CN102502552A - Method for recycling phosphorus and fluoride in sewage residue of phosphorus fertilizer plant - Google Patents
Method for recycling phosphorus and fluoride in sewage residue of phosphorus fertilizer plant Download PDFInfo
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- CN102502552A CN102502552A CN2011103196195A CN201110319619A CN102502552A CN 102502552 A CN102502552 A CN 102502552A CN 2011103196195 A CN2011103196195 A CN 2011103196195A CN 201110319619 A CN201110319619 A CN 201110319619A CN 102502552 A CN102502552 A CN 102502552A
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Abstract
The invention discloses a method for recycling phosphorus and fluoride in the sewage residue of a phosphorus fertilizer plant. According to the method, the sewage residue is decomposed by using sulfuric acid, the phosphorus and the fluoride in the sewage residue are extracted, calcium sulfate dihydrate crystal or calcium sulfate hemihydrate crystal and diluted phosphoric acid solution are generated, diluted phosphoric acid and phosphogypsum which is the by-product are obtained through solid-liquid separation, the diluted phosphoric acid is concentrated into concentrated phosphoric acid, the escaped fluorine containing gas is recycled in the process of concentrating the phosphoric acid and making acid and produced into the fluoride such as the fluosilicic acid and the like, or defluorination agent is added into the diluted phosphoric acid to recycle fluoride resources in the form of the fluoride such as the sodium fluosilicate and the like, and the obtained concentrated phosphoric acid can be used to prepare other phosphate products such as the ammonium phosphate and the like by using the traditional method. The method can be used to effectively recycle the phosphorus and fluoride resources in the sewage residue of the phosphorus fertilizer plant so that the waste materials can be changed into the valuable materials and the recycling value of the phosphorus and fluoride resources in the sewage residue of the phosphorus fertilizer plant can be improved. The method has good economic benefit and environment protection significance.
Description
Technical field
The present invention relates to WWT, relate in particular to a kind of method that reclaims phosphorus and fluorine in phosphate fertilizer plant's sewage slag.
Background technology
Phosphorus and fluorine all are the important Mineral resources in short supply of China, in national economy, play important effect.The production waste of China phosphate fertilizer plant generally contains the phosphorus and the fluorine of higher concentration; Phosphate fertilizer plant's sewage slag be this phosphorous fluorine sewage after water technology from the isolated a kind of large-tonnage waste of filtering separation device; This sewage slag contains abundant phosphorus fluorine resource; Press for it is recycled, realize turning waste into wealth.With certain state-owned phosphate fertilizer plant is example, and about 90,000 tons of annual sewage effluent sewerage slag after water technology (moisture about 50%, contain 20% the P of having an appointment in the dried slag
2O
5And about 7% F), contain P altogether
2O
5About 3150 tons of about 9000 tons and F.The domestic phosphate fertilizer plant of this sewage slag once was dried and made thick fertilizer or the fertile raw material of compound, but owing to contained P in this sewage slag
2O
5The overwhelming majority is solubility in citric acid P
2O
5, do not reach the water-soluble P that GB15063-2009 requires when being used for producing compound fertilizer
2O
5Should be not less than effective P
2O
540% requirement of content, therefore this sewage slag at home phosphate fertilizer plant generally make refuse storage bay reason, phosphorus wherein and fluorine do not obtain recycling; Phosphorus fluorine resource is wasted; And to pay the high maintenance cost of storing up, the land occupation resource is polluted surrounding enviroment.
By retrieval; Chinese patent 201010169236.X number " adopting the guanite precipitation method from waste water, to reclaim the device and the process of phosphorus " and No. 200480014765.5 " a kind of method that reclaims phosphorus " all provide the method that reclaims phosphorus, do not relate to the technical scheme that reclaims phosphorus fluorine in the sewage slag simultaneously but still have.
