CN115108541A - Method for recycling ultralow-concentration phosphorus-containing wastewater - Google Patents
Method for recycling ultralow-concentration phosphorus-containing wastewater Download PDFInfo
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- CN115108541A CN115108541A CN202210823076.9A CN202210823076A CN115108541A CN 115108541 A CN115108541 A CN 115108541A CN 202210823076 A CN202210823076 A CN 202210823076A CN 115108541 A CN115108541 A CN 115108541A
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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
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
Abstract
The invention discloses a method for recycling ultralow-concentration phosphorus-containing wastewater, which comprises the steps of carrying out neutralization reaction on the ultralow-concentration phosphorus-containing wastewater and a calcium hydroxide solution, settling, separating and dehydrating a slurry to obtain a semi-finished product for producing feed-grade monocalcium phosphate, and then sending clear liquid to sewage treatment. The method recycles the ultra-low concentration phosphorus-containing wastewater, and the generated semi-finished product is used for producing feed-grade calcium dihydrogen phosphate, replaces the traditional treatment method, converts the product into a product, realizes resource utilization of phosphorus in the wastewater, reduces the generation of sewage slag, reduces the sewage treatment cost, is simple to operate, and generates considerable economic value.
Description
Technical Field
The invention belongs to the technical field of phosphorus chemical industry, and particularly relates to a method for recycling ultralow-concentration phosphorus-containing wastewater.
Background
After the higher-concentration phosphorus-containing wastewater generated in the wet-process phosphoric acid production process is recycled through phosphorus resources, part of the generated ultralow-concentration phosphorus-containing wastewater can be discharged after being treated.
In order to solve the problems and effectively utilize the phosphorus in the wastewater, the inventor provides a method for recycling the phosphorus in the low-concentration wastewater, and a patent with application number 201910483493.1 'method and device for preparing feed-grade calcium hydrophosphate by low-concentration phosphorus-containing wastewater in a cascade mode' is applied. In the actual production, the inventor summarizes a method for preparing the ultra-low concentration phosphorus-containing wastewater into the raw material of the feed-grade monocalcium phosphate and then preparing the feed-grade monocalcium phosphate through a large number of experiments and researches.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for recycling ultralow-concentration phosphorus-containing wastewater aiming at the limited treatment mode of the ultralow-concentration phosphorus-containing wastewater in the prior art.
The technical scheme of the invention is as follows: a method for recycling ultralow-concentration phosphorus-containing wastewater comprises the following steps: (1) adding calcium hydroxide solution into the ultra-low concentration phosphorus-containing wastewater for neutralization reaction, adjusting the pH to 6.5-8.0, and reacting for 1-2h, wherein the phosphorus content of the ultra-low concentration phosphorus-containing wastewater is 0.34-0.69% (by P) 2 O 5 Calculated), the concentration of the calcium hydroxide solution is 15 percent (the CaO content is 88 to 95 percent);
(2) settling, separating and dehydrating the slurry obtained by the neutralization reaction to obtain a semi-finished product;
(3) mixing the semi-finished product with defluorinated dearsenified phosphoric acid and calcium powder, and reacting for 2h to obtain a solid mixture, wherein the defluorinated dearsenified phosphoric acid content is 46% (by P) 2 O 5 Calculated), the calcium powder is powder with the content of 98 percent;
(4) and (4) drying the solid mixture obtained in the step (3) to obtain the feed-grade monocalcium phosphate.
Further, in the step (2), the water content of the obtained semi-finished product is 59% -62%, and the content of dry-basis phosphorus is P 2 O 5 Calculated by 34 to 37 percent, the calcium content is 25 to 27 percent, and the fluorine content is 0.1 to 0.2 percent.
Preferably, in the step (3), the ratio of the defluorinated and dearsenified phosphoric acid and the calcium powder to the semi-finished product is 6.2:3.8: 1.
Preferably, in the step (4), the drying time is 1-2h, and the drying temperature is 80-100 ℃.
The invention has the beneficial effects that: the method can convert phosphorus resources in the wastewater into products, thereby changing waste into valuable. Meanwhile, the method disclosed by the invention is simple in process, low in energy consumption and low in operation difficulty, fully utilizes phosphorus resources in the wastewater as resources, and has good economic benefits and social benefits and wide industrial application prospects.
Drawings
FIG. 1 is a schematic flow diagram of the present invention;
in the figure, 1 is a wastewater adjusting tank; 2 is a calcium hydroxide solution storage tank; 3 is a reaction tank; 4 is a mixing tank; 5 is a settling tank; 6 is a dehydration system; 7 is a semi-finished product storage yard; and 8 is a feed-grade calcium dihydrogen phosphate production device.
Detailed Description
The following further describes the embodiments of the present invention with reference to the drawings and examples, and therefore the present invention is not limited to the scope of the described embodiments.
