CN101597147A - The processing method of a kind of phosphogypsum, desulphurization gypsum for preparing high strength plaster of Paris - Google Patents
The processing method of a kind of phosphogypsum, desulphurization gypsum for preparing high strength plaster of Paris Download PDFInfo
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- CN101597147A CN101597147A CNA2009100599178A CN200910059917A CN101597147A CN 101597147 A CN101597147 A CN 101597147A CN A2009100599178 A CNA2009100599178 A CN A2009100599178A CN 200910059917 A CN200910059917 A CN 200910059917A CN 101597147 A CN101597147 A CN 101597147A
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- phosphogypsum
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- paris
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
- C04B11/262—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke waste gypsum other than phosphogypsum
- C04B11/264—Gypsum from the desulfurisation of flue gases
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00025—Aspects relating to the protection of the health, e.g. materials containing special additives to afford skin protection
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to provide the processing method of a kind of phosphogypsum, desulphurization gypsum for preparing high strength plaster of Paris.This method comprises the steps: that (1) raw material consists of by mass percentage: composite curing agent 0.5~2%, and 1.5~4 parts of % of compound alkali-activator, surplus is phosphogypsum or desulfurated plaster; (2) the described raw material of step (1) is mixed after, enter calcining furnace calcining at constant temperature 2~3h in 150~200 ℃ scope; (3) with the raw material naturally cooling after step (2) calcining, cooling is after the levigate processing of ball milling; (4) the raw material ageing 3~4 after levigate is promptly with step (3).The present invention can avoid secondary environmental pollution effectively, significantly reduced in the phosphogypsum contained trace element to the harm of human body and environment, change the phosphogypsum particle simultaneously and be normal distribution, shortcomings such as the size distribution height is heavily concentrated, mobile poor, the water requirement height of agglutination material, short texture, intensity are low can prepare high-intensity half water phosphogypsum powder and desulfurated plaster powder.
Description
Technical field
The present invention relates to the processing method and the using method thereof of a kind of phosphogypsum, desulphurization gypsum for preparing high strength plaster of Paris.
Background technology
Phosphogypsum is the trade waste of Wet-process Phosphoric Acid Production process discharging in the phosphorous chemical industry, produces one ton of phosphoric acid by wet process (with P
2O
5Meter) produces 4.5~5 tons of phosphogypsums.The main component of phosphogypsum is a calcium sulfate, and chemical formula is CaSO
42H
2O contains multiple other impurity in addition.Impurity such as institute's fluoride, free phosphoric acid, organism, radioactivity are to cause phosphogypsum to cause the principal element of environmental pollution in the process of storing up in the phosphogypsum.Storing up in a large number of phosphogypsum not only occupied land resources, owing to erode, drench with rain and caused the pollution of atmosphere, water system and soil.The Long contact time phosphogypsum can cause people's pathology.
China has and enriches phosphate rock resource, and wherein Guizhou Province is China topmost phosphorous chemical industry base, but phosphorous chemical industry produces a large amount of industrial waste phosphogypsum difficult treatment, contaminate environment.Nowadays, be that the new type block brick of raw material production has begun the instead of clay brick with the phosphogypsum, become " leading role " of Guizhou construction market gradually.It is reported that building energy consumption has accounted for 28% of whole society's terminal energy consumption at present, especially the large public building energy consumption is higher, and the floor area of building less than 4% accounts for 22% of national town building area total energy consumption.And Guizhou Province's past materials for wall is ruined the field every year and is fetched earth 1.7 ten thousand mu mainly based on clay solid brick.Meanwhile, economize as the energy and aluminium industry, phosphorous chemical industry sparetime university, the trade waste of the annual discharging in Guizhou reaches up to ten million tons.
Existing comprehensive utilization of phosphogypsum rate is not high, mainly due to containing more impurity in the phosphogypsum, the 2nd, it is ripe that existing phosphogypsum prepares the technology of high-strength plaster of Paris is that all right, and there is the shortcoming that time of coagulation is long, intensity is low, flowability is poor, the standard consistency water requirement is big in the gypsum of preparation.