Summary of the invention
The objective of the invention is to the deficiency to prior art, a kind of method that realizes that phosphorus and fluorine are recycled in phosphate fertilizer plant's sewage slag is provided, to improve the value of phosphorus and fluorine recycling in phosphate fertilizer plant's sewage slag.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts may further comprise the steps:
(1) in the relieving haperacidity reactive tank, add sulfuric acid and decompose sewage slag, phosphorus and fluorine in the extraction sewage slag need to add a certain amount of phosphoric acid and return acid in the reaction, and reaction generates two water or calcium sulphate hemihydrate crystal and P
2O
5Content is 15%～28% dilute phosphoric acid solution, obtains dilute phosphoric acid and sub product phosphogypsum through solid-liquid separation; The main chemical reactions equation of above-mentioned reaction is following:
Ca
3(PO
4)
2?+?3H
2SO
4?+?6H
2O?=?3CaSO
4·2H
2O+?2H
3PO
4
CaHPO
4·2H
2O+?H
2SO
4?=?CaSO
4·2H
2O+?H
3PO
4
CaF
2?+?H
2SO
4?+?2H
2O?=?CaSO
4·2H
2O+?2HF
(2) will be condensed into P through the dilute phosphoric acid that solid-liquid separation obtains
2O
5Content is 35%～54% SPA; The traditional method that adopts those skilled in the art to know in concentration process and in the relieving haperacidity process reclaims the fluoro-gas of overflowing; Be made into fluorochemicals such as silicofluoric acid, perhaps in dilute phosphoric acid, add the form recovery fluorine resource of defluorinating agent with fluorochemicals such as Sodium Silicofluoride 98mins; The traditional method that adopts those skilled in the art to know the SPA that obtains prepares phosphate product such as ammonium phosphate.
The reaction conditions that above-mentioned sulfuric acid decomposes phosphate fertilizer plant's sewage slag is: control SO
3Concentration is 6～80g/L, and temperature of reaction is 45～95 ℃, and the reaction times is 1～8 hour, and liquid-solid ratio is 2～8:1, the sulfuric acid consumption be in the acidolysis phosphate fertilizer plant sewage slag quicklime by 95%～120% of stoichiometric calculation theoretical amount; Optimum reaction condition is: control SO
3Concentration is 25～55g/L, and temperature of reaction is 70～85 ℃, and the reaction times is 2～5 hours, and liquid-solid ratio is 4～5.5:1, the sulfuric acid consumption be in the acidolysis phosphate fertilizer plant sewage slag quicklime by 100%～115% of stoichiometric calculation theoretical amount.
Above-mentioned phosphate fertilizer plant sewage slag be the phosphorous fluorine sewage of phosphate fertilizer plant through water technology from the isolated phosphorous fluorine sewage slag of filtering separation device; This sewage slag can be removed the part free-water through super-dry also can directly be used for the reaction of sulfuric acid decomposition sewage slag without drying; This sewage slag is not contain the butt of free-water, and is phosphorous with P
2O
5Count 12%～35%, fluorine-containing is 4%～12%.
Concentration and the consumption that above-mentioned a certain amount of phosphoric acid returns acid gets for the traditional method calculating of the sulfuric acid decomposing phosphate rock known with those skilled in the art.
The above-mentioned dilute phosphoric acid that obtains through solid-liquid separation is at absolute pressure 10～11kPa, 75～80 ℃ of concentrated down SPAs that obtain.
The described fluorochemical in two places can be one or more in silicofluoric acid, ammonium silicofluoride, Sodium Silicofluoride 98min, Sodium Fluoride, Neutral ammonium fluoride, matt salt, sodium aluminum fluoride, ALUMNIUM FLUORIDE, Calcium Fluoride (Fluorspan) and the hydrogen fluoride in above-mentioned " fluoro-gas is processed fluorochemical such as silicofluoric acid or in dilute phosphoric acid, added defluorinating agent and reclaims the fluorine resource with the form of fluorochemicals such as Sodium Silicofluoride 98min ".
