CN102126738A - Method for producing nitrophosphate fertilizer and co-producing gypsum through decomposing phosphorite with nitric acid - Google Patents
Method for producing nitrophosphate fertilizer and co-producing gypsum through decomposing phosphorite with nitric acid Download PDFInfo
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Abstract
The invention provides a method for producing nitrophosphate fertilizer and co-producing high-purity gypsum through decomposing phosphorite with nitric acid, belonging to the technical field of compound fertilizer production. The method comprises the following steps: decomposing the phosphorite with the nitric acid, and filtering acid-insoluble substances; then adding ammonium sulfate or sulfuric acid for decalcification, wherein a byproduct is the high-purity gypsum; carrying out neutralization, evaporation, pelleting and the like on the decalcified acidolysis solution so as to produce the nitrophosphate fertilizer, directly neutralizing the decalcified acidolysis solution with gas ammonia so as to obtain the nitrophosphate fertilizer containing ammonium nitrate and monoammonium phosphate; and evaporating, pelleting and drying the slurry so as to obtain the nitrophosphate fertilizer. The calcium in the acidolysis solution generated after the phosphrite is decomposed by phosphoric acid is removed by using the ammonium sulfate or sulfuric acid, and other impurity ions are not added; and as a nutrient, the ammonia in the ammonium sulfate is remained in a finished product when the calcium is removed by using the ammonium sulfate. The removal rate of the calcium in the acidolysis solution is up to above 95%.
Description
Technical field:
The present invention relates to a kind of nitric acid decomposing phosphate rock and produce the method for nitrophosphate fertilizer by-product high purity gypsum, belong to composite fertilizer's production technical field, be specifically related to the method that the nitric acid decomposing phosphate rock is produced nitrophosphate fertilizer and produced high purity gypsum.
Background technology:
The nitro phosphor complex that makes with the nitric acid decomposing phosphate rock is commonly referred to nitrophosphate fertilizer.The principal feature that the nitric acid decomposing phosphate rock prepares compound fertilizer technology is that nitric acid has played dual function: both utilized the strongly-acid of nitric acid to come decomposing phosphate rock to produce phosphoric acid, replaced the sulfuric acid decomposing phosphate rock, saved sulfuric acid, itself stays its negatively charged ion in the product as the nitric nitrogen nutrient again, the utilization of fullest chemical reactant.
With the technology of nitric acid decomposing phosphate rock production composite fertilizer abroad as Europe and USSR (Union of Soviet Socialist Republics) employing be cold method.China uses cold method explained hereafter nitro-compound fertilizer that a family of a day ridge Coal Chemical Industry group company (former Shanxi fertilizer plant) is only arranged, and is to have introduced Norsk Hydro cold method nitrophosphate fertilizer device from Norway.This device is because of using the phosphorus ore production that domestic grade is low, foreign matter content is high, and nitrocalcite cold method separation difficulty still exists a lot of problems not solve at present on the technology, cause only this cover of domestic cold method nitrophosphate fertilizer device.The defective of this technology is huge, the long flow path of plant investment, to ingredient requirement harshness, complicated operation, the domestic phosphorus ore of device incompatibility etc.
Document 1 Chinese patent " a kind of processing method of producing high concentration nitric-phosphate fertilizer " (application number: 200910009223.3), it comprises the steps: that phosphorus ore adds nitric acid solution, acid non-soluble substance precipitate and separate, nitrocalcite freezing and crystallizing, nitrocalcite filtration, mother liquor neutralization, evaporation, granulation and drying, between nitrocalcite filtration and mother liquor neutralization, mother liquor degree of depth deliming step is arranged, this step comprises following process: I) the mother liquor degree of depth is removed mother liquor of calcium interpolation sulfuric acid or ammonium sulfate, and the calcium ion of mother liquor and sulfate ion generate the terra alba crystallization; II) the reaction slurry stage treatment adopts stage equipment that reaction slurry is carried out stage treatment, and the reaction slurry that has small-particle calcium sulfate returns the deliming of the mother liquor degree of depth, and the reaction slurry that has macrobead calcium sulfate is delivered to the calcium sulfate filtration; III) calcium sulfate filtering reaction slip filters through filter and washing, and during a first filtrate and a washing lotion are sent to and operation, two washing lotions are returned filter.
