CN105523533A - Method for preparing high-quality phosphoric acid and high-quality phosphogypsum by leaching rare-earth-containing phosphorite with reproducible phosphoric acid - Google Patents
Method for preparing high-quality phosphoric acid and high-quality phosphogypsum by leaching rare-earth-containing phosphorite with reproducible phosphoric acid Download PDFInfo
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- CN105523533A CN105523533A CN201610044451.4A CN201610044451A CN105523533A CN 105523533 A CN105523533 A CN 105523533A CN 201610044451 A CN201610044451 A CN 201610044451A CN 105523533 A CN105523533 A CN 105523533A
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- phosphoric acid
- quality
- rare earth
- phosphogypsum
- leaching
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
Abstract
The invention discloses a method for preparing high-quality phosphoric acid and high-quality phosphogypsum by leaching rare-earth-containing phosphorite with reproducible phosphoric acid. The method comprises the following steps: metering the rear-earth-containing phosphorite and the reproducible phosphoric acid, putting the rear-earth-containing phosphorite and the reproducible phosphoric acid into a first-segment leaching groove to carry out a leaching reaction, adding a flocculating agent into a sizing agent, allowing clear liquid to overflow into a monocalcium phosphate storage groove, pumping slag slurry into a second-segment leaching groove, adding the reproducible phosphoric acid to leach continually; at the end of a second-segment leaching reaction, adding the flocculating agent into slurry, allowing clear liquid to overflow into the monocalcium phosphate storage groove, pumping the slag slurry into a second-segment filter press, and feeding filtrate into the monocalcium phosphate storage groove to form a rare-earth-containing monocalcium phosphate solution; adding strong sulfuric acid into the solution, and reacting to obtain phosphoric acid containing phosphogypsum and rare earth; lastly, performing filter pressing to obtain rare-earth-containing high-quality phosphoric acid and high-quality phosphogypsum. By adopting the method, the high-quality phosphoric acid and the high-quality phosphogypsum can be prepared at the same time, and meanwhile a condition is created for comprehensive recycling of associated rare-earth resources. The method is suitable for middle-low grade phosphorite associated with rare earth.
Description
Technical field
The present invention relates to the compound of phosphorus, particularly relate to phosphoric acid, also relate to phosphogypsum, also relate to rare earth, furthermore, relate to the method with phosphoric acid leaching phosphorus ore preparing phosphoric acid.
Background technology
As everyone knows, traditional phosphoric acid by wet process sulfuric acid extraction phosphorus ore obtains, and a large amount of phosphogypsums produced in its production process are low due to quality, can not well be fully utilized; If used containing rare earth phosphate rock, the rare earth resources of association in phosphorus ore can enter phosphogypsum in a large number and by dilution, be difficult to obtain high-quality phosphoric acid and high-quality phosphogypsum, therefore the recycling not a duck soup of phosphorus ore middle-weight rare earths resource, therefore contains the utilization of rare earth phosphate rock also not easily.So traditional technique can not be used for containing rare earth phosphate rock.
Relate to the patent application utilized containing rare earth phosphate rock in Chinese patent database to have No. 991174135 " rare earth calcium superphosphate and production methods thereof ", No. ZL2006100571056 " a kind of rare earth addition and the rare earth calcium superphosphate containing this additive and preparation method thereof ", No. ZL2006102009881 " reducing the method for rare earth content in phosphoric acid ", No. ZL2007101797497 " a kind of be raw material wet-method phosphoric acid and therefrom Extraction of rare earth with phosphorite ore deposit processing method ", No. ZL2009100787938 " a kind of technique adopting centrifugal extraction equipment gathering trace rare earth from phosphoric acid ", No. 2010101803875 " a kind of ammonium magnesium phosphate slow release fertilizer containing double salt of rare earth and preparation method thereof ", No. 2014107642837 " methods from producing recovering rare earth the phosphorus ore slag after phosphoric acid " etc., these patented technologies above-mentioned can not solve the technical barrier from producing high-quality phosphoric acid and high-quality phosphogypsum containing rare earth phosphate rock.