Principle of the present invention is the method for preparing phosphoric acid with reference to the sulfuric acid decomposing phosphate rock; Adopt sulfuric acid to decompose phosphate fertilizer plant's sewage slag and prepare phosphoric acid; Most of fluorine resource in phosphate fertilizer plant's sewage slag also gets into phosphoric acid simultaneously; Through to containing the utilization of hexafluorophosphoric acid, as: phosphoric acid can prepare phosphate product such as ammonium phosphate, thereby the fluorine resource can be overflowed in Phosphoric Acid Concentration and in the relieving haperacidity process to reclaim fluorochemicals such as processing silicofluoric acid or in dilute phosphoric acid, add defluorinating agent and reclaimed the fluorine resource with the form of fluorochemicals such as Sodium Silicofluoride 98min; Thereby realize phosphorus fluorine resources effective is recycled, improved the utility value of phosphorus fluorine resource in phosphate fertilizer plant's sewage slag.
The present invention has following advantage:
(1) turns waste into wealth, will pile up, utilization ratio is low, and large waste phosphate fertilizer plant sewage slag fully utilizes, and realizes that phosphorus fluorine resources effective is recycled in phosphate fertilizer plant's sewage slag, has good environment protection significance;
(2) phosphoric acid is processed in the recovery of the phosphorus in phosphate fertilizer plant's sewage slag; Fluorochemicals such as silicofluoric acid, Sodium Silicofluoride 98min are processed in the recovery of fluorine in phosphate fertilizer plant's sewage slag; Make phosphorus fluorine resource further deep processing be high value added product, improved the utility value of phosphorus and fluorine in phosphate fertilizer plant's sewage slag;
(3) the utilization technology of phosphate fertilizer plant's sewage slag does not consider to reclaim the fluorine resource in this sewage slag in the past, and the present invention has reclaimed the fluorine resource in phosphate fertilizer plant's sewage slag, and the fluorine resource important Mineral resources in short supply that are China are significant;
(4) technology of the present invention is easy to promote, and for the annual a large amount of phosphate fertilizer plants sewage slag that produces of China provides one effectively to utilize approach, has very strong demonstration meaning and promotional value in China phosphorous chemical industry enterprise.
Description of drawings
Accompanying drawing 1 is a process flow sheet of the present invention.
Embodiment
Embodiment 1
Take by weighing sewage slag 1000g (P
2O
5Content 22.7%, F content 7.8%, CaO content 46.5% contains free-water 5%), 98% sulfuric acid 855g, phosphoric acid return sour 6625g (P
2O
5Content 20.0%) quantitatively continuous dosing is in the relieving haperacidity reactive tank, and with reference to the method for traditional sulfuric acid decomposing phosphate rock, reaction conditions is: control SO
3Concentration is about 45g/L, and temperature of reaction is 80 ℃, and the reaction times is 4 hours, and liquid-solid ratio is about 4:1.After reaction finishes, filter, wash, filter the dilute phosphoric acid P that obtains
2O
5Content is about 25.5%, and F content is about 8.1%, gets dilute phosphoric acid 830g and gets into concentration section as the dilute phosphoric acid product, and all the other dilute phosphoric acids and washings are mixed with phosphoric acid and return acid and return the relieving haperacidity reactive tank.
With above-mentioned 830g dilute phosphoric acid concentrated SPA 455g (P that obtains under absolute pressure 10kPa, 75 ℃ of conditions of temperature
2O
5Content is about 46.5%, F content about 1.6%), SPA adopts fertilize preparation craft that industry knows through ammonification, spray granulating production diammonium phosphate, obtains the about 452g of diammonium phosphate product, and product index is: total nutrient 64.8%, total nitrogen 18.0%, effective P
2O
5Be 46.8%, moisture 2.1%, ultimate compression strength 40N.And adopt fluorine absorber to reclaim generation silicofluoric acid (H at the fluorine of sulfuric acid decomposing phosphate rock and the effusion of dilute phosphoric acid concentration section
2SiF
6Content about 20%) about 402g is used further to produce fluorochemicals such as anhydrous hydrogen fluoride.
Embodiment 2
Take by weighing sewage slag 1667g (P
2O
5Content 13.6%, F content 4.7%, CaO content 27.9% contains free-water 40%), 98% sulfuric acid 846g, phosphoric acid return sour 5100g (P
2O
5Content 14.8%) quantitatively continuous dosing is in the relieving haperacidity reactive tank, and with reference to the method for traditional sulfuric acid decomposing phosphate rock, reaction conditions is: control SO
3Concentration is about 25g/L, and temperature of reaction is 75 ℃, and the reaction times is 3 hours, and liquid-solid ratio is about 3.5:1.After reaction finishes, filter, wash, filter the dilute phosphoric acid P that obtains
2O
5Content is about 17.2%, and F content is about 5.5%, gets dilute phosphoric acid 1251g and gets into concentration section as the dilute phosphoric acid product, and all the other dilute phosphoric acids and washings are mixed with phosphoric acid and return acid and return the relieving haperacidity reactive tank.
