CN105859167B - A method of Gao Bai, high-pure anhydrous calcium sulfate are prepared by ardealite - Google Patents
A method of Gao Bai, high-pure anhydrous calcium sulfate are prepared by ardealite Download PDFInfo
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Abstract
A method of Gao Bai, high-pure anhydrous calcium sulfate are prepared by ardealite, while handling ardealite with vitriol lixiviation method, using the organic impurities in extractant extraction ardealite, Gao Bai, high-purity anhydrous slufuric acid calcium product is made.On the one hand method of the invention uses inorganic impurity in vitriol lixiviation decomposing phosphogypsum, on the other hand organic impurities therein is extracted using extractant, simultaneously dexterously using organic flotation agent impurity to the absorption property of wherein insoluble inorganic impurity, when extracting organic flotation agent impurity, a large amount of insoluble inorganic impurity is removed, the nearly all impurity being achieved in efficient removing ardealite.The purpose that phosphogypsum slag preparation high-quality anhydrous slufuric acid calcium product can be realized using the method for the present invention, is had found for the high-grade gypsum resource of increasingly reduction instead of technology, industrial applications prospect with good economic efficiency and wide.
Description
Technical field
The invention belongs to bulk solid waste resource utilization field, in particular to it is a kind of by ardealite preparation Gao Bai,
The method of high-pure anhydrous calcium sulfate.
Background technique
It is increasing to the demand of gypsum with the fast development of China's building and building materials industry, while to the white of gypsum
Degree requirement is also higher and higher, in particular for interior painting and decorated articles.At the same time, high-grade gypsum resource gradually subtracts
It is few, therefore chemical gypsum (ardealite, fluorgypsum and desulfurized gypsum etc.) brightens through decoloration, improves purity and replace high-grade natural
Attention of the research of gypsum resource increasingly by industry and section pedant personnel.
Ardealite is to produce a kind of maximum chemical gypsum of discharge capacity, and during resulting from Wet-process Phosphoric Acid Production, solution is in acidity,
Slightly peculiar smell, because impure, appearance is in yellow-white, light gray-white or fine blackish-gray powder shape solid, and Blue Whiteness is 50 or so, prosperous
Extra white degree 70 or so, hence it is evident that requirement (magnanimous 70) of blue light lower than enterprise to similar gypsum product whiteness.1 ton of product of every production
(with P2O5Meter), 5 tons or so of ardealite will be generated.China's sulphur dioxide of phosphor chemical industry discharges about 70,000,000 tons of ardealite every year, and with
Annual 15% rate increases.It is more than 300,000,000 tons that China's ardealite, which adds up yield, at present, and storage is more than 2.5 hundred million tons, and it is provided
Source comprehensive utilization ratio is less than 10%.The accumulation of throwing aside of a large amount of ardealites does not only take up a large amount of soils, and there are huge environment
Risk.The content of calcium sulphate dihydrate is 90% or more in ardealite, and contains a small amount of quartz, undecomposed apatite, Yi Jiwei
The impurity such as phosphorus, fluorine, potassium, sodium, iron, aluminium, titanium and organic matter are measured, their presence affects the whiteness and purity of ardealite, and tight
Important place restricts its resource utilization.
Effectively to remove these impurity, the whiteness and purity of ardealite are improved, extends the application range of ardealite, both at home and abroad
Researcher has carried out a large amount of ardealite removal of impurities research and has explored, technology can substantially be divided into WATER-WASHING METHOD, lime neutralisation,
Ball-milling method, sieve method, floatation, calcination method and vitriol lixiviation method.
WATER-WASHING METHOD is high to the removal rate of soluble impurity and can remove most organic matter, but washes main scarce
Point is that production line is once invested greatly, and energy consumption is high, and sewage discharge will cause secondary pollution after washing.Obviously, washing process is not met
The national conditions that phosphate fertilizer plant, China small scale is dispersed again.
Lime neutralisation is to make phosphorus by the way that the residual acid in the alkaline matters such as quick lime, white lime and in ardealite is added
Titanium pigment, fluorine in gypsum are converted to indifferent salt, to eliminate Leaching Properties of Soluble Phosphorus, fluorine to the adverse effect of ardealite agglutination material, make
The condensation hardening of ardealite agglutination material tends to be normal, but the impurity in ardealite is there is no really removing, the whiteness of ardealite and
Purity does not also improve, and cannot eliminate influence of the organic matter to agglutination material performance.