Summary of the invention
The present invention aims to provide high-quality phosphoric acid and high-quality phosphogypsum are produced in the leaching of a kind of regeneration phosphoric acid method containing rare earth phosphate rock, both can make full use of and get back high-quality phosphoric acid and high-quality phosphogypsum containing rare earth phosphate rock resource, thus solve the difficult problem producing a large amount of phosphogypsum waste in conventional wet phosphoric acid production, reduce environmental protection pressure, and improve Business Economic Benefit.
The method producing high-quality phosphoric acid and high-quality phosphogypsum with the leaching of regeneration phosphoric acid containing rare earth phosphate rock that contriver provides, comprises the following steps:
(1) leach groove containing rare earth phosphate rock and regeneration phosphoric acid by together entering one section after measure, and making regeneration phosphoric acid and containing rare earth phosphate rock to occur one section and leach and react;
After (2) one sections of leaching reactions terminate, add flocculation agent, clear liquid is starched with slag and is separated in slip, clear liquid overflow is to monocalcium phosphate storage tank, and slag slurry, with being pumped to two sections of leaching grooves, adding regeneration phosphoric acid and proceeds leaching reaction;
After (3) two sections of leaching reactions terminate, in slip, add flocculation agent, clear liquid is starched with slag and is separated, clear liquid overflow is to monocalcium phosphate storage tank, slag slurry is with being pumped to two sections of pressure filter, and the filtrate be press-filtered out also enters monocalcium phosphate storage tank, forms the biphosphate calcium solution containing rare earth;
(4) the monocalcium phosphate solution pump containing rare earth delivers to desulfuration acid group groove, adds the vitriol oil and solution Free Calcium reacts, and obtains the phosphoric acid containing phosphogypsum and rare earth;
(5) phosphoric acid containing phosphogypsum and rare earth passes through pressure filter press filtration, and obtain the high-quality phosphoric acid containing rare earth and high-quality phosphogypsum, this phosphoric acid is regeneration phosphoric acid;
(6) the regeneration phosphoric acid part obtained returns (1) step, the leaching operation of (2) step is used for leaching containing rare earth phosphate rock, and another part is as phosphoric acid finished product; So repeatedly, high-quality phosphoric acid and high-quality phosphogypsum can be produced.
In aforesaid method (1) step, described regeneration phosphoric acid be with present method obtain, the phosphoric acid of reuse, the processing condition of described one section of leaching reaction control regeneration phosphoric acid and phosphorus concentrate liquid-solid ratio 8: 1 ~ 15: 1, temperature of reaction 30 DEG C ~ 80 DEG C, reaction times 2 ~ 6h.
In aforesaid method (2) step, described flocculation agent is negatively charged ion or cationic polyacrylamide; The processing condition of described two sections of leaching reactions control admittedly than 8: 1 ~ 15: 1, temperature of reaction 30 DEG C ~ 80 DEG C, reaction times 2 ~ 6h.
In aforesaid method (3) step, described flocculation agent is negatively charged ion or cationic polyacrylamide.
In aforesaid method (4) step, the described vitriol oil to be massfraction be 98% sulfuric acid, it is 60 ± 10 DEG C that the reaction conditions of sulfuric acid and biphosphate calcium solution controls in temperature, reaction times 2 ~ 4h, and the mol ratio of sulfate radical and calcium ion is 1:1 ~ 1.2:1.
In aforesaid method (5) step, described high-quality phosphoric acid is with P
2o
5meter concentration 23% ~ 26%, content of rare earth be 0.15 ~ 0.25g/L containing rare earth phosphoric acid; Described high-quality phosphogypsum is that whiteness is greater than 90%, the phosphogypsum that purity is greater than 97%.
Contriver points out: the above-mentioned rare earth phosphoric acid that contains can be used for recovering rare earth resource; The quality index of above-mentioned high-quality phosphogypsum after washing reaches phosphogypsum GB GB/T23456-2009 acceptable end product standard, be applicable to the high strength gypsum powder adopting dry method α, wet method α explained hereafter more than 6.0 grades, the β building gypsum plaster that direct frying obtains can reach the plaster of Paris acceptable end product standard of GB GB/T9776-2008 standard after modification grinding.
