CN113830736A - Method for recycling phosphogypsum tailing recycled wastewater resources - Google Patents
Method for recycling phosphogypsum tailing recycled wastewater resources Download PDFInfo
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- CN113830736A CN113830736A CN202111055712.XA CN202111055712A CN113830736A CN 113830736 A CN113830736 A CN 113830736A CN 202111055712 A CN202111055712 A CN 202111055712A CN 113830736 A CN113830736 A CN 113830736A
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- defluorination
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/193—Preparation from silicon tetrafluoride, fluosilicic acid or fluosilicates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/01—Treating phosphate ores or other raw phosphate materials to obtain phosphorus or phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/02—Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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Abstract
The invention discloses a method for recycling waste water resources of phosphogypsum tailings, which comprises the following steps: s1, adding lime water into the phosphogypsum tailing recycling wastewater, adjusting the pH value of the phosphogypsum tailing recycling wastewater to be more than 10, and filtering to obtain mixture solid and defluorination mother liquor; s2, adding a sulfuric acid solution into the mixture solid, and heating to 70-80 ℃ to obtain hydrogen fluoride and calcium sulfate; s3, carrying out evaporation concentration operation on the defluorination mother liquor, then detecting the concentration of potassium ions in the defluorination mother liquor, and when the concentration of the potassium ions in the defluorination mother liquor is not less than 20g/L, adding a sulfuric acid solution into the defluorination mother liquor, and adjusting the pH value of the defluorination mother liquor to 1-2; obtaining silicic acid and potassium sulfate solution after centrifugal separation operation; and S4, sequentially carrying out polymer membrane concentration and evaporation concentration on the potassium sulfate solution, and then filtering to obtain a filtered solution and potassium sulfate, wherein the filtered solution is recycled in the phosphorus chemical industry enterprises.
Description
Technical Field
The invention relates to the field of phosphogypsum production, in particular to a method for recycling phosphogypsum tailing recycling wastewater resources.
Background
The wet preparation of phosphoric acid refers to the dissolution of phosphate ore with acids such as sulfuric acid, hydrochloric acid, nitric acid, etc. And discharging the dissolved waste slag and wastewater to a tailing pond for stacking and sedimentation, and recycling the stacked and sedimentated wastewater. In the process of recycling the wastewater, the SiF in the wastewater is caused to be stored6 2-、K+、Na+The plasma is continuously enriched, the temperature of the wastewater discharged from a production workshop to a tailing pond is higher, and finally, the fluosilicate in the wastewater is supersaturated, the temperature of a conveying pipeline is reduced during recycling, and the water flow disturbance is severe, so that the fluosilicate in the wastewater is separated out and scales in the conveying pipeline, and a large amount of mineral resources are lost while the conveying pipeline is blocked, therefore, the mineral resources in the phosphogypsum tailing recycling wastewater need to be recycled.
Disclosure of Invention
The invention aims to solve the problems and provides a method for recycling phosphogypsum tailings recycled wastewater resources, which is simple to operate and high in utilization rate.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for recycling phosphogypsum tailings by using waste water resources comprises the following steps:
s1, adding lime water into the phosphogypsum tailing recycling wastewater, adjusting the pH value of the phosphogypsum tailing recycling wastewater to be more than 10, and filtering to obtain mixture solid and defluorination mother liquor;
s2, adding a sulfuric acid solution into the mixture solid, and heating to 70-80 ℃ to obtain hydrogen fluoride and calcium sulfate;
s3, carrying out evaporation concentration operation on the defluorination mother liquor, then detecting the concentration of potassium ions in the defluorination mother liquor, and enabling the defluorination mother liquor to be used for dissolving raw ores in phosphorus chemical enterprises when the concentration of the potassium ions in the defluorination mother liquor is less than 20 g/L; when the concentration of potassium ions in the defluorination mother liquor is not less than 20g/L, adding a sulfuric acid solution into the defluorination mother liquor, and adjusting the pH value of the defluorination mother liquor to 1-2; obtaining silicic acid and potassium sulfate solution after centrifugal separation operation;
and S4, sequentially carrying out polymer membrane concentration and evaporation concentration on the potassium sulfate solution, and then filtering to obtain a filtered solution and potassium sulfate, wherein the filtered solution is recycled in the phosphorus chemical industry enterprises.
