CN105603215A - Method using extraction agent and hydrochloric acid acidolysis technology to efficiently leach K, Ca, Mg and P from P and K associated ore - Google Patents

Method using extraction agent and hydrochloric acid acidolysis technology to efficiently leach K, Ca, Mg and P from P and K associated ore Download PDF

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Publication number
CN105603215A
CN105603215A CN201511020302.6A CN201511020302A CN105603215A CN 105603215 A CN105603215 A CN 105603215A CN 201511020302 A CN201511020302 A CN 201511020302A CN 105603215 A CN105603215 A CN 105603215A
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China
Prior art keywords
phosphorus potassium
associated minerals
fluoride
potassium associated
acidolysis
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CN201511020302.6A
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CN105603215B (en
Inventor
王存文
周俊锋
刘存成
马家玉
覃远航
吕仁亮
汪铁林
王为国
陈苏芳
冯魏良
唐正姣
张俊峰
吴元欣
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Wuhan Institute of Technology
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Wuhan Institute of Technology
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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
    • 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
    • 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

Abstract

The invention belongs to the field of industry, in particular to a method using extraction agent and a hydrochloric acid acidolysis technology to efficiently leach K, Ca, Mg and P from P and K associated ore. Specifically, the method comprises: mixing the P and K associated ore, fluoride, extraction agent and a hydrochloric acid solution; under stirring, heating to perform coupling reaction in which phosphoric acid extracting and P and K associated ore acidolysis are performed synchronously, after action is finished, naturally cooling, and after filtering, obtaining an extraction solution containing K, Ca, Mg and P. The phosphoric acid extracting process and P and K associated ore acidolysis process by adding fluoride are coupled, K, Ca, Mg and P can be efficiently leached from the P and K associated ore, and the leaching rate of the K, Ca, Mg and P is greatly improved; reaction temperature and reaction time are effectively reduced and the corrosion hazard to the device caused by acidolysis of the P and K associated ore is effectively reduced.