Ball-milling method makes ardealite become dispersing distribution in the grain composition of normal distribution, increases agglutination material mobility, from root
The defect of hardenite porosity height, short texture, the deimpurity adverse effect but ball-milling treatment does not disappear are improved in sheet.Sieve
Point-score is only just used when content is especially high in smaller range for impurity, and to be also directed to different grain size ardealite after sieving
Impurity content it is respectively adopted corresponding pretreatment, this complex process, and investment is high, and treating capacity is small.
When floatation is using washing, the characteristic that organic matter is kept afloat is outstanding by what is floated on the surface by floatation equipment
Floating object matter removes, and this method can remove partial organic substances and part soluble impurity, but to the insoluble impurities in ardealite,
The especially biggish quartzy impurity removal effect of partial size is unsatisfactory, can not prepare qualified paring stone using flotation pretreatment
Cream.In the production process of phosphoric acid, floating agent inevitably joined, these floating agents finally largely enter solid phase
In residue, it is securely attached to ardealite surface, is difficult in washing warp float floatation equipment in this partial organic substances to be removed,
So floatation can not significantly improve the whiteness and purity of ardealite.
Calcination method is to carry out high-temperature calcination to ardealite at a temperature of 800 DEG C, so that titanium pigment and eutectic phosphorus are converted into
Inert pyrophosphate, organic matter and soluble F in the form of HF-Volatilization, to eliminate organic matter and foreign matter of phosphor, fluorine pair
The influence of ardealite performance, while the whiteness of ardealite also greatly improves.As (forged indirectly in CN 101033118A using outer burning
Burn) and interior burning (dinectly bruning) mixed calcining new process, land plaster that meet national standards has been produced, but when due to calcining
Phosphoric acid, fluoride volatilization are had, environment will be polluted, corrode equipment, high-temperature calcination energy consumption cost is larger, and product is anhydrous stone
Cream, active very little, using will receive considerable restraint, simultaneously because the maximum impurity of content is quartz in ardealite, content is greater than
6%, calcine technology can not remove these quartzy impurity, so calcination method can not produce Gao Bai, high-purity high-quality gypsum
Product.
Vitriol lixiviation method is at a certain temperature, to carry out acidleach to ardealite with the sulfuric acid solution that concentration is 30% or so
Processing obtains the ardealite product for meeting building gypsum requirement using filter, water washing to neutrality, and pickle liquor returns to wet process phosphorus
Acid system is used for decomposing phosphate rock, and complex acid carries out circulation leaching removal of impurities to ardealite to washing water again, and entire acidleach process will not be right
Environment causes secondary pollution.The method is up to 99% to the removal efficiency of phosphorus, and for the removal efficiency of fluorine up to 84%, whiteness is also increased to blue light
Whiteness 80 or so, can be made the ardealite of higher quality.However, studies have shown that even if 35% sulfuric acid at 120 DEG C, also not
The organic matter in ardealite can be made effectively to decompose, to the gypsum product (Blue Whiteness is 90 or more) of Gao Bai is made, only with acid
Leaching processing is no longer satisfied requirements, and since sulfuric acid is not reacted with quartz impurity, acidleach still has 3% or so after handling
Quartz particles are present in ardealite, this will seriously affect the purity of ardealite.
Research finds that influencing ardealite whiteness and the major impurity of purity is organic matter, SiO2.Organic matter is mainly derived from
The floating agent added during Wet-process Phosphoric Acid Production, SiO2It is mainly derived from the phosphorus ore of exploitation.It is miscellaneous only to remove these simultaneously
Matter, can just access Gao Bai, high-purity gypsum product, however there is presently no at a lower temperature, while it is miscellaneous to remove these
The document report of Gao Bai, high purity plaster product is made in matter.
Summary of the invention
Aiming at the problems existing in the prior art, the purpose of the present invention is to provide one kind prepares Gao Bai, height by ardealite
The method of pure dead plaster.It is raw material using the ardealite of ardealite especially phosphoric acid by wet process industrial discharge, in acid item
Under part, using spe medium handle ardealite, the calcium sulfate slurry obtained through two-phase laminated flow, using filter washing preparation Gao Bai,
High-pure anhydrous calcium sulfate, acidic aqueous solution and spe medium also can be recycled.