Further, in the step S1, the concentration of the lime water is 30% to 50%.
Further, in the step S2, the mass ratio of the mixture solid to the sulfuric acid solution is 1: 10; the concentration of the sulfuric acid solution is 15-30%.
Compared with the prior art, the invention has the advantages and positive effects that:
the method comprises the steps of obtaining calcium sulfate and hydrogen fluoride from phosphogypsum tailings recycled wastewater by using lime water and sulfuric acid solution, and then obtaining potassium sulfate and other mixed solution containing mineral substances from defluorination mother liquor through concentration and filtration operation; the recovery operation of various mineral resources in the phosphogypsum tailing recycling wastewater is realized, the scaling phenomenon of fluosilicate in the wastewater is avoided while the resource recovery effect is achieved, and the recycling effect of the phosphogypsum tailing wastewater is improved; and the whole recovery process is simple to operate, convenient and quick, the recovery difficulty of mineral resources in the phosphogypsum tailing recycling wastewater is reduced, and the recovery efficiency of the mineral resources is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a block diagram of the framework of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived from the embodiments of the present invention by a person skilled in the art without any creative effort, should be included in the protection scope of the present invention.
Embodiment 1, as shown in fig. 1, this embodiment discloses a method for recycling phosphogypsum tailings recycled wastewater resources, which includes the following steps:
s1, adding lime water into the phosphogypsum tailing recycling wastewater, wherein the concentration of the lime water is 30%; adjusting the pH value of the phosphogypsum tailing reuse wastewater to 11, and filtering to obtain a mixture solid and a defluorination mother liquor; the main components of the solid of the mixture are calcium sulfate and calcium fluoride, and the main components of the defluorination mother liquor are sulfate radical, silicate radical, potassium ion, sodium ion, hydroxide radical and the like;
s2, adding a sulfuric acid solution into the mixture solid, wherein the mass ratio of the mixture solid to the sulfuric acid solution is 1: 10; the concentration of the sulfuric acid solution is 15 percent; heating to 70 ℃ to obtain hydrogen fluoride and calcium sulfate;
s3, carrying out evaporation concentration operation on the defluorination mother liquor, then detecting the concentration of potassium ions in the defluorination mother liquor, and enabling the defluorination mother liquor to be used for dissolving raw ores in phosphorus chemical enterprises when the concentration of the potassium ions in the defluorination mother liquor is less than 20 g/L; when the concentration of potassium ions in the defluorination mother liquor is not less than 20g/L, adding a sulfuric acid solution into the defluorination mother liquor, and adjusting the pH value of the defluorination mother liquor to 1; obtaining silicic acid and potassium sulfate solution after centrifugal separation operation;
s4, sequentially concentrating the potassium sulfate solution through a polymer membrane, evaporating, concentrating and filtering to obtain a filtered solution and potassium sulfate, wherein the main components of the filtered solution are sulfate radicals, potassium ions and sodium ions; the filtered solution can be recycled in phosphorus chemical enterprises.