Above-mentioned existing method is all with the nitric acid decomposing phosphate rock and prepares the relevant production method of nitrophosphate fertilizer, has close with the present invention or the part that communicates.But existing cold method technology is had relatively high expectations to phosphorus ore grade and foreign matter content, and freezing to remove nitrocalcite incomplete, and the decalcification rate is about 75%～80%, and the nitrocalcite of by-product needs metathesis to produce lime carbonate, and the flow operations complexity is invested huge.
The method of document 1 is the improvement to existing cold method nitrophosphate fertilizer technology, increased with sulfuric acid and ammonium sulfate degree of depth decalcification process, but the crystal of calcium sulfate that removes is tiny, needs classification is carried out in crystallization, mother liquor circulates in a large number, also will carry out metathesis to isolated calcium sulfate and be converted into lime carbonate.This technical process operation is complicated more, invests bigger.
Summary of the invention:
Purpose of the present invention, be to overcome existing cold method nitrophosphate fertilizer technical process complicated operation, invest the incomplete shortcoming of acid hydrolysis solution decalcification that huge shortcoming reaches existing nitric acid decomposing phosphate rock, provide a kind of nitric acid decomposing phosphate rock to produce the method for nitrophosphate fertilizer by-product gypsum.
The present invention is achieved like this: behind the nitric acid decomposing phosphate rock, earlier acid non-soluble substance and organic seston are removed by filter, acid hydrolysis solution after the purification adds industrial sulphuric acid ammonium or sulfuric acid decalcification, filters to obtain decalcification byproduct high purity gypsum, and the acid hydrolysis solution after the decalcification is used for producing nitrophosphate fertilizer again.
A kind of nitric acid decomposing phosphate rock is produced the method for nitrophosphate fertilizer by-product gypsum, may further comprise the steps:
(1) will carry out acidolysis reaction with nitric acid behind the phosphorus ore grinding;
(2) the thick acid hydrolysis solution that step (1) is obtained filters, and removes wherein acid non-soluble substance and organic seston, and filtrate is smart acid hydrolysis solution;
(3) smart acid hydrolysis solution adding ammonium sulfate or the sulfuric acid with step (2) carries out the replacement(metathesis)reaction decalcification, and reaction solution is filtered, and solid is a high purity gypsum, is gypsum product after washing drying, and filtrate is the decalcification acid hydrolysis solution.
(4) directly and the gas ammonia neutralization reaction, must contain the nitrophosphate fertilizer slip of ammonium nitrate, monoammonium phosphate, slip obtains nitrophosphate fertilizer through evaporation, granulation, drying with the decalcification acid hydrolysis solution in the step (3).
Foregoing method, preferred scheme is that the mass concentration of nitric acid is 40-70% in the step (1), is optimized for 55-65%.
Foregoing method, preferred scheme are that the mol ratio 1 of calcium ion and nitric acid in the middle phosphorus ore of step (1): 2-3 is optimized for 1: 2-2.3.
Foregoing method, preferred scheme is that temperature of reaction is 45-70 ℃ in the step (1), is optimized for 55-60 ℃.
Foregoing method, preferred scheme is that the reaction times is 0.5-4 hour in the step (1), is optimized for 1-2 hour.
Foregoing method, preferred scheme is that ammonium sulfate or sulfuric acid add-on are pressed the mol ratio 1-1.2 of calcium ion in sulfate ion and the smart acid hydrolysis solution in the step (3): 1.
Foregoing method, preferred scheme is that temperature of reaction is 55-60 ℃ in the step (3).
Foregoing method, preferred scheme is that the reaction times is 1-4 hour in the step (3), is optimized for 2-2.5 hour.
Foregoing method, preferred scheme is that the granulation mode is spray granulating, ammoniation-granulation, high tower prilling or biaxial granulation in the step (4).
A kind of nitric acid decomposing phosphate rock is produced the method for nitrophosphate fertilizer by-product gypsum, and another technical thought is that the slip in the step (4) after the neutralization is produced powder-like product without granulation with the spraying drying mode.
