CN105523533B - The method for producing high-quality phosphoric acid and high-quality ardealite containing rare earth phosphate rock with regeneration phosphoric acid leaching - Google Patents
The method for producing high-quality phosphoric acid and high-quality ardealite containing rare earth phosphate rock with regeneration phosphoric acid leaching Download PDFInfo
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- CN105523533B CN105523533B CN201610044451.4A CN201610044451A CN105523533B CN 105523533 B CN105523533 B CN 105523533B CN 201610044451 A CN201610044451 A CN 201610044451A CN 105523533 B CN105523533 B CN 105523533B
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- phosphoric acid
- rare earth
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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
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- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The method for producing high-quality phosphoric acid and high-quality ardealite containing rare earth phosphate rock with regeneration phosphoric acid leaching, be will contain rare earth phosphate rock with regeneration phosphoric acid metering it is latter with enter one section leaching groove occur leaching reaction, afterwards, flocculant is added in slurry, clear liquid overflow is to calcium dihydrogen phosphate storage tank, slurry is added regeneration phosphoric acid and is continued to leach with two sections of leaching grooves are pumped to；After two sections of leaching reactions terminate, flocculant, clear liquid overflow to calcium dihydrogen phosphate storage tank are added in slurry, slurry is also entered calcium dihydrogen phosphate storage tank, formed the biphosphate calcium solution containing rare earth with two sections of filter presses, filtrate is pumped to；The concentrated sulfuric acid is added in the solution, the phosphoric acid containing ardealite and rare earth is obtained after reaction；Finally, the high-quality phosphoric acid containing rare earth and high-quality ardealite are obtained by press filtration.High-quality phosphoric acid and high-quality ardealite can be produced simultaneously with this method, while are created conditions for synthetical recovery association rare earth resources.Suitable for the phosphorus ore of middle-low grade association rare earth.
Description
Technical field
The present invention relates to the compound of phosphorus, more particularly to phosphoric acid, ardealite is directed to, further relates to rare earth, furthermore, it is understood that
It is related to the method with phosphoric acid leaching phosphorus ore preparing phosphoric acid.
Background technology
It is well known that traditional phosphoric acid by wet process is made from sulfuric acid extraction phosphorus ore, it is caused a large amount of in its production process
Ardealite is low due to quality, it is impossible to is comprehensively utilized well；Contain rare earth phosphate rock if used, the rare earth money of association in phosphorus ore
Source can largely enter ardealite and by dilution, hardly result in high-quality phosphoric acid and high-quality ardealite, therefore phosphorus ore middle rare earth resource
Not a duck soup is recycled, therefore the utilization containing rare earth phosphate rock is not easy to.It is so traditional for that can not be used containing rare earth phosphate rock
Technique.
Being related to the patent application utilized containing rare earth phosphate rock in Chinese patent database has No. 991174135《Rare earth crosses phosphorus
Sour calcium and its production method》, No. ZL2006100571056《A kind of rare earth addition and the rare earth calcium superphosphate containing the additive
And preparation method thereof》, No. ZL2006102009881《The method for reducing rare earth content in phosphoric acid》, No. ZL2007101797497
《A kind of using phosphorite ore deposit as raw material wet-method phosphoric acid and therefrom process of Extraction of rare earth》, No. ZL2009100787938
《It is a kind of using centrifugal extraction equipment from phosphoric acid gathering trace rare earth technique》, No. 2010101803875《One kind is answered containing rare earth
Ammonium magnesium phosphate slow release fertilizer of salt and preparation method thereof》, No. 2014107642837《Reclaimed from the phosphorus ore slag after production phosphoric acid dilute
The method of soil》Can not solve to produce high-quality phosphoric acid and high-quality ardealite from containing rare earth phosphate rock Deng, these above-mentioned patented technologies
Technical barrier.