Summary of the invention
Technical problem to be solved by this invention provides the processing method of a kind of phosphogypsum, desulphurization gypsum for preparing high strength plaster of Paris, the plaster of Paris of this processing method preparation can overcome the phosphogypsum particle and be normal distribution, and the size distribution height is heavily concentrated, mobile poor, the water requirement height of agglutination material, short texture, shortcoming that intensity is low.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the processing method of a kind of phosphogypsum, desulphurization gypsum for preparing high strength plaster of Paris, comprise the steps: that (1) raw material consists of by mass percentage: composite curing agent 0.5~2%, 1.5~4 parts of % of compound alkali-activator, surplus is phosphogypsum or desulfurated plaster; (2) the described raw material of step (1) is mixed after, enter calcining furnace calcining at constant temperature 2~3h in 150~200 ℃ scope; (3) with the raw material naturally cooling after step (2) calcining, cooling is after the levigate processing of ball milling; (4) the raw material ageing after levigate 3~4 days is promptly with step (3).The calcining at constant temperature in 150~200 ℃ scope here is meant that any one temperature between 150~200 ℃ carries out calcining at constant temperature.
Particularly, raw material consists of by mass percentage in the described step (1): composite curing agent 1~2%, and 2~4 parts of % of compound alkali-activator, surplus is a phosphogypsum.Or raw material consists of by mass percentage in the described step (1): composite curing agent 0.5~1%, and 1.5~3 parts of % of compound alkali-activator, surplus is a desulfurated plaster.Described composite curing agent is metallic salts such as potassium, magnesium, aluminium, silicon, sulphur, and compound alkali-activator is calcium hydroxide, sial alkalescence waste etc.
Because the phosphogypsum and the plaster of paris difference aspect composition and mechanism, make it can not replace the plaster of paris to be directly used in the production building materials of gypsum, therefore phosphogypsum being prepared into two plaster of Paris must carry out pre-treatment to phosphogypsum, removes the influence of main detrimental impurity and improves the shortcoming that phosphogypsum time of coagulation is long, intensity is low, flowability is poor, the standard consistency water requirement is big.Because the source of phosphogypsum and phosphorus ore, and the composition of phosphorus ore and produce the phosphoric acid process condition and there are differences, make phosphogypsum impurities component quite complicated, be which type of technology of employing so when selecting phosphogypsum for use, at first will determine producer.It has been generally acknowledged that: the phosphogypsum foreign matter content of two water conservancy projects skill by-product is maximum; The phosphogypsum foreign matter content of half water~two water laws and two water~half water law by-product is less relatively.Impurity in the phosphogypsum comprises three major types: 1, free phosphoric acid and sulfuric acid are the acid of filtration residue in Wet-process Phosphoric Acid Production, and free acid can produce certain corrodibility to the structure building materials, and the setting time that also can prolong gypsum simultaneously makes the gypsum strength degradation; 2, titanium pigment (comprising free phosphoric acid and mono-calcium phosphate etc.), during aquation, can generate the tricalcium phosphate of indissoluble with the Ca ionic reaction easily, and adhere to the phosphogypsum surface, thereby stop further aquation of gypsum and stripping, make phosphogypsum prolongation time of coagulation, short texture, intensity reduce, also have fluorochemical in addition, when being higher than 0.3%, can significantly reduce fluorine content the intensity of phosphogypsum, the gypsum sets that the slows down time; 3, organic substance mainly is distributed in the phosphogypsum surface, and is bigger to the phosphogypsum quality influence, can make the plastering surface blackening, long green hair, the setting rate that slows down, reduction product strength.In sum, seek out good building gypsum plaster, must carry out pre-treatment to phosphogypsum, this is the key point of the various gypsum the finished product of preparation, have only by just can obtain the gypsum product of high strength, water-tolerant again through chemical modification to the building gypsum plaster that obtains after the phosphogypsum pre-treatment, could be more widely used at building field, otherwise will be subjected to very big restriction.The pretreatment process of phosphogypsum is a lot, comprising WATER-WASHING METHOD, neutralisation, flotation process, sudden strain of a muscle burning method etc., and WATER-WASHING METHOD technology maturation wherein, effect is better, the gypsum stable performance after the processing, external this kind method that mostly is that adopts.But this method complex process, investment is big, and water consumption and energy consumption are big, and the sewage after the washing must be handled and can discharge through specific equipment, otherwise can cause secondary pollution.Neutralisation adopts among the cheap CaO and acid, fluorine in the phosphogypsum, make it be converted into the inertia difficulty soluble salt, adjust the pH value of phosphogypsum, residual acid is to its Effect on Performance in the elimination phosphogypsum, the lime blending amount of controlling well is the key of lime neutralisation, this method technology is simple, less investment, do not produce pollution, effect is remarkable, and it is convenient to get material, and therefore adopting neutralisation that phosphogypsum is carried out pre-treatment is a kind of economic, practical, effective pretreatment mode, but this method can not be eliminated organic detrimentally affect to its performance in the phosphogypsum.Therefore, the present invention adopts method for calcinating to eliminate organic problem simultaneously.