The present invention has following feature and beneficial effect:
(1) the present invention first filter acid insolubles and organic seston before the acid hydrolysis solution decalcification of nitric acid decomposing phosphate rock, decalcification byproduct terra alba (gypsum) purity is reached more than 99%, can be used as high purity gypsum such as mould gypsum, medical gypsum, filler, no phosphogypsum discharging realizes the comprehensive utilization of resource;
(2) acid hydrolysis solution of phosphorolytic cleavage phosphorus ore of the present invention removes calcium and uses ammonium sulfate or sulfuric acid, is not with other foreign ions of people.By-product goes out behind the high purity gypsum ammonia in the ammonium sulfate and stays in the mother liquor nutrient of as fertilizer sources and stay in the product during with the ammonium sulfate decalcification;
(3) the decreasing ratio height of acidolysis liquid calcium of the present invention arrives more than 95%, and this is that cold method technology is incomparable;
(4) the present invention does not have freezing in the cold method technology, nitrocalcite to be converted into operations such as lime carbonate, simplified control, and investment significantly reduces.
Embodiment:
Describe technical scheme of the present invention in detail below in conjunction with embodiment, but protection domain is not by this restriction.
Embodiment 1:
Implement raw material: 1, ground phosphate rock: P
2O
5Content is 30.72%, and CaO is 48.28%
2, nitric acid: concentration 70%
3, industrial sulphuric acid ammonium: ammonia content 21%
The invention process process may further comprise the steps:
(1) carries out acidolysis reaction with 70% nitric acid after ground phosphate rock being added water, the mol ratio 1: 3 of calcium ion and nitric acid in the phosphorus ore; Temperature of reaction is 45 ℃, reacts 0.5 hour.
(2) the thick acid hydrolysis solution that step (1) is obtained filters, and removes wherein acid non-soluble substance and organic seston, and filtrate is smart acid hydrolysis solution.
(3) the smart acid hydrolysis solution of step (2) is added the industrial sulphuric acid ammonium and carry out replacement(metathesis)reaction, the ammonium sulfate add-on is pressed the mol ratio 1: 1 of calcium ion in ammonium sulfate and the smart acid hydrolysis solution; Temperature of reaction is 55 ℃; Reaction times is 1 hour.Reaction solution is filtered, and solid is a high purity gypsum, is the high purity gypsum product after washing drying; Filtrate is the decalcification acid hydrolysis solution.
(4) directly and the gas ammonia neutralization reaction, must contain the nitrophosphate fertilizer slip of ammonium nitrate, monoammonium phosphate with the decalcification acid hydrolysis solution in the step (3).Slip is through being evaporated to water content less than 3%, and through the granulation of biaxial granulation machine, screening obtains nitrophosphate fertilizer behind the drying roller drying.
Result of implementation:
1. high purity gypsum: the sulfate dihydrate calcium contents is 99.5% in the gypsum after testing;
2. nitrophosphate fertilizer: total nitrogen content 26.5%, phosphorus (P
2O
5) content is 11.5%.
Embodiment 2:
Implement raw material: 1, ground phosphate rock: P
2O
5Content is 29.85%, and CaO is 48.30%
2, nitric acid: concentration 40%
3, industrial sulphuric acid ammonium: ammonia content 21%
The invention process process may further comprise the steps:
(1) carries out acidolysis reaction with 40% nitric acid after ground phosphate rock being added water, the mol ratio 1: 2 of calcium ion and nitric acid in the phosphorus ore; Temperature of reaction is 70 ℃, reacts 4 hours.
(2) the thick acid hydrolysis solution that step (1) is obtained filters, and removes wherein acid non-soluble substance and organic seston, and filtrate is smart acid hydrolysis solution.
(3) the smart acid hydrolysis solution of step (2) is added the industrial sulphuric acid ammonium and carry out replacement(metathesis)reaction, the ammonium sulfate add-on is pressed the mol ratio 1.2: 1 of calcium ion in ammonium sulfate and the smart acid hydrolysis solution; Temperature of reaction is 58 ℃; Reaction times is 4 hours.Reaction solution is filtered, and solid is a high purity gypsum, is the high purity gypsum product after washing drying; Filtrate is the decalcification acid hydrolysis solution.
(4) directly and the gas ammonia neutralization reaction, must contain the nitrophosphate fertilizer slip of ammonium nitrate, monoammonium phosphate with the decalcification acid hydrolysis solution in the step (3).Slip is moisture 3% through being evaporated to, spray-dried powdery nitrophosphate fertilizer.
Result of implementation:
1. high purity gypsum: the sulfate dihydrate calcium contents is 99.6% in the gypsum after testing;
2. nitrophosphate fertilizer: total nitrogen content 27.3%, phosphorus (P
2O
5) content is 11.8%.
