CN105603215B - One kind efficiently leaches K, Ca, Mg, P method using extractant and hydrochloric acidolysis technology from phosphorus potassium associated minerals - Google Patents
One kind efficiently leaches K, Ca, Mg, P method using extractant and hydrochloric acidolysis technology from phosphorus potassium associated minerals Download PDFInfo
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- CN105603215B CN105603215B CN201511020302.6A CN201511020302A CN105603215B CN 105603215 B CN105603215 B CN 105603215B CN 201511020302 A CN201511020302 A CN 201511020302A CN 105603215 B CN105603215 B CN 105603215B
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- phosphorus potassium
- associated minerals
- potassium associated
- extractant
- fluoride
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
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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
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/2208—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with an acid or a mixture of acids other than sulfuric acid
- C01B25/2212—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with an acid or a mixture of acids other than sulfuric acid with hydrochloric acid or hydrogen chloride in aqueous medium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
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- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention belongs to industrial circle, and in particular to one kind efficiently leaches K, Ca, Mg, P method using extractant and hydrochloric acidolysis technology from phosphorus potassium associated minerals.Methods described is：Phosphorus potassium associated minerals, fluoride, extractant and hydrochloric acid solution are mixed；Under agitation, the coupled reaction that heating carries out phosphoric acid extraction and phosphorus potassium associated minerals acidolysis is synchronously carried out, after reaction terminates, after natural cooling, filtering, obtain containing K, Ca, Mg, P leaching liquid.The method of the invention is by phosphoric acid extraction technique and adds the technique of fluoride acidolysis phosphorus potassium associated minerals to be coupled together, and can efficiently leach K, Ca, Mg, P from phosphorus potassium associated minerals, substantially increase K, Ca, Mg, P leaching rate；The method of the invention can effectively reduce reaction temperature and reaction time, effectively alleviate corrosion harmfulness of the acidolysis phosphorus potassium associated minerals to equipment.
Description
Technical field
The invention belongs to industrial circle, and in particular to one kind is high from phosphorus potassium associated minerals using extractant and hydrochloric acidolysis technology
Effect leaching K, Ca, Mg, P method.
Background technology
N P and K is the three big elements for ensureing crops normal growth, and vital work is played to China's agricultural development
With.Nitrogenous fertilizer is typically obtained using synthesis ammonia technology.And there is a serious shortage in the supply in China potash fertilizer and phosphate fertilizer, particularly potash fertilizer, except China
Qinghai Lake Region has outside larger amount of soluble potassium reserves, elsewhere substantially without great amount of soluble potassium ore deposit.China is mostly
The phosphorus ore in area belongs to the phosphorus ore of middle-low grade or based on phosphorus potassium mineral intergrowth, and handles this mineral intergrowth and be often faced with skill
The problem of art and cost.
Phosphorus potassium associated minerals generate phosphoric acid, and then produce due to the presence containing P elements under acid condition existing for hydrochloric acid
Raw insoluble orthophosphates parcel or the surface for being covered in ore particle, hinder the progress of acid hemolysis process, cause even in there is fluorine
In the case of the presence of the auxiliary agents such as salt dissolving, yield less high P, K, Ca and Mg can only be also obtained using hydrochloric acidolysis phosphorus potassium associated minerals
Deng, and reaction temperature is higher, and the reaction time is longer.
The content of the invention
The present invention is in view of the shortcomings of the prior art, and it is an object of the present invention to provide a kind of utilize extractant and hydrochloric acidolysis technology from phosphorus
Potassium associated minerals efficiently leach K, Ca, Mg, P method.
For achieving the above object, the technical solution adopted by the present invention is：
One kind efficiently leaches K, Ca, Mg using extractant and hydrochloric acidolysis technology from phosphorus potassium associated minerals, P method, including
Following steps：Phosphorus potassium associated minerals, fluoride, extractant and hydrochloric acid solution are mixed；Heating carries out extraction phosphorus under agitation
The coupled reaction of acid and acidolysis phosphorus potassium associated minerals, after reaction terminates, after natural cooling, filtering, obtain containing K, Ca, Mg, P leaching
Liquid.
In such scheme, the P of the phosphorus potassium associated minerals2O5Content is 5%~15%, and potassium feldspar is with K2O meter contents are 5%
~10%, CaO meter content are that 5%~10%, MgO meter contents are 0.5%~3%.
In such scheme, the extractant is alcohols, phosphoric acid ester or polyethers.
In such scheme, phosphorus content in the phosphorus potassium associated minerals is converted into the quality of phosphoric acid, the volume of the extractant
For 0.5~4 times of phosphoric acid quality.
