CN102887535A - Method for recycling high-purity fluorine and phosphorus from wastewater of phosphogypsum residue field - Google Patents
Method for recycling high-purity fluorine and phosphorus from wastewater of phosphogypsum residue field Download PDFInfo
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- CN102887535A CN102887535A CN2012103800029A CN201210380002A CN102887535A CN 102887535 A CN102887535 A CN 102887535A CN 2012103800029 A CN2012103800029 A CN 2012103800029A CN 201210380002 A CN201210380002 A CN 201210380002A CN 102887535 A CN102887535 A CN 102887535A
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Abstract
The invention relates to a method for recycling high-purity fluorine and phosphorus from a wastewater of phosphogypsum residue field. According to the different reaction conditions of calcium fluoride and magnesium ammonium phosphate, the implementation of the method is divided into two stages: in the first stage of recycling high-purity calcium fluoride: adjusting the pH (Potential Of Hydrogen) value of the wastewater of the phosphogypsum residue field by a sodium hydroxide solution to 3-6 to enable the fluoride ions and calcium ions in the wastewater to be reacted to generate calcium fluoride precipitate, filtering and recycling calcium fluoride; and the second stage of recycling high-purity magnesium ammonium phosphate: adjusting the pH value of the wastewater after the first section of recycling high-purity calcium fluoride by the sodium hydroxide solution to 7.5-9.5, adding a magnesium source and an ammonia source at the same time, generating magnesium ammonium phosphate, magnesium ammonium phosphate analogs or phosphate compounds in a crystalline state in a magnesium ammonium phosphate crystallization reactor, filtering and recycling magnesium ammonium phosphate. The water treated by the method disclosed by the invention has low impurity content and can be directly used as the industrial water and circulating cooling water in a phosphorus chemical production system.
Description
Technical field
The present invention relates to field of waste water treatment, particularly relate to phosphogypsum slag field fluorine in wastewater and reclaim with the Calcium Fluoride (Fluorspan) form, phosphorus reclaims with the form of magnesium ammonium phosphate slow release fertilizer.
Background technology
Phosphogypsum is the by product in the Wet-process Phosphoric Acid Production, and phosphoric acid per ton will be produced 4.5-5.5 ton (butt) phosphogypsum, and its composition is relevant with used phosphorus ore and technical process.Contain water miscible Vanadium Pentoxide in FLAKES and fluorion in the phosphogypsum, along with China's phosphoric acid and high concentration phosphate fertilizer industrial expansion, the phosphogypsum quantity of annual discharging is increasing, pollution to environment also is tending towards serious, especially phosphogypsum is behind rain, and the pollutent of its stripping is understood polluted surface water, underground water and soil.Phosphogypsum slag field waste water comprise phosphogypsum again pulp-water, backwater, percolating water and phosphogypsum rain glassware for drinking water be corrosive by force, therefore fluorine and phosphorus content high need to be processed phosphogypsum slag field waste water.
Conventional phosphogypsum slag field waste water is only processed backwater, and purifying treatment scheme commonly used is that unslaked lime method neutralization precipitation method is processed slag field backwater, unslaked lime is added in the backwater of slag field, and the PH=4.5-9 of control backwater, and make wherein water-soluble P
2O
5Phosphoric acid salt and fluorochemical with F generation insoluble.Return phosphoric acid plant through the backwater after the clarification, as the filter cake washing water of phosphoric acid filter, wash-down water and pulp-water again.
The advantage of this scheme is that technical process is simple, and equipment is few, and floor space is little, and energy consumption is economized.But its shortcoming is that the water quality discharge quality after process (1) is the more difficult stably reaching standard of fluorine especially, water-soluble P in (2) phosphogypsum
2O
5Can not recycle with F, waste resource, (3) backwater neutralization reaction produces the solid sludge with a certain amount of silica gel, and the clarified separation difficulty is processed trouble, and (4) do not have the creation of value, and production cost is high, and working expense is high.
Summary of the invention
The following problem that purpose of the present invention exists for the prior art that solves: conventional phosphogypsum slag field backwater adopts fluorion and the calcium ion in the unslaked lime processing precipitator method technique removal waste water, the fluctuation of effluent quality fluorion is larger, be difficult to up to standard, and fluorine and phosphorus are removed mainly with the form of contamination precipitation, not only generate a large amount of mud, and the waste resource.In view of technology and environmental angle, the invention provides a kind of method that from the waste water of phosphogypsum slag field, reclaims high-purity fluorine and phosphorus, wherein fluorine exists with the Calcium Fluoride (Fluorspan) form, purity can realize recovery and the utilization of fluorine more than 90%, and phosphorus exists with the slow release fertilizer form of magnesium ammonium phosphate, purity is more than 90%, the rate of recovery of fluorine is not less than 85% in the whole technical process, and the rate of recovery of phosphorus is not less than 70%, has created economic worth.