Above-mentioned 1251g dilute phosphoric acid is obtained SPA 608g (P absolute pressure 11kPa, 80 ℃ of following concentrating
2O
5Content is about 35.4%, F content about 2.4%), the fertilize preparation craft that SPA adopts industry to know is produced monoammonium phosphate through ammonification, granulation, the about 425g of the monoammonium phosphate product that obtains, product index is: total nutrient 60.7%, total nitrogen 10.6%, effective P
2O
5Be 50.1%, moisture 1.2%, ultimate compression strength 49N.And adopt fluorine absorber to reclaim generation silicofluoric acid (H at the fluorine of sulfuric acid decomposing phosphate rock and the effusion of dilute phosphoric acid concentration section
2SiF
6Content about 21%) about 328g is used further to produce fluorochemicals such as anhydrous hydrogen fluoride.
Embodiment 3
Take by weighing sewage slag 1333g (P
2O
5Content 24.8%, F content 8.63%, CaO content 35.3% contains free-water 25%), 98% sulfuric acid 1007g, phosphoric acid return sour 2377g (P
2O
5Content 20.9%) quantitatively continuous dosing is in the relieving haperacidity reactive tank, and with reference to the method for traditional sulfuric acid decomposing phosphate rock, reaction conditions is: control SO
3Concentration is about 80g/L, and temperature of reaction is 95 ℃, and the reaction times is 1 hour, and liquid-solid ratio is about 2:1.After reaction finishes, filter, wash, filter the dilute phosphoric acid P that obtains
2O
5Content is about 28%, and F content is about 9.1%, gets dilute phosphoric acid 1109g and gets into concentration section as the dilute phosphoric acid product, and all the other dilute phosphoric acids and washings are mixed with phosphoric acid and return acid and return the relieving haperacidity reactive tank.
Above-mentioned 1109g dilute phosphoric acid is obtained SPA 577g (P absolute pressure 10kPa, 78 ℃ of following concentrating
2O
5Content is about 53.6%, F content about 1.2%), SPA adopts fertilize preparation craft that industry knows through ammonification, granulation production diammonium phosphate, the about 664g of the diammonium phosphate product that obtains, product index is: total nutrient 64.5%, total nitrogen 18.1%, effective P
2O
5Be 46.4%, moisture 1.3%, ultimate compression strength 43N.And adopt fluorine absorber to reclaim generation silicofluoric acid (H at the fluorine of sulfuric acid decomposing phosphate rock and the effusion of dilute phosphoric acid concentration section
2SiF
6Content about 21%) about 585g is used further to produce fluorochemicals such as anhydrous hydrogen fluoride.
Embodiment 4
Take by weighing sewage slag 1176g (P
2O
5Content 11.9%, F content 4.68%, CaO content 29.8% contains free-water 15%), 98% sulfuric acid 594g, phosphoric acid return sour 8654g (P
2O
5Content 14.0%) quantitatively continuous dosing is in the relieving haperacidity reactive tank, and with reference to the method for traditional sulfuric acid decomposing phosphate rock, reaction conditions is: control SO
3Concentration is about 6g/L, and temperature of reaction is 45 ℃, and the reaction times is 8 hours, and liquid-solid ratio is about 8:1.After reaction finishes, filter, wash, filter the dilute phosphoric acid P that obtains
2O
5Content is about 15.3%, and F content is about 5.6%, gets dilute phosphoric acid 875g and gets into concentration section as the dilute phosphoric acid product, and all the other dilute phosphoric acids and washings are mixed with phosphoric acid and return acid and return the relieving haperacidity reactive tank.