In such scheme, the fluoride is calcirm-fluoride, sodium fluoride or hydrogen fluoride.
In such scheme, the mass concentration of the hydrochloric acid solution is 15%~37%.
In such scheme, the mass ratio of the fluoride and phosphorus potassium associated minerals is 1:5~20；The hydrochloric acid solution and phosphorus potassium
The liquid-solid ratio of associated minerals is 2~5:1.
In such scheme, the granularity of the phosphorus potassium associated minerals was 200 mesh sieves, and screen over-size is less than 5%.
In such scheme, the reaction temperature of the coupled reaction is 70 DEG C~90 DEG C, and the reaction time is 3h~6h.
Beneficial effects of the present invention are as follows：(1) the method for the invention by phosphoric acid extraction technique and adds fluoride acidolysis phosphorus
The technique of potassium associated minerals is coupled together, and phosphoric acid caused by hydrochloric acidolysis and reaction system are separated using extractant, avoid giving birth to
The progress that substantial amounts of orthophosphates hinders acidolysis is produced, this method can efficiently leach K, Ca, Mg, P from phosphorus potassium associated minerals, carry significantly
High K, Ca, Mg, P leaching rate；(2) the method for the invention can effectively reduce reaction temperature and reaction time, effectively slow
Solve corrosion harmfulness of the acidolysis phosphorus potassium associated minerals to equipment.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
In following examples, agents useful for same is commercially available chemical reagent unless otherwise instructed.
In following examples, the P of the phosphorus potassium associated minerals2O5Content is 5%~15%, and potassium feldspar is with K2O counts content
5%~10%, CaO meter content are that 5%~10%, MgO meter contents are 0.5%~3%.The granularity of the phosphorus potassium associated minerals was
200 mesh sieves, screen over-size are less than 5%.
Embodiment 1
One kind efficiently leaches K, Ca, Mg using extractant and hydrochloric acidolysis technology from phosphorus potassium associated minerals, P method, including
Following steps：Weigh phosphorus potassium associated minerals 20g, CaF21.8g, 22.5% (mass concentration) HCl 68ml, tributyl phosphate 2ml,
Three-necked flask is put into successively, is heated up, opens stirring, the washing filtering after 75 DEG C of reaction 4h, obtains containing K, Ca, Mg, P leaching
Liquid.
K in leaching liquid is determined using atomic absorption light spectral method+, Ca2+, Mg2+Content, using ammonium molybdate titration method survey
Determine H in leaching liquid3PO4Content, be calculated and phosphorus potassium associated minerals handled using the present embodiment method, the leaching rate of wherein phosphorus reaches
To 98.3%；The leaching rate of potassium is 96.2%；Ca leaching rate is 97.5%；Mg leaching rate is 96.7%.
Embodiment 2
One kind efficiently leaches K, Ca, Mg using extractant and hydrochloric acidolysis technology from phosphorus potassium associated minerals, P method, including
Following steps：Weigh phosphorus potassium associated minerals 20g, CaF23.0g, 30% (mass concentration) HCl 52ml, n-heptanol 2.5ml, successively
Three-necked flask is put into, heating, opens stirring, the washing filtering after 80 DEG C of reaction 3h, obtains containing K, Ca, Mg, P leaching liquid.
K in leaching liquid is determined using atomic absorption light spectral method+, Ca2+, Mg2+Content, using ammonium molybdate titration method survey
Determine H in leaching liquid3PO4Content, be calculated and phosphorus potassium associated minerals handled using the present embodiment method, the leaching rate of wherein phosphorus reaches
To 99.1%；The leaching rate of potassium is 98.5%；Ca leaching rate is 98.4%；Mg leaching rate is 95.9%.
Embodiment 3
One kind efficiently leaches K, Ca, Mg using extractant and hydrochloric acidolysis technology from phosphorus potassium associated minerals, P method, including
Following steps：Weigh phosphorus potassium associated minerals 20g, CaF21.2g, 27%HCl (mass concentration) 65ml, PPG MN-
10002.5ml, three-necked flask is put into successively, heated up, open stirring, the washing filtering after 70 DEG C of reaction 4h, obtain containing K, Ca,
Mg, P leaching liquid.
K in leaching liquid is determined using atomic absorption light spectral method+, Ca2+, Mg2+Content, using ammonium molybdate titration method survey
Determine H in leaching liquid3PO4Content, be calculated and phosphorus potassium associated minerals handled using the present embodiment method, the leaching rate of wherein phosphorus reaches
To 99.5%；The leaching rate of potassium is 97.8%；Ca leaching rate is 99.3%；Mg leaching rate is 96.1%.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change or change therefore amplified
Move within still in the protection domain of the invention.