Technical scheme of the present invention is:
A kind of method that from the waste water of phosphogypsum slag field, reclaims high-purity fluorine and phosphorus, different according to Calcium Fluoride (Fluorspan) and magnesium ammonium phosphate reaction conditions, the enforcement of the method is divided into two sections, it is characterized in that concrete steps are:
First paragraph reclaims high purity and fluoridizes calcium: the pH value of regulating phosphogypsum slag field waste water with sodium hydroxide solution is 3-6, so that the fluorion in the waste water and calcium ion reaction generate the Calcium Fluoride (Fluorspan) precipitation, filtered and recycled Calcium Fluoride (Fluorspan), purity reach more than 90%, and the rate of recovery of fluorine is not less than 85%; If there is remaining fluorine to add calcium chloride or magnesium chloride solution removal in the processed waste water, remove if there is remaining calcium to add ammonium bicarbonate soln, introduce in addition the reaction that ammonium ion can participate in the second segment magnesium ammonium phosphate;
Second segment reclaims high-purity phosphoric acid ammonium magnesium: regulate first paragraph with sodium hydroxide solution and reclaim high purity and fluoridize that the pH value of waste water is 7.5-9.5 behind the calcium, add simultaneously magnesium source and ammonia source, in the ammoniomagnesium phosphate crystal reactor, generate magnesium ammonium phosphate, magnesium ammonium phosphate analogue or the phosphate compounds with crystalline state, the filtered and recycled magnesium ammonium phosphate, wherein magnesium ammonium phosphate purity reaches more than 90%, and the rate of recovery of phosphorus is not less than 70%.
Described phosphogypsum slag field waste water comprises phosphogypsum slag field again pulp-water, phosphogypsum rain water and/or phosphogypsum transudate.
Described phosphogypsum slag field waste water is acid strong, and pH is between 1-3.
Contain a large amount of water-soluble fluorines, phosphorus, calcium, magnesium, iron and silicate ion in the waste water of described phosphogypsum slag field.
The content of phosphogypsum slag field fluorine in wastewater, calcium and phosphorus is high, fluorine content 500ppm-5000ppm, phosphorus content 500ppm-10000ppm, calcium contents 500ppm-8000ppm.
The magnesium source that adds is magnesium chloride.
The ammonia source that adds is ammoniacal liquor, ammonium chloride, volatile salt or bicarbonate of ammonia.
Water outlet behind the process reactor can reach the secondary standard of " integrated wastewater discharge standard ", can arrive phosphorous chemical industry production system, perhaps qualified discharge by direct reuse.
The present invention compared with prior art, its advantage mainly comprises:
One, employing two-stage method technique reclaim respectively fluorine and phosphorus, and the rate of recovery is high, and purity is high, realizes resource circulation utilization.
Two, adopt sodium hydroxide solution to regulate the pH of waste water, so that the fluorion in the waste water and calcium ion spontaneous reaction generate Calcium Fluoride (Fluorspan) precipitation and a small amount of calcium phosphate precipitation, the purity of Calcium Fluoride (Fluorspan) has higher economic worth up to recycling fluorine more than 90%.
If three, unnecessary fluorion generates the removal of Calcium Fluoride (Fluorspan) precipitation by adding calcium chloride or magnesium chloride in the waste water, unnecessary calcium ion can generate the precipitation of calcium carbonate removal by adding bicarbonate of ammonia, fluorine removal in the waste water is stable and clearance is high, does not affect the recovery of next step phosphorus.