The present invention adopts the technical process of neutralisation and mechanism to be: 1, at first the phosphogypsum of phosphogypsum manufacturer production is carried out facies analysis, draw the content of free phosphoric acid, fluorine, and draw the volume that adds unslaked lime or composite curing agent, compound alkali-activator by experiment.2, will determine that good above-mentioned raw materials mixes; 3, calcining, usually phosphogypsum contains 20~30% free-water and 20% crystal water, also is referred to as phosphogypsum dihydrate, and the phosphogypsum dihydrate heating condition can transform temperature difference, transformation efficiency difference to semi-hydrated gypsum, dehydrated gyp-down.Want half good water plaster of Paris of processability, require semi-hydrated gypsum content height, dehydrated gyp-content is low, so just must select suitable temperature.It is similar to the plaster of paris that phosphogypsum is converted into the dewatering Principle of plaster of Paris, but because of the existence of impurity in the phosphogypsum, itself and plaster of paris dehydration temperaturre are had than big difference.Usually along with calcining temperature raises, transformation ratio and intensity are ascendant trends, and when peaking, this temperature can be defined as the calcining temperature of this phosphogypsum.Simultaneously, experiment shows, because gypsum is the poor conductor of heat, after so the gypsum particle surface temperature reaches design temperature, its internal temperature but is lower than design temperature, can cause the structure phase skewness of phosphogypsum, therefore, need certain constant temperature time, along with the prolongation of constant temperature time, plaster of Paris intensity and transformation ratio increase, but long intensity can descend to some extent, consider that from over-all properties and energy-conservation angle 2h is a best constant temperature time point.4, ball-milling processing, there are significant difference in the phosphogypsum microstructure and the plaster of paris, and dihydrate gypsum crystal is based on six panel shapes in the phosphogypsum, and particle is normal distribution, crystal is even, regular, this particle characteristic make its mobile poor, water requirement is high, short texture, intensity are lower.Just eliminate the influence of main detrimental impurity in the phosphogypsum by preprocessing means such as neutralization, screening, calcinings, and the size distribution of phosphogypsum, form etc. are not exerted an influence, and be to improve the effective means of phosphogypsum grain pattern by ball-milling processing, can make even, the regular platy structure of phosphogypsum present column, diversified particle form such as granular, simultaneously can increase consolidating material, its water requirement is reduced significantly, increased flowability, made hardenite clearance rate defective high and short texture be able to basic solution.Show that by a large amount of experiments ball milling combines with compound pre-treatment such as neutralization, calcinings, just can prepare the high-grade plaster of Paris.Adverse consequencess such as 6, ageing owing to contain a certain amount of dehydrated gyp-phase in the building gypsum plaster of calcining gained, causes the plaster of Paris water consumption to beat, and time of coagulation is long, and hardening strength is lower, for improving the performance of plaster of Paris, must be through ageing after a while.Along with the prolongation of digestion time, consumptive use of water normal consistence reduces, and resistance to compression, folding strength improve, and concrete digestion time can be drawn by experimental data.
The plaster of Paris of the present invention's preparation can be widely used in building productses such as high-performance light composite gypsum body of wall, building block, light wall brick, brushing gypsum, gesso.
To sum up, the invention has the beneficial effects as follows:
1, the present invention can remove impurity such as phosphorus, fluorine, organism to phosphogypsum, makes its volatilization or is converted into harmless inert substance, as Calcium Pyrophosphate and phosphoric acid salt, aluminate class etc.The present invention can avoid secondary environmental pollution effectively, has significantly reduced in the phosphogypsum contained trace element to the harm of human body and environment.Changed the phosphogypsum particle simultaneously and be normal distribution, shortcoming such as the size distribution height is heavily concentrated, mobile poor, the water requirement height of agglutination material, short texture, intensity are low.