Above-mentioned 875g dilute phosphoric acid is obtained SPA 371g (P absolute pressure 10.8kPa, 78 ℃ of following concentrating
2O
5Content is about 35.9%, F content about 2.3%), the fertilize preparation craft that SPA adopts industry to know is produced monoammonium phosphate through ammonification, granulation, the about 263g of the monoammonium phosphate product that obtains, product index is: total nutrient 60.5%, total nitrogen 10.2%, effective P
2O
5Be 50.3%, moisture 1.4%, ultimate compression strength 42N.And adopt fluorine absorber to reclaim generation silicofluoric acid (H at the fluorine of sulfuric acid decomposing phosphate rock and the effusion of dilute phosphoric acid concentration section
2SiF
6Content about 20%) about 264g is used further to produce fluorochemicals such as anhydrous hydrogen fluoride.
The above; It only is preferred embodiment of the present invention; Be not that the present invention is done any pro forma restriction; Anyly do not break away from technical scheme content of the present invention, to any simple modification, equivalent variations and modification that above embodiment did, all still belong in the scope of technical scheme of the present invention according to technical spirit of the present invention.
Claims (10)
1. method that reclaims phosphorus and fluorine in phosphate fertilizer plant's sewage slag is characterized in that this method may further comprise the steps:
(1) add sulfuric acid and decompose sewage slag, the phosphorus fluorine resource in the extraction sewage slag needs to add a certain amount of phosphoric acid and returns acid in the reaction, and reaction generates two water or calcium sulphate hemihydrate crystal and P
2O
5Content is 15%～28% dilute phosphoric acid solution, obtains dilute phosphoric acid and sub product phosphogypsum through solid-liquid separation; The main chemical reactions equation of above-mentioned reaction is following:
Ca
3(PO
4)
2?+?3H
2SO
4?+?6H
2O?=?3CaSO
4·2H
2O+?2H
3PO
4
CaHPO
4·2H
2O+?H
2SO
4?=?CaSO
4·2H
2O+?H
3PO
4
CaF
2?+?H
2SO
4?+?2H
2O?=?CaSO
4·2H
2O+?2HF
(2) will be condensed into SPA through the dilute phosphoric acid that solid-liquid separation obtains, the traditional method that adopts those skilled in the art to know in the Phosphoric Acid Concentration process and in the relieving haperacidity process reclaims the fluoro-gas of overflowing and processes fluorochemical such as silicofluoric acid or in dilute phosphoric acid, add defluorinating agent and reclaim the fluorine resource with the form of fluorochemicals such as Sodium Silicofluoride 98min; The traditional method that the SPA that obtains can adopt those skilled in the art to know prepares phosphate product such as ammonium phosphate.
2. the method for phosphorus and fluorine in the recovery according to claim 1 phosphate fertilizer plant sewage slag is characterized in that the reaction conditions that described sulfuric acid decomposes sewage slag is: control SO
3Concentration is 6～80g/L, and temperature of reaction is 45～95 ℃, and the reaction times is 1～8 hour, and liquid-solid ratio is 2～8:1, the sulfuric acid consumption be in the acidolysis sewage slag quicklime by 95%～120% of the stoichiometric calculation theoretical amount.
3. according to the method for phosphorus in claim 1 and the 2 described recovery phosphate fertilizer plant sewage slags and fluorine, it is characterized in that the optimum reaction condition that described sulfuric acid decomposes sewage slag is: control SO
3Concentration is 25～55g/L, and temperature of reaction is 70～85 ℃, and the reaction times is 2～5 hours, and liquid-solid ratio is 4～5.5:1, the sulfuric acid consumption be in the acidolysis sewage slag quicklime by 100%～115% of the stoichiometric calculation theoretical amount.
4. the method for phosphorus and fluorine in the recovery according to claim 1 phosphate fertilizer plant sewage slag; It is characterized in that described phosphate fertilizer plant sewage slag be the phosphorous fluorine sewage of phosphate fertilizer plant through water technology from the isolated phosphorous fluorine sewage slag of filtering separation device, this sewage slag can be removed the part free-water through super-dry and also can directly be used for sulfuric acid without drying and decompose the sewage slag reaction.