Description

One utilizes extractant and hydrochloric acidolysis technology efficiently to leach K from phosphorus potassium associated minerals, Ca, Mg, the method for P
Technical field
The invention belongs to industrial circle, be specifically related to one and utilize extractant and hydrochloric acidolysis technology efficiently to leach from phosphorus potassium associated mineralsK, Ca, Mg, the method for P.
Background technology
Nitrogen phosphorus potassium is the three large elements that ensure crops normal growth, and China's agricultural development is played to vital effect. Nitrogenous fertilizerThe general synthetic ammonia technology that adopts obtains. And China's there is a serious shortage in the supply potash fertilizer and phosphate fertilizer, particularly potash fertilizer, except the Qinghai Lake ground of ChinaDistrict has outside relatively large soluble potassium reserves, and other places are substantially without great amount of soluble potassium ore deposit. The phosphorus ore of China most areas allLow-grade phosphorus ore or taking phosphorus potassium mineral intergrowth as main in belonging to, is often faced with asking of technology and cost and process this mineral intergrowthTopic.
Phosphorus potassium associated minerals, due to the existence that contains P elements, generate phosphoric acid under the acid condition existing, and then produce insoluble at hydrochloric acidProperty orthophosphates parcel or cover the surface of ore particle, hindered the carrying out of acidolysis process, having fluoride salt etc. to help even if causeExisting in situation of agent, adopts hydrochloric acidolysis phosphorus potassium associated minerals also can only obtain the P that yield is not too high, K, and Ca and Mg etc.,And reaction temperature is higher, the reaction time is longer.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, object is to provide one to utilize extractant and hydrochloric acidolysis technology from the association of phosphorus potassiumOre deposit efficiently leaches K, Ca, Mg, the method for P.
For achieving the above object, the technical solution used in the present invention is:
One utilizes extractant and hydrochloric acidolysis technology efficiently to leach K from phosphorus potassium associated minerals, Ca, Mg, the method for P, comprise asLower step: phosphorus potassium associated minerals, fluoride, extractant and hydrochloric acid solution are mixed; Under stirring condition, heat up and carry out phosphoric acid extractionWith the coupled reaction of acidolysis phosphorus potassium associated minerals, reaction finish after, naturally cooling, filter after, obtain contain K, Ca, Mg, P'sLeaching liquid.
In such scheme, the P of described phosphorus potassium associated minerals2O5Content is 5%～15%, and potassic feldspar is with K2O meter content is 5%～10%,CaO meter content is that 5%～10%, MgO meter content is 0.5%～3%.
In such scheme, described extractant is alcohols, phosphoric acid ester or polyethers.
In such scheme, phosphorus content in described phosphorus potassium associated minerals is converted to the quality of phosphoric acid, the volume of described extractant is phosphoric acid0.5～4 times of quality.
In such scheme, described fluoride is calcirm-fluoride, sodium fluoride or hydrogen fluoride.
In such scheme, the mass concentration of described hydrochloric acid solution is 15%～37%.
In such scheme, the mass ratio of described fluoride and phosphorus potassium associated minerals is 1:5～20; Described hydrochloric acid solution and phosphorus potassium associated mineralsLiquid-solid ratio be 2～5:1.
In such scheme, the granularity of described phosphorus potassium associated minerals was 200 mesh sieves, and screen over-size is less than 5%.
In such scheme, the reaction temperature of described coupled reaction is 70 DEG C～90 DEG C, and the reaction time is 3h～6h.
Beneficial effect of the present invention is as follows: (1) the method for the invention is by phosphoric acid extraction technique and add fluoride acidolysis phosphorus potassium companionThe technique of rawore is coupled together, and phosphoric acid and the reaction system of utilizing extractant that hydrochloric acidolysis is produced are separated, and avoids producing a large amount ofOrthophosphates hinder the carrying out of acidolysis, the method can efficiently leach K from phosphorus potassium associated minerals, Ca, Mg, P, improves greatlyK, Ca, Mg, the leaching rate of P; (2) the method for the invention can effectively reduce reaction temperature and reaction time, effectivelyAlleviate the corrosion harmfulness of acidolysis phosphorus potassium associated minerals to equipment.
Detailed description of the invention
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention is notOnly be confined to the following examples.
In following examples, agents useful for same is commercially available chemical reagent if no special instructions.
In following examples, the P of described phosphorus potassium associated minerals2O5Content is 5%～15%, and potassic feldspar is with K2O meter content is5%～10%, CaO meter content is that 5%～10%, MgO meter content is 0.5%～3%. The granularity of described phosphorus potassium associated minerals was200 mesh sieves, screen over-size is less than 5%.
Embodiment 1
One utilizes extractant and hydrochloric acidolysis technology efficiently to leach K from phosphorus potassium associated minerals, Ca, Mg, the method for P, comprise asLower step: take phosphorus potassium associated minerals 20g, CaF21.8g, 22.5% (mass concentration) HCl68ml, tributyl phosphate 2ml,Drop into successively there-necked flask, heat up, open and stir, filter in 75 DEG C of reaction 4h after washings, obtain containing K Ca, Mg, PLeaching liquid.
Adopt atomic absorption light spectral method to measure K in leaching liquid+，Ca2+，Mg2+Content, adopt ammonium molybdate titration method to measureH in leaching liquid3PO4Content, calculate and adopt the present embodiment method to process phosphorus potassium associated minerals, wherein the leaching rate of phosphorus reaches98.3%; The leaching rate of potassium is 96.2%; The leaching rate of Ca is 97.5%; The leaching rate of Mg is 96.7%.
Embodiment 2
One utilizes extractant and hydrochloric acidolysis technology efficiently to leach K from phosphorus potassium associated minerals, Ca, Mg, the method for P, comprise asLower step: take phosphorus potassium associated minerals 20g, CaF23.0g, 30% (mass concentration) HCl52ml, n-heptanol 2.5ml, successivelyDrop into there-necked flask, heat up, open and stir, filter in 80 DEG C of reaction 3h after washings, obtain containing K, Ca, Mg, P soaksGet liquid.
Adopt atomic absorption light spectral method to measure K in leaching liquid+，Ca2+，Mg2+Content, adopt ammonium molybdate titration method to measureH in leaching liquid3PO4Content, calculate and adopt the present embodiment method to process phosphorus potassium associated minerals, wherein the leaching rate of phosphorus reaches99.1%; The leaching rate of potassium is 98.5%; The leaching rate of Ca is 98.4%; The leaching rate of Mg is 95.9%.
Embodiment 3
One utilizes extractant and hydrochloric acidolysis technology efficiently to leach K from phosphorus potassium associated minerals, Ca, Mg, the method for P, comprise asLower step: take phosphorus potassium associated minerals 20g, CaF21.2g, 27%HCl (mass concentration) 65ml, PPG MN-10002.5ml, drops into there-necked flask successively, heats up, and opens and stirs, and filters in 70 DEG C of reaction 4h after washings, obtain containing K, and Ca,Mg, the leaching liquid of P.
Adopt atomic absorption light spectral method to measure K in leaching liquid+，Ca2+，Mg2+Content, adopt ammonium molybdate titration method to measureH in leaching liquid3PO4Content, calculate and adopt the present embodiment method to process phosphorus potassium associated minerals, wherein the leaching rate of phosphorus reaches99.5%; The leaching rate of potassium is 97.8%; The leaching rate of Ca is 99.3%; The leaching rate of Mg is 96.1%.
Obviously, above-described embodiment is to be only the example that clearly explanation is done, and the not restriction to embodiment. For instituteThe those of ordinary skill in genus field, can also make other changes in different forms on the basis of the above description.Here without also giving exhaustive to all embodiments. And the apparent variation therefore amplified or variation still inWithin the protection domain of the invention.