Method of the present invention can process the mid low grade phosphate rock that association content of rare earth is only 0.06% ~ 0.13%, high-quality phosphogypsum can be obtained while producing high-quality phosphoric acid by this technique, simultaneously for the comprehensive reutilization of association rare earth resources creates condition, by controlling suitable processing condition, the leaching yield of phosphorus can reach 95% ~ 99%, the leaching yield of rare earth can reach 85% ~ 90%, is conducive to the utilization containing rare earth phosphate rock resource.High-quality phosphogypsum is convenient to application, solves in conventional wet phosphoric acid production the difficult problem producing a large amount of phosphogypsum waste and be difficult to utilize, greatly reduces environmental protection pressure, and improve the economic benefit of Wet-process Phosphoric Acid Production.Be applicable to the phosphorus ore of middle-low grade association rare earth.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the inventive method.
Embodiment
Embodiment:
Groove will be leached by together entering one section after measuring containing rare earth phosphate rock and regeneration phosphoric acid, make regeneration phosphoric acid and occur one section containing rare earth phosphate rock and leach and react, the processing condition of reaction control regeneration phosphoric acid and phosphorus concentrate liquid-solid ratio 8: 1 ~ 15: 1, temperature of reaction 30 DEG C ~ 80 DEG C, reaction times 2 ~ 6h; After one section of leaching reaction terminates, flocculation agent polyacrylamide is added in slip, clear liquid is starched with slag be separated, clear liquid overflow is to monocalcium phosphate storage tank, slag slurry is with being pumped to two sections of leaching grooves, and add regeneration phosphoric acid and proceed leaching reaction, the processing condition of reaction control admittedly than 8: 1 ~ 15: 1, temperature of reaction 30 DEG C ~ 80 DEG C, reaction times 2 ~ 6h; After two sections of leaching reactions terminate, in slip, add flocculation agent polyacrylamide, clear liquid is starched with slag and is separated, clear liquid overflow is to monocalcium phosphate storage tank, slag slurry is with being pumped to two sections of pressure filter, and the filtrate be press-filtered out also enters monocalcium phosphate storage tank, forms the biphosphate calcium solution containing rare earth; Monocalcium phosphate solution pump containing rare earth delivers to desulfuration acid group groove, add the vitriol oil that massfraction is 98%, it is 60 ± 10 DEG C that the reaction conditions of sulfuric acid and biphosphate calcium solution controls in temperature, reaction times 2 ~ 4h, the mol ratio of sulfate radical and calcium ion is 1:1 ~ 1.2:1, wherein sulfate radical and solution Free Calcium are reacted, obtains the phosphoric acid containing phosphogypsum and rare earth; Finally, the phosphoric acid containing phosphogypsum and rare earth, by pressure filter press filtration, obtains being greater than 90%, the high-quality phosphogypsum that purity is greater than 97% containing the high-quality phosphoric acid of rare earth and whiteness; Wherein high-quality phosphoric acid is with P
2o
5meter concentration 23% ~ 26%, content of rare earth be 0.15 ~ 0.25g/L containing rare earth phosphoric acid; The regeneration phosphoric acid part obtained returns (1) step, the leaching operation of (2) step is used for leaching containing rare earth phosphate rock, and another part is as phosphoric acid finished product; So repeatedly, high-quality phosphoric acid and high-quality phosphogypsum can be produced.