2, the present invention can generate the C-S-H (hydrated calcium silicate gel) with gellifying property to desulfurated plaster, and aquation generates Ca (OH) on the other hand
2, can change the solubleness and the dissolution rate of gypsum, make desulfurated plaster have the gelling material of air-setting and hydraulicity double properties, its intensity is improved a lot.
Embodiment
The processing method of phosphogypsum of the present invention, desulphurization gypsum for preparing high strength plaster of Paris comprises the steps:
(1) raw material consists of by mass percentage: composite curing agent 0.5~2%, 1.5~4 parts of % of compound alkali-activator, surplus is phosphogypsum or desulfurated plaster, composite curing agent is metallic salts such as potassium, magnesium, aluminium, silicon, sulphur, and compound alkali-activator is calcium hydroxide, sial alkalescence waste etc.;
(2) raw material after the described raw material of step (1) is mixed enters calcining furnace calcining at constant temperature 2h in 150~200 ℃ scope;
(3) with the raw material naturally cooling after step (2) calcining, cooling is after the levigate processing of ball milling;
(4) the raw material ageing after levigate 3~4 days is promptly with step (3).
Each raw materials quality per-cent is formed and can be seen table among the present embodiment preparation method:
Proportioning embodiment | Phosphogypsum | Desulfurated plaster | Composite curing agent | Compound alkali-activator |
1 | 97 | 0 | 1 | 2 |
2 | 94 | 0 | 2 | 4 |
3 | 96.1 | 0 | 1.5 | 2.4 |
4 | 95 | 0 | 1.2 | 3.8 |
5 | 95.9 | 0 | 1.9 | 2.2 |
6 | 0 | 98 | 0.5 | 1.5 |
7 | 0 | 96 | 1 | 3 |
8 | 0 | 98.2 | 0.6 | 1.2 |
9 | 0 | 96.4 | 0.8 | 2.8 |
Each embodiment proportioning in the last table detects through overtesting through the plaster of Paris of processing method preparation of the present invention, and the correlation detection result is as shown in the table:
Detect index | Technical requirements | Detected result |
Ultimate compression strength (MPa) | ≥2.9 | 6.0 |
Folding strength (MPa) | ≥1.8 | 4.2 |
Presetting period (min) | ≥6 | 15 |
Final setting time (min) | ≤30 | 22 |
Claims (5)
1, the processing method of a kind of phosphogypsum, desulphurization gypsum for preparing high strength plaster of Paris is characterized in that, comprises the steps:
(1) raw material consists of by mass percentage: composite curing agent 0.5~2%, and 1.5~4 parts of % of compound alkali-activator, surplus is phosphogypsum or desulfurated plaster;
(2) the described raw material of step (1) is mixed after, enter calcining furnace calcining at constant temperature 2~3h in 150~200 ℃ scope;
(3) with the raw material naturally cooling after step (2) calcining, cooling is after the levigate processing of ball milling;
(4) the raw material ageing after levigate 3~4 days is promptly with step (3).
2, the processing method of phosphogypsum according to claim 1, desulphurization gypsum for preparing high strength plaster of Paris, it is characterized in that, raw material consists of by mass percentage in the described step (1): composite curing agent 1~2%, and 2~4 parts of % of compound alkali-activator, surplus is a phosphogypsum.
3, the processing method of phosphogypsum according to claim 1, desulphurization gypsum for preparing high strength plaster of Paris, it is characterized in that, raw material consists of by mass percentage in the described step (1): composite curing agent 0.5~1%, and 1.5~3 parts of % of compound alkali-activator, surplus is a desulfurated plaster.
4, the processing method of phosphogypsum according to claim 1, desulphurization gypsum for preparing high strength plaster of Paris is characterized in that, described composite curing agent is the metallic salt of potassium, magnesium, aluminium, silicon, sulphur.
5, the processing method of phosphogypsum according to claim 1, desulphurization gypsum for preparing high strength plaster of Paris is characterized in that, described compound alkali-activator is calcium hydroxide, sial alkalescence waste.