Four, adopt sodium hydroxide solution to regulate the pH value of waste water, add magnesium source and ammonia source, the water miscible phosphorus in the waste water of phosphogypsum slag field is existed with magnesium ammonium phosphate slow release fertilizer form, have higher social value and economic worth.Adopt two-stage method technique, the clearance of fluorine is stable, and phosphorous recovery is higher, and the final outflow water foreign matter content can arrive phosphorous chemical industry production system or qualified discharge by direct reuse.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
Embodiment 1
Certain phosphogypsum slag field, chemical plant wastewater discharge 5000m3/d, wherein Phosphorus From Wastewater content 5200mg/l, fluorine content 1500mg/l, calcium ion content 2300mg/l, wastewater pH 2.3; First paragraph process using volumetric molar concentration is that the 1mol/l sodium hydroxide solution is regulated phosphogypsum slag field wastewater pH 5.3, there are Calcium Fluoride (Fluorspan) precipitation and a small amount of calcium phosphate precipitation to generate, Calcium Fluoride (Fluorspan) purity 95% by analysis, the rate of recovery of fluorine is 99%, wherein residual fluorine is 15mg/l in the waste water, phosphorus is 4698mg/l, and calcium is 20mg/l; Second segment process using volumetric molar concentration is that the 1mol/l sodium hydroxide solution is regulated phosphogypsum slag field wastewater pH 8.2, adding concentration is that 1mol/l ammonium chloride solution 750ml and concentration are the magnesium chloride 780ml solution of 1mol/l, reaction in the ammoniomagnesium phosphate crystal reaction, generate magnesium ammonium phosphate granulated fertilizer purity 92%, the rate of recovery of phosphorus is 90.1%, end reaction device water outlet phosphorus content 15mg/l, fluorine content 7mg/l can directly use as the phosphorous chemical industry recirculated cooling water.
Embodiment 2
Certain phosphogypsum slag field, chemical plant wastewater discharge 5000m3/d, wherein Phosphorus From Wastewater content 10000mg/l, fluorine content 500mg/l, calcium ion content 1300mg/l, wastewater pH 1.0; First paragraph process using volumetric molar concentration is that the 1mol/l sodium hydroxide solution is regulated phosphogypsum slag field wastewater pH 3.0, there are Calcium Fluoride (Fluorspan) precipitation and a small amount of calcium phosphate precipitation to generate, Calcium Fluoride (Fluorspan) purity 96% by analysis, the rate of recovery of fluorine is 98%, wherein residual fluorine is 10mg/l in the waste water, phosphorus is 9200mg/l, and calcium is 15mg/l; Second segment process using volumetric molar concentration is that the 1mol/l sodium hydroxide solution is regulated phosphogypsum slag field wastewater pH 7.5, adding concentration is that 2mol/l ammonium bicarbonate soln 740ml and concentration are the magnesium chloride solution 780ml of 2mol/l, reaction in the ammoniomagnesium phosphate crystal reaction, generate magnesium ammonium phosphate granulated fertilizer purity 94%, the rate of recovery of phosphorus is 91.8%, end reaction device water outlet phosphorus content 12mg/l, fluorine content 5mg/l can directly use as the phosphorous chemical industry process water.
Embodiment 3
Certain phosphogypsum slag field, chemical plant wastewater discharge 5000m3/d, wherein Phosphorus From Wastewater content 7000mg/l, fluorine content 3500mg/l, calcium ion content 6000mg/l, wastewater pH 3.0; First paragraph process using volumetric molar concentration is that the 1mol/l sodium hydroxide solution is regulated phosphogypsum slag field wastewater pH 6.0, there are Calcium Fluoride (Fluorspan) precipitation and a small amount of calcium phosphate precipitation to generate, Calcium Fluoride (Fluorspan) purity 99% by analysis, the rate of recovery of fluorine is 99.7%, wherein residual fluorine is 15mg/l in the waste water, and phosphorus is 5800mg/l, and calcium is 25mg/l, add again amount of ammonium bicarbonate in the processed waste water and remove calcium ion, introduce the reaction that ammonium ion can participate in the second segment magnesium ammonium phosphate; Second segment process using volumetric molar concentration is that the 1mol/l sodium hydroxide solution is regulated phosphogypsum slag field wastewater pH 9.5, adding concentration is that 1mol/l sal volatile 940ml and concentration are the magnesium chloride solution 980ml of 1mol/l, reaction in the ammoniomagnesium phosphate crystal reaction, generate magnesium ammonium phosphate granulated fertilizer purity 96%, the rate of recovery of phosphorus is 82.8%, end reaction device water outlet phosphorus content 3mg/l, fluorine content 2mg/l, directly qualified discharge.
Adopt two-stage method technique, realized the recovery of phosphogypsum slag field fluorine in wastewater and phosphorus, the Calcium Fluoride (Fluorspan) of generation and magnesium ammonium phosphate purity are high, can realize resource circulation utilization, and have higher commercial value.