The content of the invention
The present invention is intended to provide a kind of produce high-quality phosphoric acid and high-quality ardealite with regeneration phosphoric acid leaching containing rare earth phosphate rock
Method, resource containing rare earth phosphate rock can have both been made full use of to get back high-quality phosphoric acid and high-quality ardealite, so as to solve conventional wet phosphorus
The problem of a large amount of ardealite discarded objects is produced in acid production, reduces environmental protection pressure, and improve Business Economic Benefit.
The method for producing high-quality phosphoric acid and high-quality ardealite containing rare earth phosphate rock with regeneration phosphoric acid leaching that inventor provides, bag
Include following steps：
(1) it is latter with one section of leaching groove is entered by measuring with regeneration phosphoric acid that rare earth phosphate rock will be contained, make regeneration phosphoric acid with containing
One section of leaching reaction occurs for rare earth phosphate rock；
After (2) one sections of leaching reactions terminate, flocculant is added in slurry, clear liquid is separated with slurry, clear liquid overflow is extremely
Calcium dihydrogen phosphate storage tank, slurry are added regeneration phosphoric acid and are continued leaching reaction with two sections of leaching grooves are pumped to；
After (3) two sections of leaching reactions terminate, flocculant is added in slurry, clear liquid is separated with slurry, clear liquid overflow is extremely
Calcium dihydrogen phosphate storage tank, slurry also enter calcium dihydrogen phosphate storage tank with two sections of filter presses, the filtrate being press-filtered out is pumped to, and formation contains
The biphosphate calcium solution of rare earth；
(4) the calcium dihydrogen phosphate solution containing rare earth is pumped to desulfuration acid group groove, adds the concentrated sulfuric acid and free calcium in solution is anti-
Should, obtain the phosphoric acid containing ardealite and rare earth；
(5) phosphoric acid containing ardealite and rare earth obtains the high-quality phosphoric acid containing rare earth and high-quality phosphorus by filter press press filtration
Gypsum, the namely regenerated phosphoric acid of the phosphoric acid；
(6) the regeneration phosphoric acid part obtained returns to (1) step, the leaching operation of (2) step is used to leach phosphorus containing rare earth
Ore deposit, another part is as phosphoric acid finished product；So repeatedly, you can produce high-quality phosphoric acid and high-quality ardealite.
In the above method (1) step, the regeneration phosphoric acid be made with this method, the phosphoric acid of reuse, one section of leaching
The process conditions of reaction are control regeneration phosphoric acid and phosphorus concentrate liquid-solid ratioes 8: 1~15: 1,30 DEG C~80 DEG C of reaction temperature, during reaction
Between 2~6h.
In the above method (2) step, the flocculant is anion or PAMC；Two sections of leachings are anti-
The process conditions answered are controlled admittedly than 8: 1~15: 1,30 DEG C~80 DEG C of reaction temperature, 2~6h of reaction time.
In the above method (3) step, the flocculant is anion or PAMC.
In the above method (4) step, the concentrated sulfuric acid is the sulfuric acid that mass fraction is 98%, and sulfuric acid is molten with calcium dihydrogen phosphate
It is 60 ± 10 DEG C, 2~4h of reaction time that the reaction condition of liquid, which is controlled in temperature, and the mol ratio of sulfate radical and calcium ion is 1:1~
1.2:1。
In the above method (5) step, the high-quality phosphoric acid is with P2O5Count concentration 23%~26%, content of rare earth be 0.15~
0.25g/L phosphoric acid containing rare earth；The high-quality ardealite is that whiteness is more than 90%, and purity is more than 97% ardealite.
Inventor points out：Above-mentioned phosphoric acid containing rare earth can be used for recovering rare earth resource；Above-mentioned high-quality ardealite is after washing
Quality index reaches ardealite national standard GB/T23456-2009 Grade A standards, is adapted to using dry method α, wet method α technique productions 6.0
High strength gypsum powder more than level, national standard GB/ can be reached after the modified grinding of β building gypsum plasters that direct frying obtains
The plaster of Paris Grade A standard of T9776-2008 standards.