Embodiment 3:
Implement raw material: 1, ground phosphate rock: P
2O
5Content is 31.05%, and CaO is 47.65%
2, nitric acid: concentration 60%
3, industrial sulphuric acid: concentration 98%
The invention process process may further comprise the steps:
(1) carries out acidolysis reaction with 60% nitric acid after ground phosphate rock being added water, the mol ratio 1: 2.3 of calcium ion and nitric acid in the phosphorus ore; Temperature of reaction is 45 ℃, reacts 1.5 hours.
(2) the thick acid hydrolysis solution that step (1) is obtained filters, and removes wherein acid non-soluble substance and organic seston, and filtrate is smart acid hydrolysis solution.
(3) the smart acid hydrolysis solution of step (2) is added industrial sulphuric acid and carry out replacement(metathesis)reaction, the sulfuric acid add-on is pressed the mol ratio 1.1: 1 of calcium ion in sulfate ion and the smart acid hydrolysis solution; Temperature of reaction is 60 ℃; Reaction times is 3 hours.Reaction solution is filtered, and solid is a high purity gypsum, is the high purity gypsum product after washing drying; Filtrate is the decalcification acid hydrolysis solution.
(4) directly and the gas ammonia neutralization reaction, must contain the nitrophosphate fertilizer slip of ammonium nitrate, monoammonium phosphate with the decalcification acid hydrolysis solution in the step (3).Slip is through being evaporated to water content less than 3%, and through the ammoniation granulator granulation, screening obtains nitrophosphate fertilizer behind the drying roller drying.
Result of implementation:
1. high purity gypsum: the sulfate dihydrate calcium contents is 99.4% in the gypsum after testing;
2. nitrate-based compound fertilizer: total nitrogen content 25.2%, phosphorus (P
2O
5) content is 13.9%.
Embodiment 4:
Implement raw material: 1, ground phosphate rock: P
2O
5Content is 29.75%, and CaO is 48.40%
2, nitric acid: concentration 60%
3, industrial sulphuric acid ammonium: ammonia content 21%
The invention process process may further comprise the steps:
(1) carries out acidolysis reaction with 60% nitric acid after ground phosphate rock being added water, the mol ratio 1: 2 of calcium ion and nitric acid in the phosphorus ore; Temperature of reaction is 58 ℃, reacts 3.5 hours.
(2) the thick acid hydrolysis solution that step (1) is obtained filters, and removes wherein acid non-soluble substance and organic seston, and filtrate is smart acid hydrolysis solution.
(3) the smart acid hydrolysis solution of step (2) is added the industrial sulphuric acid ammonium and carry out replacement(metathesis)reaction, the ammonium sulfate add-on is pressed the mol ratio 1.2: 1 of calcium ion in ammonium sulfate and the smart acid hydrolysis solution; Temperature of reaction is 58 ℃; Reaction times is 4 hours.Reaction solution is filtered, and solid is a high purity gypsum, is the high purity gypsum product after washing drying; Filtrate is the decalcification acid hydrolysis solution.
(4) directly and the gas ammonia neutralization reaction, must contain the nitrophosphate fertilizer slip of ammonium nitrate, monoammonium phosphate with the decalcification acid hydrolysis solution in the step (3).Slip is moisture 3% through being evaporated to, spray-dried powdery nitrophosphate fertilizer.
Result of implementation:
1. high purity gypsum: the sulfate dihydrate calcium contents is 99.6% in the gypsum after testing;
2. nitrophosphate fertilizer: total nitrogen content 27.3%, phosphorus (P
2O
5) content is 11.8%.
Claims (10)
1. the method that the nitric acid decomposing phosphate rock is produced the nitrophosphate fertilizer by-product gypsum is characterized in that, may further comprise the steps:
(1) will carry out acidolysis reaction with nitric acid behind the phosphorus ore grinding;
(2) the thick acid hydrolysis solution that step (1) is obtained filters, and removes wherein acid non-soluble substance and organic seston, and filtrate is smart acid hydrolysis solution;
(3) smart acid hydrolysis solution adding ammonium sulfate or the sulfuric acid with step (2) carries out the replacement(metathesis)reaction decalcification, and reaction solution is filtered, and solid is a high purity gypsum, is gypsum product after washing drying, and filtrate is the decalcification acid hydrolysis solution.