In order to achieve the above object, the present invention adopts the following technical scheme:
A method of Gao Bai, high-pure anhydrous calcium sulfate are prepared by ardealite, handle the same of ardealite with vitriol lixiviation method
When, using the organic impurities in extractant extraction ardealite, the inorganic impurity and organic impurities in ardealite can be removed simultaneously,
Gao Bai, high-purity anhydrous slufuric acid calcium product is made.
Preferably, the extractant is selected from sulfonated kerosene, atoleine, oleic acid, di-(2-ethylhexyl)phosphoric acid ester, ring
One or more of hexane, tributyl phosphate, gasoline, benzene.
Due to containing a large amount of inorganic impurity and organic impurities in ardealite, using conventional impurity and purification method, it is difficult
While improving whiteness, then improve purity.Organic impurities in ardealite is added during being mainly derived from phosphoric acid production
Floating agent, these floating agents are firmly adhered to ardealite surface, are difficult to remove by washing, can only be forged using high temperature
Burn off is gone, but it is high to calcine not only energy consumption, but also cannot effectively remove the such as impurity quartz of the inorganic impurity in ardealite again.
However the present invention passes through largely research shows that these floating agent organic impurities are to the inorganic impurity in ardealite
With very strong collecting ability, if handle ardealite with vitriol lixiviation method, using in extractant extraction ardealite
Organic impurities can remove inorganic impurity and organic impurities in ardealite simultaneously.
The present invention obtains the whiteness of Gao Bai, high-purity anhydrous slufuric acid calcium product 90 or more, and the purity of calcium sulfate exists substantially
99% or more.
Preferably, the method, comprising the following steps:
(1) after mixing by sulfuric acid solution and ardealite, it is added in kettle；
(2) it after extractant being added in the mixed slurry obtained to step (1), stirs, reaction；
(3) it stands after reaction, mixed slurry is released, but do not release extractant organic layer, to realize extractant
Layer is separated with pulp layer；
(4) mixed slurry that step (3) obtains is filtered, washed to obtain Gao Bai, high-purity anhydrous slufuric acid calcium product.
The method that the present invention is combined using acidleach and extraction phase, at a lower temperature, while removing having in ardealite
Machine object, inorganic impurity such as SiO2Equal impurity, prepare Gao Bai, high-pure anhydrous calcium sulfate, and can make acidic aqueous solution and spe medium
It is recycled, is achieved in ardealite and simply and effectively decolourizes to brighten, improve purity.
Preferably, ardealite described in step (1) is the industrial residue phosphorus generated in phosphoric acid by wet process industrial processes
Gypsum.
Preferably, the ardealite is screened, and the partial size after preferably sieving is 20 mesh hereinafter, preferably 20~200 mesh.
Preferably, the mass concentration of the sulfuric acid solution is 5~50%.
Preferably, the liquid-solid ratio of the sulfuric acid solution and ardealite is 10~1:1mL/g.From economy and purify product
Quality consideration, liquid-solid ratio are greater than 10:1mL/g, can waste sulfuric acid solution significantly, increase operating cost, and small and 1:1mL/g again can shadow
The effect of purification is rung, just there is practical value within the above range, therefore, it is 10~1 that the present invention, which selects the range of liquid-solid ratio:
1mL/g。)
Preferably, the kettle is enamel still, preferably the enamel still with stirring and heating mantle.
Preferably, the mass ratio of step (2) extractant and ardealite is 5~0.5:1.It is produced from economy and purification
The quality of product considers that mass ratio is greater than 5:1, can waste extractant significantly, increase operating cost, can reduce again less than 0.5:1 net
The effect of change cannot get the purification gypsum of high-purity Gao Bai, just have practical value within the above range, therefore, the present invention selects for institute
The range for selecting the mass ratio of extractant and ardealite is 5~0.5:1.)
Preferably, the temperature of step (2) described reaction is 50~120 DEG C, the time of reaction is 20~60min.(temperature
Setting be according to optimization of process conditions: the too low whiteness and purity that can reduce product of temperature, temperature is too high not only to waste heat
Can and it make operating difficulties, so the present invention selects the range of temperature for 50~120 DEG C.Setting and root about the time
According to optimization of process conditions: the time is too short, reacts without carrying out reacting too long, and will increase cost completely, so the present invention selects
The range in reaction time is 20~60min.