The method of the present invention can handle the mid low grade phosphate rock that association content of rare earth is only 0.06%~0.13%, with this work
Skill can obtain high-quality ardealite while high-quality phosphoric acid is produced, while be created for the comprehensive reutilization of association rare earth resources
Condition, by controlling suitable process conditions, the leaching rate of phosphorus can reach 95%~99%, and the leaching rate of rare earth can reach 85%
~90%, be advantageous to the utilization of the resource containing rare earth phosphate rock.High-quality ardealite is easy to apply, and solves in conventional wet phosphoric acid production
The problem that a large amount of ardealite discarded objects are difficult by is produced, greatly reduces environmental protection pressure, and improve Wet-process Phosphoric Acid Production
Economic benefit.Suitable for the phosphorus ore of middle-low grade association rare earth.
Brief description of the drawings
Fig. 1 is the process flow diagram of the inventive method.
Embodiment
Embodiment：
It is latter with one section of leaching groove is entered by measuring with regeneration phosphoric acid that rare earth phosphate rock will be contained, make regeneration phosphoric acid and contain rare earth
One section of leaching reaction occurs for phosphorus ore, and the process conditions of reaction are that control regenerates phosphoric acid and phosphorus concentrate liquid-solid ratio 8: 1~15: 1, reaction
30 DEG C~80 DEG C of temperature, 2~6h of reaction time；After one section of leaching reaction terminates, flocculant polyacrylamide is added in slurry,
Clear liquid is set to be separated with slurry, clear liquid overflow to calcium dihydrogen phosphate storage tank, slurry adds regeneration phosphoric acid with two sections of leaching grooves are pumped to
Continue leaching reaction, the process conditions of reaction are controlled admittedly than 8: 1~15: 1,30 DEG C~80 DEG C of reaction temperature, during reaction
Between 2~6h；After two sections of leaching reactions terminate, flocculant polyacrylamide is added in slurry, clear liquid is separated with slurry, clear liquid
To calcium dihydrogen phosphate storage tank, slurry also enters calcium dihydrogen phosphate storage tank with two sections of filter presses, the filtrate being press-filtered out is pumped to for overflow,
Form the biphosphate calcium solution containing rare earth；Calcium dihydrogen phosphate solution containing rare earth is pumped to desulfuration acid group groove, adds quality point
Number is 98% concentrated sulfuric acid, and it is 60 ± 10 DEG C that the reaction condition of sulfuric acid and biphosphate calcium solution, which control in temperature, the reaction time 2
The mol ratio of~4h, sulfate radical and calcium ion is 1:1~1.2:1, wherein sulfate radical is reacted with free calcium in solution, contained
There is the phosphoric acid of ardealite and rare earth；Finally, the phosphoric acid containing ardealite and rare earth is obtained containing the excellent of rare earth by filter press press filtration
Matter phosphoric acid and whiteness are more than 90%, and purity is more than 97% high-quality ardealite；Wherein high-quality phosphoric acid is with P2O5Meter concentration 23%~
26%th, content of rare earth is 0.15~0.25g/L phosphoric acid containing rare earth；An obtained regeneration phosphoric acid part returns to (1) step, (2)
The leaching operation of step, which is used to leach, contains rare earth phosphate rock, and another part is as phosphoric acid finished product；So repeatedly, you can produce high-quality phosphoric acid
With high-quality ardealite.