Claims (10)
1. method that from the waste water of phosphogypsum slag field, reclaims high-purity fluorine and phosphorus, different according to Calcium Fluoride (Fluorspan) and magnesium ammonium phosphate reaction conditions, the enforcement of the method is divided into two sections, it is characterized in that concrete steps are:
First paragraph reclaims high purity and fluoridizes calcium: the pH value of regulating phosphogypsum slag field waste water with sodium hydroxide solution is 3-6, so that the fluorion in the waste water and calcium ion reaction generate Calcium Fluoride (Fluorspan) precipitation, filtered and recycled Calcium Fluoride (Fluorspan);
Second segment reclaims high-purity phosphoric acid ammonium magnesium: regulate first paragraph with sodium hydroxide solution and reclaim high purity and fluoridize that the pH value of waste water is 7.5-9.5 behind the calcium, add simultaneously magnesium source and ammonia source, in the ammoniomagnesium phosphate crystal reactor, generate magnesium ammonium phosphate, magnesium ammonium phosphate analogue or the phosphate compounds with crystalline state, filtered and recycled magnesium ammonium phosphate.
2. it is characterized in that in accordance with the method for claim 1: described phosphogypsum slag field waste water comprises phosphogypsum slag field again pulp-water, phosphogypsum rain water and/or phosphogypsum transudate.
3. in accordance with the method for claim 1, it is characterized in that: described phosphogypsum slag field waste water is acid strong, and pH is between 1-3.
4. it is characterized in that in accordance with the method for claim 1: contain a large amount of water-soluble fluorines, phosphorus, calcium, magnesium, iron and silicate ion in the waste water of described phosphogypsum slag field.
5. in accordance with the method for claim 1, it is characterized in that: the content of phosphogypsum slag field fluorine in wastewater, calcium and phosphorus is high, fluorine content 500ppm-5000ppm, phosphorus content 500ppm-10000ppm, calcium contents 500ppm-8000ppm.
6. according to one of any described method of claim 1-5, it is characterized in that: first paragraph reclaims high purity and fluoridizes behind the calcium in the waste water remaining fluorine or calcium and remove by outer adding medicine, wherein fluorion is removed by adding calcium chloride or magnesium chloride solution generation Calcium Fluoride (Fluorspan) precipitation, and calcium ion is removed by adding bicarbonate of ammonia generation precipitation of calcium carbonate.
7. according to one of any described method of claim 1-5, it is characterized in that: the magnesium source that adds is magnesium chloride.
8. according to one of any described method of claim 1-5, it is characterized in that: the ammonia source that adds is ammoniacal liquor, ammonium chloride, volatile salt or bicarbonate of ammonia.
9. in accordance with the method for claim 1, it is characterized in that: the Calcium Fluoride (Fluorspan) purity of described recovery reaches more than 90%, and the rate of recovery of fluorine is not less than 85%.
10. in accordance with the method for claim 1, it is characterized in that: the magnesium ammonium phosphate purity of described recovery reaches more than 90%, and the rate of recovery of phosphorus is not less than 70%.
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103241861A (en) * | 2013-05-07 | 2013-08-14 | 湖北富邦科技股份有限公司 | Method for treating phosphorus- and/or fluorine-containing acid waste water and preparing granular magnesium ammonium phosphate |
| CN103435084A (en) * | 2013-08-26 | 2013-12-11 | 四川理工学院 | Method for preparing artificial fluorite from fluorine-containing waste gas in phosphorus chemical industry |
| CN104086019A (en) * | 2014-06-17 | 2014-10-08 | 湖北富邦科技股份有限公司 | Industrial high-concentration phosphorus-containing wastewater treatment method |
| CN105442047A (en) * | 2015-12-25 | 2016-03-30 | 华东理工大学 | Method for extracting fluorine element from industrial gypsum |
| CN106277005A (en) * | 2016-08-27 | 2017-01-04 | 盛隆资源再生（无锡）有限公司 | A kind of recovery cryolite, calcium carbonate and method of sodium sulfate from calcium fluoride sludge resource |
| CN110104848A (en) * | 2019-06-17 | 2019-08-09 | 武汉兴天宇环境股份有限公司 | A kind of ardealite dump leaching wastewater treatment method |