(4) directly and the gas ammonia neutralization reaction, must contain the nitrophosphate fertilizer slip of ammonium nitrate, monoammonium phosphate, slip obtains nitrophosphate fertilizer through evaporation, granulation, drying with the decalcification acid hydrolysis solution in the step (3).
2. method according to claim 1 is characterized in that, the mass concentration of nitric acid is 40-70% in the step (1), is optimized for 55-65%, more is optimized for 60%.
3. method according to claim 1 is characterized in that, the mol ratio 1 of calcium ion and nitric acid in the middle phosphorus ore of step (1): 2-3 is optimized for 1: 2-2.3.
4. method according to claim 1 is characterized in that, temperature of reaction is 45-70 ℃ in the step (1), is optimized for 55-60 ℃, more is optimized for 58 ℃.
5. method according to claim 1 is characterized in that, the reaction times is 0.5-4 hour in the step (1), is optimized for 1-2 hour.
6. method according to claim 1 is characterized in that, ammonium sulfate or sulfuric acid add-on are pressed the mol ratio 1-1.2 of calcium ion in sulfate ion and the smart acid hydrolysis solution in the step (3): 1.
7. method according to claim 1 is characterized in that, temperature of reaction is 55-60 ℃ in the step (3), more is optimized for 58 ℃.
8. method according to claim 1 is characterized in that, the reaction times is 1-4 hour in the step (3), is optimized for 2-2.5 hour.
9. method according to claim 1 is characterized in that, the granulation mode is spray granulating, ammoniation-granulation, high tower prilling or biaxial granulation in the step (4).
10. method according to claim 1 is characterized in that, the slip in the step (4) after the neutralization is produced powder-like product without granulation with the spraying drying mode.
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|---|---|---|---|---|
| CN103524151A (en) * | 2013-10-21 | 2014-01-22 | 贵州省化工研究院 | Method for preparing nitric phosphate-potassium fertilizer by decomposing phosphorite by nitric acid with co-production of phosphoric acid and calcium carbonate |
| CN104108969A (en) * | 2014-07-04 | 2014-10-22 | 贵州芭田生态工程有限公司 | Granulation method of phosphorus-potassium nitrate fertilizer |
| CN104108968A (en) * | 2014-07-04 | 2014-10-22 | 贵州芭田生态工程有限公司 | Granulating method of nitric phosphate |
| CN104108969B (en) * | 2014-07-04 | 2016-11-30 | 贵州芭田生态工程有限公司 | A kind of granulation process of phosphorus-potassium nitrate fertilizer |
| CN106277012A (en) * | 2015-06-09 | 2017-01-04 | 铜仁市万山区盛和矿业有限责任公司 | A kind of comprehensive utilization mid low grade phosphate rock method |
| CN109485527A (en) * | 2019-01-22 | 2019-03-19 | 郑利 | A kind of nitro fertilizer and preparation method thereof containing activation mineral resources humic acid |
| CN111377421A (en) * | 2020-05-22 | 2020-07-07 | 四川大学 | α method for preparing gypsum and method for preparing phosphoric acid and α gypsum by using phosphorite |
| CN111498892A (en) * | 2020-04-21 | 2020-08-07 | 贵州大学 | Method for preparing α high-strength gypsum from byproduct calcium nitrate tetrahydrate of nitrophosphate fertilizer by freezing method |
| CN111533154A (en) * | 2020-04-21 | 2020-08-14 | 贵州大学 | Method for removing calcium and byproduct alpha high-strength gypsum by decomposing phosphate rock acidolysis solution with nitric acid |
| CN111559754A (en) * | 2020-04-21 | 2020-08-21 | 贵州大学 | Method for removing calcium and byproduct alpha-type building gypsum by decomposing phosphate rock acidolysis solution with nitric acid |
| CN112758903A (en) * | 2021-01-27 | 2021-05-07 | 金正大生态工程集团股份有限公司 | Medium-low grade phosphorite pretreatment method |
| CN114455562A (en) * | 2022-01-30 | 2022-05-10 | 贵州芭田生态工程有限公司 | Method for preparing iron phosphate and method for preparing fertilizer by using byproducts |