Embodiment 2, as shown in fig. 1, this embodiment discloses a method for recycling phosphogypsum tailings recycled wastewater resources, which includes the following steps:
s1, adding lime water into the phosphogypsum tailing recycling wastewater, wherein the concentration of the lime water is 40%; adjusting the pH value of the phosphogypsum tailing reuse wastewater to 12, and filtering to obtain a mixture solid and a defluorination mother liquor; the main components of the solid of the mixture are calcium sulfate and calcium fluoride, and the main components of the defluorination mother liquor are sulfate radical, silicate radical, potassium ion, sodium ion, hydroxide radical and the like;
s2, adding a sulfuric acid solution into the mixture solid, wherein the mass ratio of the mixture solid to the sulfuric acid solution is 1: 10; the concentration of the sulfuric acid solution is 20 percent; heating to 75 ℃ to obtain hydrogen fluoride and calcium sulfate;
s3, carrying out evaporation concentration operation on the defluorination mother liquor, then detecting the concentration of potassium ions in the defluorination mother liquor, and enabling the defluorination mother liquor to be used for dissolving raw ores in phosphorus chemical enterprises when the concentration of the potassium ions in the defluorination mother liquor is less than 20 g/L; when the concentration of potassium ions in the defluorination mother liquor is not less than 20g/L, adding a sulfuric acid solution into the defluorination mother liquor, and adjusting the pH value of the defluorination mother liquor to be 2; obtaining silicic acid and potassium sulfate solution after centrifugal separation operation;
s4, sequentially concentrating the potassium sulfate solution through a polymer membrane, evaporating, concentrating and filtering to obtain a filtered solution and potassium sulfate, wherein the main components of the filtered solution are sulfate radicals, potassium ions and sodium ions; the filtered solution can be recycled in phosphorus chemical enterprises.
Embodiment 3, as shown in fig. 1, this embodiment discloses a method for recycling phosphogypsum tailings recycled wastewater resources, which includes the following steps:
s1, adding lime water into the phosphogypsum tailing recycling wastewater, wherein the concentration of the lime water is 50%; adjusting the pH value of the phosphogypsum tailing reuse wastewater to 14, and filtering to obtain a mixture solid and a defluorination mother liquor; the main components of the solid of the mixture are calcium sulfate and calcium fluoride, and the main components of the defluorination mother liquor are sulfate radical, silicate radical, potassium ion, sodium ion, hydroxide radical and the like;
s2, adding a sulfuric acid solution into the mixture solid, wherein the mass ratio of the mixture solid to the sulfuric acid solution is 1: 10; the concentration of the sulfuric acid solution is 30 percent; heating to 80 ℃ to obtain hydrogen fluoride and calcium sulfate;
s3, carrying out evaporation concentration operation on the defluorination mother liquor, then detecting the concentration of potassium ions in the defluorination mother liquor, and enabling the defluorination mother liquor to be used for dissolving raw ores in phosphorus chemical enterprises when the concentration of the potassium ions in the defluorination mother liquor is less than 20 g/L; when the concentration of potassium ions in the defluorination mother liquor is not less than 20g/L, adding a sulfuric acid solution into the defluorination mother liquor, and adjusting the pH value of the defluorination mother liquor to be 2; obtaining silicic acid and potassium sulfate solution after centrifugal separation operation;
s4, sequentially concentrating the potassium sulfate solution through a polymer membrane, evaporating, concentrating and filtering to obtain a filtered solution and potassium sulfate, wherein the main components of the filtered solution are sulfate radicals, potassium ions and sodium ions; the filtered solution can be recycled in phosphorus chemical enterprises.
The method comprises the steps of obtaining calcium sulfate and hydrogen fluoride from phosphogypsum tailings recycled wastewater by using lime water and sulfuric acid solution, and then obtaining potassium sulfate and other mixed solution containing mineral substances from defluorination mother liquor through concentration and filtration operation; the recovery operation of various mineral resources in the phosphogypsum tailing recycling wastewater is realized, the scaling phenomenon of fluosilicate in the wastewater is avoided while the resource recovery effect is achieved, and the recycling effect of the phosphogypsum tailing wastewater is improved; and the whole recovery process is simple to operate, convenient and quick, the recovery difficulty of mineral resources in the phosphogypsum tailing recycling wastewater is reduced, and the recovery efficiency of the mineral resources is improved.