5. according to the method for phosphorus in claim 1 and the 4 described recovery phosphate fertilizer plant sewage slags and fluorine, it is characterized in that described sewage slag not contain the butt of free-water, phosphorous with P
2O
5Count 12%～35%, fluorine-containing is 4%～12%.
6. the method for phosphorus and fluorine in the recovery according to claim 1 phosphate fertilizer plant sewage slag is characterized in that concentration and consumption that said a certain amount of phosphoric acid returns acid get for the traditional method calculating of the sulfuric acid decomposing phosphate rock known with those skilled in the art.
7. the method for phosphorus and fluorine in the recovery according to claim 1 phosphate fertilizer plant sewage slag is characterized in that said through dilute phosphoric acid that solid-liquid separation the obtains concentrated SPA that obtains under absolute pressure 10～11kPa, 75～80 ℃ of conditions.
8. the method for phosphorus and fluorine in the recovery according to claim 1 phosphate fertilizer plant sewage slag is characterized in that the P of said dilute phosphoric acid
2O
5Content is 15%～28%.
9. the method for phosphorus and fluorine in the recovery according to claim 1 phosphate fertilizer plant sewage slag is characterized in that the P of said SPA
2O
5Content is 35%～54%.
10. the method for phosphorus and fluorine in the recovery according to claim 1 phosphate fertilizer plant sewage slag is characterized in that described fluorochemical can be in silicofluoric acid, ammonium silicofluoride, Sodium Silicofluoride 98min, Sodium Fluoride, Neutral ammonium fluoride, matt salt, sodium aluminum fluoride, ALUMNIUM FLUORIDE, Calcium Fluoride (Fluorspan) and the hydrogen fluoride one or more.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992288A (en) * | 2012-12-12 | 2013-03-27 | 贵州开磷（集团）有限责任公司 | Method for preparing high pure phosphoric acid from calcium hydrogen phosphate |
| CN103553722A (en) * | 2013-10-24 | 2014-02-05 | 瓮福（集团）有限责任公司 | Method for preparing super phosphate by use of ardealite slag site sewage |
| CN104529008A (en) * | 2014-12-30 | 2015-04-22 | 中国天辰工程有限公司 | Treatment system and technology for wastewater containing fluorine and phosphorus used for nitric phosphate production technology |
| CN105367161A (en) * | 2015-10-30 | 2016-03-02 | 贵州开磷集团股份有限公司 | Method for preparing compound fertilizer by utilizing phosphorus-containing sewage |
| CN106430267A (en) * | 2016-08-31 | 2017-02-22 | 池州西恩新材料科技有限公司 | Resource recycling method for aluminum polishing phosphoric acid waste liquid |
| CN106745969A (en) * | 2016-12-06 | 2017-05-31 | 甘肃瓮福化工有限责任公司 | Sodium ion residual titration is applied to prodan production and carries out the system and method for wastewater treatment |
| CN109761238A (en) * | 2019-03-22 | 2019-05-17 | 盛隆资源再生（无锡）有限公司 | A method of utilizing fluorine-containing phosphorous devil liquor recovery prodan and phosphoric acid |
| CN110395705A (en) * | 2019-04-15 | 2019-11-01 | 江西南氏锂电新材料有限公司 | The utilization process of lepidolite extracted lithium tailings tertiary sodium phosphate |
| CN110540179A (en) * | 2019-09-03 | 2019-12-06 | 贵州开磷集团矿肥有限责任公司 | Method and equipment for removing harmful elements in wet-process phosphoric acid and derivative products thereof |
| CN110563198A (en) * | 2019-09-04 | 2019-12-13 | 广西长润环境工程有限公司 | Chemical fertilizer wastewater treatment method and treatment equipment |
| CN111392702A (en) * | 2020-03-20 | 2020-07-10 | 贵州川恒化工股份有限公司 | Method for preparing concentrated phosphoric acid and gypsum powder by semi-hydrated dihydrate process |