| CN116002740A (en) * | 2022-12-30 | 2023-04-25 | 贵州芭田生态工程有限公司 | Method for preparing and purifying calcium sulfate in nitric acid solution |
| CN116040596A (en) * | 2022-01-09 | 2023-05-02 | 四川大学 | Comprehensive utilization method of phosphoric acid by wet method with nitric acid method |
| EP4253314A1 (en) | 2022-03-28 | 2023-10-04 | Saudi Arabian Mining Company (Ma'aden) | Integrated process to upgrade low grade calcareous phosphate ore with low co2 emissions and low phosphogypsum waste |
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|---|---|---|---|---|
| CN103524151B (en) * | 2013-10-21 | 2015-09-16 | 贵州省化工研究院 | The method of decomposing phosphorite by using nitric acid phosphorus-potassium nitrate fertilizer coproduction phosphoric acid and calcium carbonate |
| CN103524151A (en) * | 2013-10-21 | 2014-01-22 | 贵州省化工研究院 | Method for preparing nitric phosphate-potassium fertilizer by decomposing phosphorite by nitric acid with co-production of phosphoric acid and calcium carbonate |
| CN104108969A (en) * | 2014-07-04 | 2014-10-22 | 贵州芭田生态工程有限公司 | Granulation method of phosphorus-potassium nitrate fertilizer |
| CN104108968A (en) * | 2014-07-04 | 2014-10-22 | 贵州芭田生态工程有限公司 | Granulating method of nitric phosphate |
| CN104108969B (en) * | 2014-07-04 | 2016-11-30 | 贵州芭田生态工程有限公司 | A kind of granulation process of phosphorus-potassium nitrate fertilizer |
| CN106277012A (en) * | 2015-06-09 | 2017-01-04 | 铜仁市万山区盛和矿业有限责任公司 | A kind of comprehensive utilization mid low grade phosphate rock method |
| CN106277012B (en) * | 2015-06-09 | 2018-06-08 | 铜仁市万山区盛和矿业有限责任公司 | A kind of comprehensive utilization mid low grade phosphate rock method |
| CN109485527A (en) * | 2019-01-22 | 2019-03-19 | 郑利 | A kind of nitro fertilizer and preparation method thereof containing activation mineral resources humic acid |
| CN111533154B (en) * | 2020-04-21 | 2023-06-02 | 贵州大学 | Method for decomposing phosphate rock acidolysis solution by nitric acid to remove calcium and obtain byproduct alpha high-strength gypsum |
| CN111498892A (en) * | 2020-04-21 | 2020-08-07 | 贵州大学 | Method for preparing α high-strength gypsum from byproduct calcium nitrate tetrahydrate of nitrophosphate fertilizer by freezing method |
| CN111533154A (en) * | 2020-04-21 | 2020-08-14 | 贵州大学 | Method for removing calcium and byproduct alpha high-strength gypsum by decomposing phosphate rock acidolysis solution with nitric acid |
| CN111559754A (en) * | 2020-04-21 | 2020-08-21 | 贵州大学 | Method for removing calcium and byproduct alpha-type building gypsum by decomposing phosphate rock acidolysis solution with nitric acid |
| CN111377421A (en) * | 2020-05-22 | 2020-07-07 | 四川大学 | α method for preparing gypsum and method for preparing phosphoric acid and α gypsum by using phosphorite |
| CN112758903B (en) * | 2021-01-27 | 2023-01-31 | 金正大生态工程集团股份有限公司 | Medium-low grade phosphorite pretreatment method |
| CN112758903A (en) * | 2021-01-27 | 2021-05-07 | 金正大生态工程集团股份有限公司 | Medium-low grade phosphorite pretreatment method |
| CN116040596A (en) * | 2022-01-09 | 2023-05-02 | 四川大学 | Comprehensive utilization method of phosphoric acid by wet method with nitric acid method |
| CN114455562A (en) * | 2022-01-30 | 2022-05-10 | 贵州芭田生态工程有限公司 | Method for preparing iron phosphate and method for preparing fertilizer by using byproducts |
| EP4253314A1 (en) | 2022-03-28 | 2023-10-04 | Saudi Arabian Mining Company (Ma'aden) | Integrated process to upgrade low grade calcareous phosphate ore with low co2 emissions and low phosphogypsum waste |
| CN116002740A (en) * | 2022-12-30 | 2023-04-25 | 贵州芭田生态工程有限公司 | Method for preparing and purifying calcium sulfate in nitric acid solution |
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