Claims (3)
1. A method for recycling phosphogypsum tailings by using waste water resources is characterized by comprising the following steps: the method comprises the following steps:
s1, adding lime water into the phosphogypsum tailing recycling wastewater, adjusting the pH value of the phosphogypsum tailing recycling wastewater to be more than 10, and filtering to obtain mixture solid and defluorination mother liquor;
s2, adding a sulfuric acid solution into the mixture solid, and heating to 70-80 ℃ to obtain hydrogen fluoride and calcium sulfate;
s3, carrying out evaporation concentration operation on the defluorination mother liquor, then detecting the concentration of potassium ions in the defluorination mother liquor, and enabling the defluorination mother liquor to be used for dissolving raw ores in phosphorus chemical enterprises when the concentration of the potassium ions in the defluorination mother liquor is less than 20 g/L; when the concentration of potassium ions in the defluorination mother liquor is not less than 20g/L, adding a sulfuric acid solution into the defluorination mother liquor, and adjusting the pH value of the defluorination mother liquor to 1-2; obtaining silicic acid and potassium sulfate solution after centrifugal separation operation;
and S4, sequentially carrying out polymer membrane concentration and evaporation concentration on the potassium sulfate solution, and then filtering to obtain a filtered solution and potassium sulfate, wherein the filtered solution is recycled in the phosphorus chemical industry enterprises.
2. The method for recycling the resource of the phosphogypsum tailings reclaimed wastewater of claim 1, which is characterized in that: in the step S1, the concentration of the lime water is 30-50%.
3. The method for recycling the resource of the phosphogypsum tailings reclaimed wastewater according to claim 2, which is characterized in that: in the step S2, the mass ratio of the mixture solid to the sulfuric acid solution is 1: 10; the concentration of the sulfuric acid solution is 15-30%.
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| CN202111055712.XA CN113830736A (en) | 2021-09-09 | 2021-09-09 | Method for recycling phosphogypsum tailing recycled wastewater resources |
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| CN202111055712.XA CN113830736A (en) | 2021-09-09 | 2021-09-09 | Method for recycling phosphogypsum tailing recycled wastewater resources |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1650611A1 (en) * | 1989-01-16 | 1991-05-23 | Воскресенский филиал Научно-исследовательского института по удобрениям и инсектофунгицидам им.проф.Я.В.Самойлова Научно-производственного объединения "Минудобрения" | Method for waste water complex treating |
| CN102351590A (en) * | 2011-07-18 | 2012-02-15 | 贵州省化工研究院 | Method for producing high-water solubility nitrophosphate fertilizer by phosphorite nitrolysis and calcium nitrate freezing |
| CN102887535A (en) * | 2012-10-09 | 2013-01-23 | 湖北富邦科技股份有限公司 | Method for recycling high-purity fluorine and phosphorus from wastewater of phosphogypsum residue field |
| CN105502730A (en) * | 2015-11-30 | 2016-04-20 | 湖北宜化集团有限责任公司 | Physicochemical treatment method for mixed type chemical fertilizer production wastewater |
-
2021
- 2021-09-09 CN CN202111055712.XA patent/CN113830736A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1650611A1 (en) * | 1989-01-16 | 1991-05-23 | Воскресенский филиал Научно-исследовательского института по удобрениям и инсектофунгицидам им.проф.Я.В.Самойлова Научно-производственного объединения "Минудобрения" | Method for waste water complex treating |
| CN102351590A (en) * | 2011-07-18 | 2012-02-15 | 贵州省化工研究院 | Method for producing high-water solubility nitrophosphate fertilizer by phosphorite nitrolysis and calcium nitrate freezing |
| CN102887535A (en) * | 2012-10-09 | 2013-01-23 | 湖北富邦科技股份有限公司 | Method for recycling high-purity fluorine and phosphorus from wastewater of phosphogypsum residue field |
| CN105502730A (en) * | 2015-11-30 | 2016-04-20 | 湖北宜化集团有限责任公司 | Physicochemical treatment method for mixed type chemical fertilizer production wastewater |
Non-Patent Citations (2)
| Title |
|---|
| 夏海建: "磷石膏渣场地水循环利用过程中防堵塞技术研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 荆晓等: "《中学化学词典》", 30 April 1998, 中国人民公安大学出版社 * |
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