Claims (6)
1. the method for producing high-quality phosphoric acid and high-quality ardealite containing rare earth phosphate rock with regeneration phosphoric acid leaching, it is characterised in that this method
Comprise the following steps：
(1) it is latter with one section of leaching groove is entered by measuring with regeneration phosphoric acid that rare earth phosphate rock will be contained, make regeneration phosphoric acid and contain rare earth
One section of leaching reaction occurs for phosphorus ore；
After (2) one sections of leaching reactions terminate, flocculant is added in slurry, clear liquid is separated with slurry, clear liquid overflow to phosphoric acid
Calcium dihydrogen storage tank, slurry are added regeneration phosphoric acid and are continued leaching reaction with two sections of leaching grooves are pumped to；
After (3) two sections of leaching reactions terminate, flocculant is added in slurry, clear liquid is separated with slurry, clear liquid overflow to phosphoric acid
Calcium dihydrogen storage tank, slurry also enter calcium dihydrogen phosphate storage tank with two sections of filter presses, the filtrate being press-filtered out is pumped to, and formation contains rare earth
Biphosphate calcium solution；
(4) the calcium dihydrogen phosphate solution containing rare earth is pumped to desulfuration acid group groove, adds the concentrated sulfuric acid and is reacted with free calcium in solution,
Obtain the phosphoric acid containing ardealite and rare earth；
(5) phosphoric acid containing ardealite and rare earth obtains the high-quality phosphoric acid containing rare earth and high-quality phosphorus stone by filter press press filtration
Cream, the namely regenerated phosphoric acid of the phosphoric acid；
(6) the regeneration phosphoric acid part obtained returns to (1) step, the leaching operation of (2) step is used for leaching and contains rare earth phosphate rock,
Another part is as phosphoric acid finished product；So repeatedly, you can produce high-quality phosphoric acid and high-quality ardealite.
2. the method as described in claim 1, it is characterised in that in (1) step, the regeneration phosphoric acid is to be made, returned with this method
Phosphoric acid, the process conditions of one section of leaching reaction are that control regenerates phosphoric acid and phosphorus concentrate liquid-solid ratio 8: 1~15: 1, reaction
30 DEG C~80 DEG C of temperature, 2~6h of reaction time.
3. the method as described in claim 1, it is characterised in that in (2) step, the flocculant is that anion or cation gather
Acrylamide；The process conditions of two sections of leachings reaction are controlled admittedly than 8: 1~15: 1,30 DEG C~80 DEG C of reaction temperature, instead
2~6h between seasonable.
4. the method as described in claim 1, it is characterised in that in (3) step, the flocculant is that anion or cation gather
Acrylamide.
5. the method as described in claim 1, it is characterised in that in (4) step, the concentrated sulfuric acid is the sulphur that mass fraction is 98%
Acid, it is 60 ± 10 DEG C, 2~4h of reaction time that the reaction condition of sulfuric acid and biphosphate calcium solution, which control in temperature, sulfate radical and
The mol ratio of calcium ion is 1:1~1.2:1.
6. the method as described in claim 1, it is characterised in that in (5) step, the high-quality phosphoric acid is with P2O5Count concentration 23%
~26%, content of rare earth is 0.15~0.25g/L phosphoric acid containing rare earth；The high-quality ardealite is that whiteness is more than 90%, and purity is big
In 97% ardealite.
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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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| 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 |
| CN103213960A (en) * | 2013-05-17 | 2013-07-24 | 成都川科化工有限公司 | Method for producing phosphoric acid by decomposing low-grade phosphate rock with wet-process phosphoric acid |
| 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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- 2016-01-22 CN CN201610044451.4A patent/CN105523533B/en active Active
Patent Citations (4)
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| 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 |
| CN102220488A (en) * | 2011-05-31 | 2011-10-19 | 北京矿冶研究总院 | Method for separating rare earth from phosphate ore |
| CN103213960A (en) * | 2013-05-17 | 2013-07-24 | 成都川科化工有限公司 | Method for producing phosphoric acid by decomposing low-grade phosphate rock with wet-process phosphoric acid |
| 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 |
Non-Patent Citations (1)
| Title |
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| 含稀土磷精矿酸解过程稀土的分布规律;赵平等;《有色金属（冶炼部分）》;20151130(第11期);第33-35页 * |
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