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Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101798193A (en) * | 2010-03-19 | 2010-08-11 | 王强 | Electrical heating method for chemical gypsum |
CN102659330A (en) * | 2012-04-18 | 2012-09-12 | 山西太钢不锈钢股份有限公司 | Desulfurization gypsum recycling method |
CN104628276A (en) * | 2015-02-02 | 2015-05-20 | 河南聚能新型建材有限公司 | Phosphogypsum treatment method |
CN105293961A (en) * | 2015-11-23 | 2016-02-03 | 江苏一夫科技股份有限公司 | Method for preparation of building gypsum powder from phosphogypsum |
CN105384372A (en) * | 2015-11-27 | 2016-03-09 | 山东先罗输送机械有限公司 | Method and device for preparing building gypsum from desulfurized gypsum |
CN105985036A (en) * | 2015-02-13 | 2016-10-05 | 郑州三迪建筑科技有限公司 | Processing method for phosphogypsum |
CN106007429A (en) * | 2016-05-23 | 2016-10-12 | 北新集团建材股份有限公司 | Method for preparing building gypsum |
CN106145726A (en) * | 2016-05-24 | 2016-11-23 | 成都市斯贝佳科技有限公司 | The process of high-strength building gypsum prepared by a kind of ardealite |
CN106145727A (en) * | 2016-05-24 | 2016-11-23 | 成都市斯贝佳科技有限公司 | A kind of process of desulphurization gypsum for preparing high strength plaster of Paris |
CN106431034A (en) * | 2016-08-31 | 2017-02-22 | 贵州川恒化工股份有限公司 | Method for producing building gypsum powder from semi-hydrate phosphogypsum |
CN107324676A (en) * | 2017-07-24 | 2017-11-07 | 武汉理工大学 | The method that β semi-hydrated gypsums are prepared using low grade coal calcined phosphogypsum and carbide slurry |
CN109665731A (en) * | 2018-12-29 | 2019-04-23 | 泰山石膏有限公司 | A kind of preparation method of the full desulphurization building gypsum of plastering mortar |
CN109694098A (en) * | 2017-10-23 | 2019-04-30 | 北新集团建材股份有限公司 | Ardealite preprocess method and ardealite Thistle board and preparation method thereof |
CN110204231A (en) * | 2019-06-03 | 2019-09-06 | 杨舜轲 | A method of building gypsum is prepared using power plant's solid waste desulfurized gypsum |
CN110282892A (en) * | 2019-08-13 | 2019-09-27 | 云南磷化集团有限公司 | A kind of phosphogypsum for production of thistle board shortens the preprocess method of setting time |
CN111170668A (en) * | 2020-01-10 | 2020-05-19 | 江苏一夫科技股份有限公司 | Calcination treatment method of phosphogypsum and application of obtained phosphogypsum |
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CN102659330A (en) * | 2012-04-18 | 2012-09-12 | 山西太钢不锈钢股份有限公司 | Desulfurization gypsum recycling method |
CN104628276A (en) * | 2015-02-02 | 2015-05-20 | 河南聚能新型建材有限公司 | Phosphogypsum treatment method |
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CN107324676A (en) * | 2017-07-24 | 2017-11-07 | 武汉理工大学 | The method that β semi-hydrated gypsums are prepared using low grade coal calcined phosphogypsum and carbide slurry |
CN107324676B (en) * | 2017-07-24 | 2019-11-26 | 武汉理工大学 | β-semi-hydrated gypsum method is prepared using low grade coal calcined phosphogypsum and carbide slurry |
CN109694098A (en) * | 2017-10-23 | 2019-04-30 | 北新集团建材股份有限公司 | Ardealite preprocess method and ardealite Thistle board and preparation method thereof |
CN109665731A (en) * | 2018-12-29 | 2019-04-23 | 泰山石膏有限公司 | A kind of preparation method of the full desulphurization building gypsum of plastering mortar |
CN109665731B (en) * | 2018-12-29 | 2021-12-24 | 泰山石膏有限公司 | Preparation method of full-desulfurization building gypsum for plastering mortar |
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CN111620577A (en) * | 2019-04-04 | 2020-09-04 | 北新集团建材股份有限公司 | Machine-sprayed surface layer plastering gypsum with purification function and preparation method thereof |
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CN110282892B (en) * | 2019-08-13 | 2021-04-27 | 云南磷化集团有限公司 | Pretreatment method for shortening setting time of phosphogypsum for producing gypsum plasterboard |
CN111170668A (en) * | 2020-01-10 | 2020-05-19 | 江苏一夫科技股份有限公司 | Calcination treatment method of phosphogypsum and application of obtained phosphogypsum |
CN111170668B (en) * | 2020-01-10 | 2022-07-12 | 江苏一夫科技股份有限公司 | Calcination treatment method of phosphogypsum and application of obtained phosphogypsum |
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