Preferably, the extraction oxidant layer that step (3) obtains is filtered, extractant liquid phase and solid phase residue are isolated
Phase, extractant liquid phase are re-used for realizing and be recycled that it is white that solid phase residue is mutually adhered to the influence of ardealite surface in step (2)
The impurity of degree and purity, the inside contains a large amount of valuable material, can further extract separation.
Preferably, step (4) washing is washing to weak acid-alkalescent, preferably to neutral.
Preferably, filtered filtrate can return to phosphoric acid by wet process workshop section for decomposing phosphate rock.
Preferably, washing water can be re-used for configuration sulfuric acid solution recycling.
The beneficial effects of the present invention are:
On the one hand using inorganic impurity in vitriol lixiviation decomposing phosphogypsum, on the other hand have using extractant extraction is therein
Machine impurity, while dexterously using organic flotation agent impurity to the absorption property of wherein insoluble inorganic impurity, it is organic floating extracting
When selecting agent impurity, a large amount of insoluble inorganic impurity is removed, is achieved in nearly all miscellaneous in efficient removing ardealite
Matter；
It can realize the purpose of phosphogypsum slag preparation high-quality anhydrous slufuric acid calcium product, using the method for the present invention increasingly to subtract
Few high-grade gypsum resource has found instead of technology, industrial applications prospect with good economic efficiency and wide.
Detailed description of the invention
Fig. 1 is the Gao Bai prepared involved in the embodiment of the present invention 3 by ardealite, high-pure anhydrous calcium sulfate XRD diagram；
Fig. 2 is to be schemed involved in the embodiment of the present invention 3 by Gao Bai, the high-pure anhydrous calcium sulfate SEM of ardealite preparation.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for helping to understand the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1.
Certain the ammonium phosphate plant ardealite selected in the present embodiment, wherein CaO content is 33.64%, SO3Content 56.92%, it is miscellaneous
Matter SiO2Content 6.31%, Blue Whiteness 50.67, Hunter whiteness 72.75, specific embodiment is as follows:
(1) ardealite is sized to less than 20 mesh partial sizes；
(2) sulfuric acid solution that configuration concentration is 5%；
(3) sulfuric acid solution obtained by step (2) and step (1) resulting ardealite are uniformly mixed according to liquid-solid ratio 10:1
Afterwards, it is added in the enamel still with stirring and heating mantle；
(4) it after the extractant of extractant and phosphogypsum quality ratio 5:1 are added in the mixed slurry obtained to step (3), opens
Beginning stirs at speed of agitator 300rpm；
(5) 120 DEG C are set to the enamel still with heating mantle in step (3), starts timing after being warming up to set temperature, makes
The mixed slurry that step (3) obtains sufficiently reacts 60min；
(6) to end of reaction, stop heating and stirring, release mixed slurry from enamel still bottom after standing a period of time,
But extractant organic layer is not released, realizes extraction oxidant layer and pulp layer separation；
(7) mixed slurry that step (6) obtains is filtered, washs to neutrality and obtains anhydrous slufuric acid calcium product, filtrate
It returns to phosphoric acid by wet process workshop section and is used for decomposing phosphate rock, washing water is re-used for step (2) configuration sulfuric acid solution and is recycled；
(8) the extraction oxidant layer that step (6) obtains is filtered, isolates extractant liquid phase and solid phase residue phase, liquid phase
Extractant is re-used for realizing and be recycled that solid phase residue, which is adhered to ardealite surface, influences whiteness and purity in step (4)
Impurity, to further extract separation.
(9) anhydrous slufuric acid calcium product is obtained in an oven at 80 DEG C after dry 2h to step (7), carries out whiteness and purity is surveyed
Examination, result are Blue Whiteness 90.5, Hunter whiteness 94.56, dead plaster purity 99.2%, impurity SiO2Content
0.20%.
Embodiment 2.