| CN110282783A (en) * | 2019-07-23 | 2019-09-27 | 格丰科技材料有限公司 | A kind of processing system and processing method of phosphorus ammonium wastewater from chemical industry |
| 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 |
| 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 |
| CN111498940A (en) * | 2020-05-11 | 2020-08-07 | 江苏一夫科技股份有限公司 | Separation treatment method of phosphorus-containing and fluorine-containing phosphogypsum washing waste liquid |
| 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 |
| CN113121035A (en) * | 2020-12-13 | 2021-07-16 | 中南民族大学 | Treatment device and treatment method for recycling phosphogypsum leachate |
| CN113336356A (en) * | 2021-05-08 | 2021-09-03 | 武汉工程大学 | Phosphogypsum leachate recycling treatment and utilization method |
| CN113548765A (en) * | 2021-08-20 | 2021-10-26 | 湖南中天青鼎工程科技股份有限公司 | Resource recovery method for phosphogypsum recycling wastewater |
| CN113830736A (en) * | 2021-09-09 | 2021-12-24 | 湖南中天青鼎工程科技股份有限公司 | Method for recycling phosphogypsum tailing recycled wastewater resources |
| CN114275756A (en) * | 2021-12-30 | 2022-04-05 | 中国科学院地球化学研究所 | Method for recovering phosphorus resource and byproduct magnesium ammonium phosphate in phosphogypsum |
| CN115073242A (en) * | 2022-07-22 | 2022-09-20 | 中南民族大学 | Composite soil conditioner based on phosphorus chemical alkaline residue and preparation method and application thereof |
| CN115611401A (en) * | 2022-12-16 | 2023-01-17 | 淄博包钢灵芝稀土高科技股份有限公司 | Recycling separation and purification method for alkaline high-content fluorine and phosphorus wastewater from rare earth ore hydrometallurgy |
| CN115784238A (en) * | 2022-10-18 | 2023-03-14 | 宜都兴发化工有限公司 | Method for recovering soluble fluorine in phosphogypsum |
| CN116037631A (en) * | 2022-12-29 | 2023-05-02 | 贵州鼎瑞环保科技有限公司 | Phosphogypsum raw slag harmless treatment method |
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| CN103241861A (en) * | 2013-05-07 | 2013-08-14 | 湖北富邦科技股份有限公司 | Method for treating phosphorus- and/or fluorine-containing acid waste water and preparing granular magnesium ammonium phosphate |
| CN103435084A (en) * | 2013-08-26 | 2013-12-11 | 四川理工学院 | Method for preparing artificial fluorite from fluorine-containing waste gas in phosphorus chemical industry |
| CN104086019A (en) * | 2014-06-17 | 2014-10-08 | 湖北富邦科技股份有限公司 | Industrial high-concentration phosphorus-containing wastewater treatment method |
| CN105442047A (en) * | 2015-12-25 | 2016-03-30 | 华东理工大学 | Method for extracting fluorine element from industrial gypsum |
| CN105442047B (en) * | 2015-12-25 | 2018-02-16 | 华东理工大学 | A kind of method that fluorine element is extracted from industrial gypsum |
| CN106277005A (en) * | 2016-08-27 | 2017-01-04 | 盛隆资源再生（无锡）有限公司 | A kind of recovery cryolite, calcium carbonate and method of sodium sulfate from calcium fluoride sludge resource |
| CN110104848A (en) * | 2019-06-17 | 2019-08-09 | 武汉兴天宇环境股份有限公司 | A kind of ardealite dump leaching wastewater treatment method |
| CN110282783A (en) * | 2019-07-23 | 2019-09-27 | 格丰科技材料有限公司 | A kind of processing system and processing method of phosphorus ammonium wastewater from chemical industry |
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| CN114275756A (en) * | 2021-12-30 | 2022-04-05 | 中国科学院地球化学研究所 | Method for recovering phosphorus resource and byproduct magnesium ammonium phosphate in phosphogypsum |
| CN115073242A (en) * | 2022-07-22 | 2022-09-20 | 中南民族大学 | Composite soil conditioner based on phosphorus chemical alkaline residue and preparation method and application thereof |
| CN115073242B (en) * | 2022-07-22 | 2024-02-27 | 中南民族大学 | Composite soil conditioner based on alkaline residues of phosphorus chemical industry and preparation method and application thereof |
| CN115784238A (en) * | 2022-10-18 | 2023-03-14 | 宜都兴发化工有限公司 | Method for recovering soluble fluorine in phosphogypsum |
| CN115784238B (en) * | 2022-10-18 | 2024-03-12 | 宜都兴发化工有限公司 | Method for recycling soluble fluorine in phosphogypsum |
| CN115611401A (en) * | 2022-12-16 | 2023-01-17 | 淄博包钢灵芝稀土高科技股份有限公司 | Recycling separation and purification method for alkaline high-content fluorine and phosphorus wastewater from rare earth ore hydrometallurgy |
| CN116037631A (en) * | 2022-12-29 | 2023-05-02 | 贵州鼎瑞环保科技有限公司 | Phosphogypsum raw slag harmless treatment method |
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