfuric acid reaction, obtain the mixed solution of sulfuric acid and potassium acid sulfate: potassium acid sulfate mass content is
30% ~ 65%, it is mixed with the filter cake slurry in step (3), reaction temperature is 70 ~ 90 DEG C, the reaction time is 2.5 ~ 4.5h, crosses and filters out
Ardealite obtains the mixed solution of phosphoric acid and potassium dihydrogen phosphate；
(5) with the mixed solution in lime white neutralization procedure (4), adjustment ph value is 5 ~ 8, and calcium monohydrogen phosphate and di(2-ethylhexyl)phosphate is obtained by filtration
Hydrogen potassium filtrate；
(6) by filtrate concentration, the crystallization in process (5), crystallization is filtered, washed, obtains potassium dihydrogen phosphate crystal after dry.
2. the method according to claim 1, wherein the hybrid mode of the phosphate ore pulp and ammonium sulfate, hydrochloric acid is
One of the following is several:
By phosphorus ore and ammonium sulfate simultaneous grinding after metering, mixed ore pulp and hydrochloric acid reaction are obtained；By the phosphorus ore ore pulp after grinding
It is mixed with ammonium sulfate through metering, obtains mixed ore pulp and hydrochloric acid reaction；Phosphate ore pulp, ammonium sulfate, hydrochloric acid are added separately to extract
It is reacted in slot；After phosphate ore pulp and hydrochloric acid reaction, ammonium sulfate is added；
The method according to claim 1, wherein the fluosilicate is one of the following or several:
Prodan, potassium fluosilicate.
3. the method according to claim 1, wherein mode of washing in step (3) is classification washing 3-5 times,
Chloride ion content in filter cake is 0 ~ 0.3%；In step (4) in the nitration mixture of potassium acid sulfate and sulfuric acid chloride ion content be 0 ~
0.15%；
The method according to claim 1, wherein the return step (1) before unsaturation of the filtrate in step (3) is matched
Phosphorus ore slurry processed；Washing lotion in step (4) is as acid reflux return step (3)；Filtrate in step (6) is excessive in foreign ion
When, it is used as other purposes such as fertilizer production, no longer return step (4) uses.
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| CN201710391249.3A CN108946689A (en) | 2017-05-27 | 2017-05-27 | A kind of production method of potassium dihydrogen phosphate |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2354962A1 (en) * | 1976-06-15 | 1978-01-13 | Pennzoil Co | PROCESS FOR THE PRODUCTION OF PHOSPHORIC ACID AND PHOSPHATE WITHOUT FLUORINE |
| US4191734A (en) * | 1976-06-15 | 1980-03-04 | Pennzoil Company | Fluoride-free phosphate reactions |
| CN1060084A (en) * | 1990-09-29 | 1992-04-08 | 门伟 | The production method of potassium primary phosphate, vitriolate of tartar |
| CN1789117A (en) * | 2004-12-14 | 2006-06-21 | 自贡鸿鹤化工股份有限公司 | Method for producing potassium dihydrogen phosphate and gypsum using hydrochloric acid method |
| CN101054170A (en) * | 2007-04-13 | 2007-10-17 | 宜昌市仁和矿业有限责任公司 | Method for preparing potassium dihydrogen phosphate from calcium hydrogen phosphate |
| CN101337657A (en) * | 2008-08-06 | 2009-01-07 | 黄明科 | Process for disassembling phosphate ore by mixed acid and coproducing potassium dihydrogen phosphate, hydrogen phosphate and combined fertilizer |
| CN104311190A (en) * | 2014-10-09 | 2015-01-28 | 云南省化工研究院 | Method for producing high concentration chlorine-based composite fertilizer by partially decalcifying hydrochloric acid decomposed phosphorite |
-
2017
- 2017-05-27 CN CN201710391249.3A patent/CN108946689A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2354962A1 (en) * | 1976-06-15 | 1978-01-13 | Pennzoil Co | PROCESS FOR THE PRODUCTION OF PHOSPHORIC ACID AND PHOSPHATE WITHOUT FLUORINE |
| US4191734A (en) * | 1976-06-15 | 1980-03-04 | Pennzoil Company | Fluoride-free phosphate reactions |
| CN1060084A (en) * | 1990-09-29 | 1992-04-08 | 门伟 | The production method of potassium primary phosphate, vitriolate of tartar |
| CN1789117A (en) * | 2004-12-14 | 2006-06-21 | 自贡鸿鹤化工股份有限公司 | Method for producing potassium dihydrogen phosphate and gypsum using hydrochloric acid method |
| CN101054170A (en) * | 2007-04-13 | 2007-10-17 | 宜昌市仁和矿业有限责任公司 | Method for preparing potassium dihydrogen phosphate from calcium hydrogen phosphate |
| CN101337657A (en) * | 2008-08-06 | 2009-01-07 | 黄明科 | Process for disassembling phosphate ore by mixed acid and coproducing potassium dihydrogen phosphate, hydrogen phosphate and combined fertilizer |
| CN104311190A (en) * | 2014-10-09 | 2015-01-28 | 云南省化工研究院 | Method for producing high concentration chlorine-based composite fertilizer by partially decalcifying hydrochloric acid decomposed phosphorite |
Non-Patent Citations (1)
| Title |
|---|
| 贡长生主编: "《现代工业化学》", 31 August 1999, 湖北科学技术出版社 * |
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Application publication date: 20181207 |