| CN113023698A (en) * | 2021-04-26 | 2021-06-25 | 陕西科原环保节能科技有限公司 | Neutralization slag treatment method in ammonium dihydrogen phosphate production process |
| CN113286760A (en) * | 2018-12-28 | 2021-08-20 | 苏尔瓦瑞斯公司 | Micronized sulphur powder |
| CN113603249A (en) * | 2021-08-24 | 2021-11-05 | 云南弘祥化工有限公司 | Process for precipitating sewage in phosphogypsum slag field for sodium fluosilicate production |
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2011
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| CN102992288A (en) * | 2012-12-12 | 2013-03-27 | 贵州开磷（集团）有限责任公司 | Method for preparing high pure phosphoric acid from calcium hydrogen phosphate |
| CN103553722A (en) * | 2013-10-24 | 2014-02-05 | 瓮福（集团）有限责任公司 | Method for preparing super phosphate by use of ardealite slag site sewage |
| CN104529008A (en) * | 2014-12-30 | 2015-04-22 | 中国天辰工程有限公司 | Treatment system and technology for wastewater containing fluorine and phosphorus used for nitric phosphate production technology |
| CN105367161A (en) * | 2015-10-30 | 2016-03-02 | 贵州开磷集团股份有限公司 | Method for preparing compound fertilizer by utilizing phosphorus-containing sewage |
| CN105367161B (en) * | 2015-10-30 | 2019-02-15 | 贵州开磷集团股份有限公司 | A kind of method of phosphorus-containing wastewater slag preparation compound fertilizer |
| CN106430267A (en) * | 2016-08-31 | 2017-02-22 | 池州西恩新材料科技有限公司 | Resource recycling method for aluminum polishing phosphoric acid waste liquid |
| CN106745969A (en) * | 2016-12-06 | 2017-05-31 | 甘肃瓮福化工有限责任公司 | Sodium ion residual titration is applied to prodan production and carries out the system and method for wastewater treatment |
| CN113286760A (en) * | 2018-12-28 | 2021-08-20 | 苏尔瓦瑞斯公司 | Micronized sulphur powder |
| CN109761238B (en) * | 2019-03-22 | 2021-04-06 | 盛隆资源再生（无锡）有限公司 | Method for recovering sodium fluosilicate and phosphoric acid by using fluorine-containing and phosphorus-containing waste liquid |
| CN109761238A (en) * | 2019-03-22 | 2019-05-17 | 盛隆资源再生（无锡）有限公司 | A method of utilizing fluorine-containing phosphorous devil liquor recovery prodan and phosphoric acid |
| CN110395705A (en) * | 2019-04-15 | 2019-11-01 | 江西南氏锂电新材料有限公司 | The utilization process of lepidolite extracted lithium tailings tertiary sodium phosphate |
| CN110540179A (en) * | 2019-09-03 | 2019-12-06 | 贵州开磷集团矿肥有限责任公司 | Method and equipment for removing harmful elements in wet-process phosphoric acid and derivative products thereof |
| CN110563198A (en) * | 2019-09-04 | 2019-12-13 | 广西长润环境工程有限公司 | Chemical fertilizer wastewater treatment method and treatment equipment |
| CN111392702A (en) * | 2020-03-20 | 2020-07-10 | 贵州川恒化工股份有限公司 | Method for preparing concentrated phosphoric acid and gypsum powder by semi-hydrated dihydrate process |
| CN111392702B (en) * | 2020-03-20 | 2021-11-26 | 贵州川恒化工股份有限公司 | Method for preparing concentrated phosphoric acid and gypsum powder by semi-hydrated dihydrate process |
| CN113023698A (en) * | 2021-04-26 | 2021-06-25 | 陕西科原环保节能科技有限公司 | Neutralization slag treatment method in ammonium dihydrogen phosphate production process |
| CN113023698B (en) * | 2021-04-26 | 2023-04-28 | 陕西科原环保节能科技有限公司 | Neutralizing slag treatment method in ammonium dihydrogen phosphate production process |
| CN113603249A (en) * | 2021-08-24 | 2021-11-05 | 云南弘祥化工有限公司 | Process for precipitating sewage in phosphogypsum slag field for sodium fluosilicate production |
| CN113603249B (en) * | 2021-08-24 | 2023-10-31 | 云南弘祥化工有限公司 | Process for precipitating sewage in phosphogypsum slag field for sodium fluosilicate production |
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