Certain the ammonium phosphate plant ardealite selected in the present embodiment, wherein CaO content is 33.64%, SO3Content 56.92%, it is miscellaneous
Matter SiO2Content 6.31%, Blue Whiteness 50.67, Hunter whiteness 72.75, specific embodiment is as follows:
(1) ardealite is sized to less than 200 mesh partial sizes；
(2) sulfuric acid solution that configuration concentration is 50%；
(3) by sulfuric acid solution obtained by step (2) and step (1) resulting ardealite according to liquid-solid ratio 1:1 after mixing,
It is added in the enamel still with stirring and heating mantle；
(4) it after the extractant of extractant and phosphogypsum quality ratio 1:1 are added in the mixed slurry obtained to step (3), opens
Beginning stirs at speed of agitator 300rpm；
(5) 50 DEG C are set to the enamel still with heating mantle in step (3), starts timing after being warming up to set temperature, makes
The mixed slurry that step (3) obtains sufficiently reacts 30min；
(6) to end of reaction, stop heating and stirring, release mixed slurry from enamel still bottom after standing a period of time,
But extractant organic layer is not released, realizes extraction oxidant layer and pulp layer separation；
(7) mixed slurry that step (6) obtains is filtered, washs to neutrality and obtains anhydrous slufuric acid calcium product, filtrate
It returns to phosphoric acid by wet process workshop section and is used for decomposing phosphate rock, washing water is re-used for step (2) configuration sulfuric acid solution and is recycled；
(8) the extraction oxidant layer that step (6) obtains is filtered, isolates extractant liquid phase and solid phase residue phase, liquid phase
Extractant is re-used for realizing and be recycled that solid phase residue, which is adhered to ardealite surface, influences whiteness and purity in step (4)
Impurity, to further extract separation.
(9) anhydrous slufuric acid calcium product is obtained in an oven at 80 DEG C after dry 2h to step (7), carries out whiteness and purity is surveyed
Examination, result are Blue Whiteness 90.7, Hunter whiteness 95.1, dead plaster purity 99.3%, impurity SiO2Content 0.18%.
Embodiment 3.
Certain the ammonium phosphate plant ardealite selected in the present embodiment, wherein CaO content is 33.64%, SO3Content 56.92%, it is miscellaneous
Matter SiO2Content 6.31%, Blue Whiteness 50.67, Hunter whiteness 72.75, specific embodiment is as follows:
(1) ardealite is sized to less than 50 mesh partial sizes；
(2) sulfuric acid solution that configuration concentration is 35%；
(3) by sulfuric acid solution obtained by step (2) and step (1) resulting ardealite according to liquid-solid ratio 5:1 after mixing,
It is added in the enamel still with stirring and heating mantle；
(4) it after the extractant of extractant and phosphogypsum quality ratio 3:1 are added in the mixed slurry obtained to step (3), opens
Beginning stirs at speed of agitator 300rpm；
(5) 80 DEG C are set to the enamel still with heating mantle in step (3), starts timing after being warming up to set temperature, makes
The mixed slurry that step (3) obtains sufficiently reacts 30min；
(6) to end of reaction, stop heating and stirring, release mixed slurry from enamel still bottom after standing a period of time,
But extractant organic layer is not released, realizes extraction oxidant layer and pulp layer separation；
(7) mixed slurry that step (6) obtains is filtered, washs to neutrality and obtains anhydrous slufuric acid calcium product, filtrate
It returns to phosphoric acid by wet process workshop section and is used for decomposing phosphate rock, washing water is re-used for step (2) configuration sulfuric acid solution and is recycled；
(8) the extraction oxidant layer that step (6) obtains is filtered, isolates extractant liquid phase and solid phase residue phase, liquid phase
Extractant is re-used for realizing and be recycled that solid phase residue, which is adhered to ardealite surface, influences whiteness and purity in step (4)
Impurity, to further extract separation.
(9) anhydrous slufuric acid calcium product is obtained in an oven at 80 DEG C after dry 2h to step (7), carries out whiteness and purity is surveyed
Examination, result are Blue Whiteness 90.18, Hunter whiteness 92.35, dead plaster purity 99.0%, impurity SiO2Content
0.30%.
Fig. 1 is the Gao Bai prepared involved in the present embodiment by ardealite, high-pure anhydrous calcium sulfate XRD diagram.It can from Fig. 1
To find out that product prepared by the present embodiment contains only dead plaster object phase, other objects are not detected and mutually exist.Fig. 2 is this
Schemed involved in embodiment by Gao Bai, the high-pure anhydrous calcium sulfate SEM of ardealite preparation.As can be seen from Figure 2 the present embodiment
Prepared product is rod-shpaed particle, and no other pattern particles exist.Thus it can illustrate the present embodiment combined with Figure 1 and Figure 2,
Prepared product is Gao Bai, high-pure anhydrous calcium sulfate.
Embodiment 4.