Claims (9)
1. one kind efficiently leaches K, Ca, Mg, P method, its feature using extractant and hydrochloric acidolysis technology from phosphorus potassium associated minerals
It is, comprises the following steps：Phosphorus potassium associated minerals, fluoride, extractant and hydrochloric acid solution are mixed；Under agitation, heat up
The coupled reaction that progress phosphoric acid extraction and phosphorus potassium associated minerals acidolysis are synchronously carried out, after reaction terminates, after natural cooling, filtering, obtain
To containing K, Ca, Mg, P leaching liquid.
2. according to the method for claim 1, it is characterised in that the P of the phosphorus potassium associated minerals2O5Content is 5% ~ 15%, potassium length
Stone is with K2O meter contents are 5% ~ 10%, and CaO content is 5% ~ 10%, and content of MgO is 0.5% ~ 3%.
3. according to the method for claim 1, it is characterised in that the extractant is alcohols, phosphoric acid ester or polyethers.
4. according to the method for claim 1, it is characterised in that phosphorus content in the phosphorus potassium associated minerals is converted into phosphoric acid
Quality, the volume of the extractant are 0.5 ~ 4 times of phosphoric acid quality.
5. according to the method for claim 1, it is characterised in that the granularity of the phosphorus potassium associated minerals was 200 mesh sieves, was tailed over
Amount is less than 5%.
6. according to the method for claim 1, it is characterised in that the reaction temperature of the coupled reaction is 70 DEG C ~ 90 DEG C, instead
It is 3h ~ 6h between seasonable.
7. according to the method for claim 1, it is characterised in that the fluoride is calcirm-fluoride, sodium fluoride or hydrogen fluoride.
8. according to the method for claim 1, it is characterised in that the mass concentration of the hydrochloric acid solution is 15% ~ 37%.
9. according to the method for claim 1, it is characterised in that the mass ratio of the fluoride and phosphorus potassium associated minerals is 1:5~
20；The liquid-solid ratio of the hydrochloric acid solution and phosphorus potassium associated minerals is 2 ~ 5:1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511020302.6A CN105603215B (en) | 2015-12-30 | 2015-12-30 | One kind efficiently leaches K, Ca, Mg, P method using extractant and hydrochloric acidolysis technology from phosphorus potassium associated minerals |
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| CN201511020302.6A CN105603215B (en) | 2015-12-30 | 2015-12-30 | One kind efficiently leaches K, Ca, Mg, P method using extractant and hydrochloric acidolysis technology from phosphorus potassium associated minerals |
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| CN105603215A CN105603215A (en) | 2016-05-25 |
| CN105603215B true CN105603215B (en) | 2017-12-19 |
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| CN106278391B (en) * | 2016-07-22 | 2019-05-28 | 武汉工程大学 | A kind of direct method for decomposing phosphorus potassium associated minerals and phosphorus ore composite ore under cryogenic using hydrochloric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4995894A (en) * | 1973-01-19 | 1974-09-11 | ||
| US4196180A (en) * | 1973-07-04 | 1980-04-01 | Hoechst Aktiengesellschaft | Purification of phosphoric acid by means of organic solvents |
| CN1006222B (en) * | 1986-07-12 | 1989-12-27 | 湖北省化学研究所 | Recovery of calcium chloride from waste liquid of |
| US7687046B2 (en) * | 2002-06-28 | 2010-03-30 | Ecophos | Method of producing phosphoric acid salt |
| CN101343051A (en) * | 2008-09-02 | 2009-01-14 | 武汉凌派化工科技有限公司 | Method for decomposing phosphorus ore and phosphorus ore containing article with hydrochloric acid to produce phosphoric acid and ammonium phosphate salt |
| CN102134063B (en) * | 2011-01-12 | 2012-07-04 | 上海协达精细化工研发有限公司 | Method for manufacturing industrial phosphoric acid, industrial ammonium phosphate and food-grade phosphoric acid from medium and low-grade phosphorite by one-step extraction of hydrochloric acid method |
| CN104230448A (en) * | 2014-10-16 | 2014-12-24 | 云南省化工研究院 | Method for preparing N-P-K (Nitrogen-Phosphorus-Potassium) compound fertilizer by using hydrochloric acid to decompose phosphorite acidified solution |
| CN104744175B (en) * | 2015-04-03 | 2017-09-29 | 武汉工程大学 | The method that nitrogen-phosphorus-potassium compound fertilizer is produced using phosphorus potassium associated minerals |
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