Claims (9)

1. utilize extractant and hydrochloric acidolysis technology efficiently to leach a K from phosphorus potassium associated minerals, Ca, Mg, the method for P, its featureBe, comprise the steps: phosphorus potassium associated minerals, fluoride, extractant and hydrochloric acid solution to mix; Under stirring condition, riseTemperature is carried out the coupled reaction that phosphoric acid extraction and the acidolysis of phosphorus potassium associated minerals are synchronously carried out, after reaction finishes, and after naturally cooling, filtration,Obtain containing K Ca, Mg, the leaching liquid of P.
2. method according to claim 1, is characterized in that, the P of described phosphorus potassium associated minerals2O5Content is 5%～15%, potassiumFeldspar is with K2O meter content is that 5%～10%, CaO meter content is that 5%～10%, MgO meter content is 0.5%～3%.
3. method according to claim 1, is characterized in that, described extractant is alcohols, phosphoric acid ester or polyethers.
4. method according to claim 1, is characterized in that, phosphorus content in described phosphorus potassium associated minerals is converted to the matter of phosphoric acidAmount, the volume of described extractant is phosphoric acid quality 0.5～4 times.
5. method according to claim 1, is characterized in that, the granularity of described phosphorus potassium associated minerals was 200 mesh sieves, tailed overAmount is less than 5%.
6. method according to claim 1, is characterized in that, the reaction temperature of described coupled reaction is 70 DEG C～90 DEG C, anti-Time is 3h～6h.
7. method according to claim 1, is characterized in that, described fluoride is calcirm-fluoride, sodium fluoride or hydrogen fluoride.
8. method according to claim 1, is characterized in that, the mass concentration of described hydrochloric acid solution is 15%～37%.
9. method according to claim 1, is characterized in that, the mass ratio of described fluoride and phosphorus potassium associated minerals is 1:5～20;The liquid-solid ratio of described hydrochloric acid solution and phosphorus potassium associated minerals is 2～5:1.
CN201511020302.6A 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 Active CN105603215B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106278391A (en) * 2016-07-22 2017-01-04 武汉工程大学 A kind of hydrochloric acid that directly utilizes decomposes phosphorus potassium associated minerals and the method for phosphorus ore composite ore under cryogenic

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US3919396A (en) * 1973-01-19 1975-11-11 Toy Soda Manufacturing Co Ltd Phosphoric acid purification
US4196180A (en) * 1973-07-04 1980-04-01 Hoechst Aktiengesellschaft Purification of phosphoric acid by means of organic solvents
CN86104840A (en) * 1986-07-12 1987-07-22 湖北省化学研究所 Decomposing phosphate rock by chlorhydric acid liquid-liquid extraction preparation phosphoric acid does not have the discharging of waste liquid circulation technology
US20080267850A1 (en) * 2002-06-28 2008-10-30 Mohamed Takhim 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
CN102134063A (en) * 2011-01-12 2011-07-27 姚鼎文 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
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CN104744175A (en) * 2015-04-03 2015-07-01 武汉工程大学 Method for producing nitrogen-phosphorus-potassium mixed fertilizer by utilizing phosphorus-potassium associated ore

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US3919396A (en) * 1973-01-19 1975-11-11 Toy Soda Manufacturing Co Ltd Phosphoric acid purification
US4196180A (en) * 1973-07-04 1980-04-01 Hoechst Aktiengesellschaft Purification of phosphoric acid by means of organic solvents
CN86104840A (en) * 1986-07-12 1987-07-22 湖北省化学研究所 Decomposing phosphate rock by chlorhydric acid liquid-liquid extraction preparation phosphoric acid does not have the discharging of waste liquid circulation technology
US20080267850A1 (en) * 2002-06-28 2008-10-30 Mohamed Takhim 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
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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
CN104744175A (en) * 2015-04-03 2015-07-01 武汉工程大学 Method for producing nitrogen-phosphorus-potassium mixed fertilizer by utilizing phosphorus-potassium associated ore

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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