Claims (6)
1. produce the method for high-quality phosphoric acid and high-quality phosphogypsum with the leaching of regeneration phosphoric acid containing rare earth phosphate rock, it is characterized in that the method comprises the following steps:
(1) leach groove containing rare earth phosphate rock and regeneration phosphoric acid by together entering one section after measure, and making regeneration phosphoric acid and containing rare earth phosphate rock to occur one section and leach and react;
After (2) one sections of leaching reactions terminate, add flocculation agent, clear liquid is starched with slag and is separated in slip, clear liquid overflow is to monocalcium phosphate storage tank, and slag slurry, with being pumped to two sections of leaching grooves, adding regeneration phosphoric acid and proceeds leaching reaction;
After (3) two sections of leaching reactions terminate, in slip, add flocculation agent, clear liquid is starched with slag and is separated, clear liquid overflow is to monocalcium phosphate storage tank, slag slurry is with being pumped to two sections of pressure filter, and the filtrate be press-filtered out also enters monocalcium phosphate storage tank, forms the biphosphate calcium solution containing rare earth;
(4) the monocalcium phosphate solution pump containing rare earth delivers to desulfuration acid group groove, adds the vitriol oil and solution Free Calcium reacts, and obtains the phosphoric acid containing phosphogypsum and rare earth;
(5) phosphoric acid containing phosphogypsum and rare earth passes through pressure filter press filtration, and obtain the high-quality phosphoric acid containing rare earth and high-quality phosphogypsum, this phosphoric acid is regeneration phosphoric acid;
(6) the regeneration phosphoric acid part obtained returns (1) step, the leaching operation of (2) step is used for leaching containing rare earth phosphate rock, and another part is as phosphoric acid finished product; So repeatedly, high-quality phosphoric acid and high-quality phosphogypsum can be produced.
2. the method for claim 1, it is characterized in that in (1) step, described regeneration phosphoric acid be with present method obtain, the phosphoric acid of reuse, the processing condition of described one section of leaching reaction control regeneration phosphoric acid and phosphorus concentrate liquid-solid ratio 8: 1 ~ 15: 1, temperature of reaction 30 DEG C ~ 80 DEG C, reaction times 2 ~ 6h.
3. the method for claim 1, is characterized in that in (2) step, and described flocculation agent is negatively charged ion or cationic polyacrylamide; The processing condition of described two sections of leaching reactions control admittedly than 8: 1 ~ 15: 1, temperature of reaction 30 DEG C ~ 80 DEG C, reaction times 2 ~ 6h.
4. the method for claim 1, is characterized in that in (3) step, and described flocculation agent is negatively charged ion or cationic polyacrylamide.
5. the method for claim 1, it is characterized in that in (4) step, the described vitriol oil to be massfraction be 98% sulfuric acid, it is 60 ± 10 DEG C that the reaction conditions of sulfuric acid and biphosphate calcium solution controls in temperature, reaction times 2 ~ 4h, the mol ratio of sulfate radical and calcium ion is 1:1 ~ 1.2:1.
6. the method for claim 1, is characterized in that in (5) step, and described high-quality phosphoric acid is with P
2o
5meter concentration 23% ~ 26%, content of rare earth be 0.15 ~ 0.25g/L containing rare earth phosphoric acid; Described high-quality phosphogypsum is that whiteness is greater than 90%, the phosphogypsum that purity is greater than 97%.
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| CN201610044451.4A CN105523533B (en) | 2016-01-22 | 2016-01-22 | The method for producing high-quality phosphoric acid and high-quality ardealite containing rare earth phosphate rock with regeneration phosphoric acid leaching |
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| CN201610044451.4A CN105523533B (en) | 2016-01-22 | 2016-01-22 | The method for producing high-quality phosphoric acid and high-quality ardealite containing rare earth phosphate rock with regeneration phosphoric acid leaching |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117053A (en) * | 2017-12-22 | 2018-06-05 | 应城市嘉鸿技术服务科技有限公司 | It is a kind of to handle hardened soil with phytase so as to optimize the method for ardealite preparation process |
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| CN102220488A (en) * | 2011-05-31 | 2011-10-19 | 北京矿冶研究总院 | Method for separating rare earth from phosphate ore |
| CN102312089A (en) * | 2010-07-01 | 2012-01-11 | 北京矿冶研究总院 | Method for recovering rare earth from rare earth-containing phosphorite |
| CN103213964A (en) * | 2013-05-17 | 2013-07-24 | 成都川科化工有限公司 | Method for producing wet-process phosphoric acid by utilizing low-grade phosphorite |
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| CN103213964A (en) * | 2013-05-17 | 2013-07-24 | 成都川科化工有限公司 | Method for producing wet-process phosphoric acid by utilizing low-grade phosphorite |
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Cited By (1)
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| CN108117053A (en) * | 2017-12-22 | 2018-06-05 | 应城市嘉鸿技术服务科技有限公司 | It is a kind of to handle hardened soil with phytase so as to optimize the method for ardealite preparation process |
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