Certain the ammonium phosphate plant ardealite selected in the present embodiment, wherein CaO content is 33.64%, SO3Content 56.92%, it is miscellaneous
Matter SiO2Content 6.31%, Blue Whiteness 50.67, Hunter whiteness 72.75, specific embodiment is as follows:
(1) ardealite is sized to less than 100 mesh partial sizes；
(2) sulfuric acid solution that configuration concentration is 20%；
(3) by sulfuric acid solution obtained by step (2) and step (1) resulting ardealite according to liquid-solid ratio 3:1 after mixing,
It is added in the enamel still with stirring and heating mantle；
(4) it after the extractant of extractant and phosphogypsum quality ratio 4:1 are added in the mixed slurry obtained to step (3), opens
Beginning stirs at speed of agitator 300rpm；
(5) 75 DEG C are set to the enamel still with heating mantle in step (3), starts timing after being warming up to set temperature, makes
The mixed slurry that step (3) obtains sufficiently reacts 45min；
(6) to end of reaction, stop heating and stirring, release mixed slurry from enamel still bottom after standing a period of time,
But extractant organic layer is not released, realizes extraction oxidant layer and pulp layer separation；
(7) mixed slurry that step (6) obtains is filtered, washs to neutrality and obtains anhydrous slufuric acid calcium product, filtrate
It returns to phosphoric acid by wet process workshop section and is used for decomposing phosphate rock, washing water is re-used for step (2) configuration sulfuric acid solution and is recycled；
(8) the extraction oxidant layer that step (6) obtains is filtered, isolates extractant liquid phase and solid phase residue phase, liquid phase
Extractant is re-used for realizing and be recycled that solid phase residue, which is adhered to ardealite surface, influences whiteness and purity in step (4)
Impurity, to further extract separation.
(9) anhydrous slufuric acid calcium product is obtained in an oven at 80 DEG C after dry 2h to step (7), carries out whiteness and purity is surveyed
Examination, result are Blue Whiteness 90.1, Hunter whiteness 93.35, dead plaster purity 98.98%, impurity SiO2Content
0.33%.
Embodiment 5.
Certain the ammonium phosphate plant ardealite selected in the present embodiment, wherein CaO content is 33.64%, SO3Content 56.92%, it is miscellaneous
Matter SiO2Content 6.31%, Blue Whiteness 50.67, Hunter whiteness 72.75, specific embodiment is as follows:
(1) ardealite is sized to less than 150 mesh partial sizes；
(2) sulfuric acid solution that configuration concentration is 45%；
(3) by sulfuric acid solution obtained by step (2) and step (1) resulting ardealite according to liquid-solid ratio 2:1 after mixing,
It is added in the enamel still with stirring and heating mantle；
(4) after the extractant of extractant and phosphogypsum quality ratio 0.5:1 are added in the mixed slurry obtained to step (3),
Start to stir at speed of agitator 300rpm；
(5) 90 DEG C are set to the enamel still with heating mantle in step (3), starts timing after being warming up to set temperature, makes
The mixed slurry that step (3) obtains sufficiently reacts 40min；
(6) to end of reaction, stop heating and stirring, release mixed slurry from enamel still bottom after standing a period of time,
But extractant organic layer is not released, realizes extraction oxidant layer and pulp layer separation；
(7) mixed slurry that step (6) obtains is filtered, washs to neutrality and obtains anhydrous slufuric acid calcium product, filtrate
It returns to phosphoric acid by wet process workshop section and is used for decomposing phosphate rock, washing water is re-used for step (2) configuration sulfuric acid solution and is recycled；
(8) the extraction oxidant layer that step (6) obtains is filtered, isolates extractant liquid phase and solid phase residue phase, liquid phase
Extractant is re-used for realizing and be recycled that solid phase residue, which is adhered to ardealite surface, influences whiteness and purity in step (4)
Impurity, to further extract separation.
(9) anhydrous slufuric acid calcium product is obtained in an oven at 80 DEG C after dry 2h to step (7), carries out whiteness and purity is surveyed
Examination, result are Blue Whiteness 90.76, Hunter whiteness 94.87, dead plaster purity 99.26%, impurity SiO2Content
0.21%.
Embodiment 6.
Certain the ammonium phosphate plant ardealite selected in the present embodiment, wherein CaO content is 33.64%, SO3Content 56.92%, it is miscellaneous
Matter SiO2Content 6.31%, Blue Whiteness 50.67, Hunter whiteness 72.75, specific embodiment is as follows:
(1) ardealite is sized to less than 60 mesh partial sizes；
(2) sulfuric acid solution that configuration concentration is 30%；
(3) by sulfuric acid solution obtained by step (2) and step (1) resulting ardealite according to liquid-solid ratio 4:1 after mixing,
It is added in the enamel still with stirring and heating mantle；
(4) after the extractant of extractant and phosphogypsum quality ratio 0.5:1 are added in the mixed slurry obtained to step (3),
Start to stir at speed of agitator 300rpm；
(5) 85 DEG C are set to the enamel still with heating mantle in step (3), starts timing after being warming up to set temperature, makes
The mixed slurry that step (3) obtains sufficiently reacts 35min；
(6) to end of reaction, stop heating and stirring, release mixed slurry from enamel still bottom after standing a period of time,
But extractant organic layer is not released, realizes extraction oxidant layer and pulp layer separation；
(7) mixed slurry that step (6) obtains is filtered, washs to neutrality and obtains anhydrous slufuric acid calcium product, filtrate
It returns to phosphoric acid by wet process workshop section and is used for decomposing phosphate rock, washing water is re-used for step (2) configuration sulfuric acid solution and is recycled；
(8) the extraction oxidant layer that step (6) obtains is filtered, isolates extractant liquid phase and solid phase residue phase, liquid phase
Extractant is re-used for realizing and be recycled that solid phase residue, which is adhered to ardealite surface, influences whiteness and purity in step (4)
Impurity, to further extract separation.
(9) anhydrous slufuric acid calcium product is obtained in an oven at 80 DEG C after dry 2h to step (7), carries out whiteness and purity is surveyed
Examination, result are Blue Whiteness 91.36, Hunter whiteness 94.73, dead plaster purity 99.38%, impurity SiO2Content
0.15%.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (11)
1. a kind of method for preparing Gao Bai, high-pure anhydrous calcium sulfate by ardealite, which is characterized in that handle phosphorus with vitriol lixiviation method
While gypsum, using the organic impurities in extractant extraction ardealite, Gao Bai, high-purity anhydrous slufuric acid calcium product, tool is made
Body the following steps are included:
(1) it after mixing sulfuric acid solution and ardealite, is added in kettle；
(2) after extractant being added in the mixed slurry obtained to step (1), stirring, in 50~120 DEG C of 20~60min of reaction；
(3) it stands after reaction, releases mixed slurry, realize extraction oxidant layer and pulp layer separation；
(4) mixed slurry that step (3) obtains is filtered, washed to obtain Gao Bai, high-purity anhydrous slufuric acid calcium product；
The extractant is selected from sulfonated kerosene, atoleine, oleic acid, di-(2-ethylhexyl)phosphoric acid ester, hexamethylene, tricresyl phosphate fourth
One or more of ester, gasoline, benzene；
The liquid-solid ratio of sulfuric acid solution described in step (1) and ardealite is 10~1:1mL/g；
The kettle is the enamel still with stirring and heating mantle.
2. the method according to claim 1, wherein the mass ratio of the extractant and ardealite is 5~0.5:
1。
3. according to the method described in claim 2, it is characterized in that, ardealite described in step (1) is raw for phosphoric acid by wet process industry
The industrial residue phosphogypsum generated during producing.
4. according to the method described in claim 3, partial size after screening is 20 mesh it is characterized in that, the ardealite is screened
Below.
5. according to the method described in claim 4, it is characterized in that, the ardealite is screened, the partial size after screening is 20~
200 mesh.
6. the method according to claim 1, wherein the mass concentration of the sulfuric acid solution is 5~50%.
7. method according to claim 1-6, which is characterized in that the extraction oxidant layer for obtaining step (3) carries out
Extractant liquid phase and solid phase residue phase are isolated in filtering, and extractant liquid phase is re-used for realizing in step (2) and be recycled, Gu
Contain valuable material inside phase residue phase, further extracts separation.
8. method according to claim 1-6, which is characterized in that step (4) washing is washing to weak acid-
Alkalescent.
9. according to the method described in claim 8, it is characterized in that, step (4) washing is washing to neutrality.
10. method according to claim 1-6, which is characterized in that the filtered filtrate of step (4) returns to wet process
Phosphoric acid workshop section is used for decomposing phosphate rock.
11. according to the method described in claim 8, it is characterized in that, washing water is re-used for configuration sulfuric acid solution recycling.
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