Example 1
Phosphorus-containing wastewater P in this example 2 O 5 And the contents of F are respectively as follows: 0.55 percent, 0.0010 percent and 15 percent of calcium hydroxide solution concentration (the CaO content is 90.29 percent); defluorination dearsenification phosphoric acid P 2 O 5 F, As contents are respectively: 45.96%, 0.10%, 0.0009%; the calcium powder content is 98 percent. The specific scheme is as follows:
(1) the ultra-low concentration phosphorus-containing wastewater enters a wastewater adjusting tank 1 for stabilization, is conveyed to a reaction tank 3 through a pump to be stirred and reacted with a calcium hydroxide solution from a storage tank 2, the pH value is adjusted to 6.8, and slurry overflows into a mixing tank 4 for reaction time of 1 hour;
(2) overflowing the slurry into a settling tank 5, and adding a flocculating agent for settling;
(3) the slurry at the bottom of the settling tank 5 is conveyed to a dewatering system 6 by a pump to obtain a semi-finished product, and the semi-finished product is discharged into a storage yard 7; wherein the water content of the semi-finished product is 59.34 percent, and the content of dry phosphorus is 35.72 percent (by P) 2 O 5 Calculated), the calcium content is 24.47%, the fluorine content is 0.11%, and the arsenic content is 0.0064%；
(4) Conveying the semi-finished product to a feed-grade monocalcium phosphate device, reacting with defluorinated dearsenic acid and calcium powder at normal temperature for 2 hours, and then drying at the drying temperature of 80 ℃, wherein the ratio of defluorinated dearsenic phosphoric acid to calcium powder to the semi-finished product is 6.2:3.8: 1; obtaining the feed-grade calcium dihydrogen phosphate product (the product quality P content is 22.7 percent, the Ca content is 13.4 percent, the F content is 1359mg/kg, and the As content is 13 mg/kg).
Example 2
Phosphorus-containing wastewater P in this example 2 O 5 And the contents of F are respectively as follows: 0.38 percent, 0.0011 percent and 15 percent of calcium hydroxide solution concentration (the CaO content is 89.75 percent); defluorination dearsenification phosphoric acid P 2 O 5 F, As contents are respectively: 45.31%, 0.13%, 0.0003%; the calcium powder content is 98 percent. The specific scheme is as follows:
(1) the phosphorus-containing wastewater with ultra-low concentration enters a wastewater adjusting tank 1 for stabilization, is conveyed to a reaction tank 3 through a pump to be stirred and reacted with a calcium hydroxide solution from a storage tank 2, the pH is adjusted to be 7.0, and slurry overflows into a mixing tank 4 for reaction for 1 h;
(2) overflowing the slurry into a settling tank 5, and adding a flocculating agent for settling;
(3) the slurry at the bottom of the settling tank 5 is conveyed to a dehydration system 6 by a pump to obtain a semi-finished product which is discharged into a storage yard 7; wherein the water content of the semi-finished product is 60.9 percent, and the content of dry phosphorus is 36.43 percent (by P) 2 O 5 Calculated), the calcium content is 27.4%, the fluorine content is 0.096%, and the As content is 0.0076%;
(4) conveying the semi-finished product to a feed-grade monocalcium phosphate device, reacting with defluorinated dearsenic acid and calcium powder at normal temperature for 2h, and drying at the drying temperature of 80 ℃, wherein the ratio of defluorinated dearsenic phosphoric acid to calcium powder to the semi-finished product is 6.2:3.8: 1; obtaining the feed-grade calcium dihydrogen phosphate product (the product quality P content is 22.7 percent, the Ca content is 13.5 percent, the F content is 1428mg/kg, and the As content is 16 mg/kg).
Claims (4)
1. A method for recycling ultralow-concentration phosphorus-containing wastewater is characterized by comprising the following steps:
(1) adding calcium hydroxide solution into the ultra-low concentration phosphorus-containing wastewaterCarrying out neutralization reaction, adjusting the pH value to 6.5-8.0, and reacting for 1-2h, wherein the phosphorus content of the ultra-low concentration phosphorus-containing wastewater is P 2 O 5 Calculated by the weight percentage, 0.34 to 0.69 percent, 15 percent of calcium hydroxide solution and 88 to 95 percent of CaO;
(2) settling, separating and dehydrating the slurry obtained by the neutralization reaction to obtain a semi-finished product;
(3) mixing the semi-finished product with defluorinated dearsenified phosphoric acid and calcium powder, and reacting for 2h to obtain a solid mixture, wherein the defluorinated dearsenified phosphoric acid content is P 2 O 5 Calculated as 46 percent, the calcium powder is powder with the content of 98 percent;
(4) and (4) drying the solid mixture obtained in the step (3) to obtain the feed-grade monocalcium phosphate.
2. The method for recycling the ultra-low concentration phosphorus-containing wastewater as claimed in claim 1, wherein in the step (2), the water content of the obtained semi-finished product is 59% -62%, and the content of the dry phosphorus is P 2 O 5 Calculated by 34 to 37 percent, the calcium content is 25 to 27 percent, and the fluorine content is 0.1 to 0.2 percent.
3. The method for recycling the ultralow-concentration phosphorus-containing wastewater according to claim 1, wherein in the step (3), the ratio of the defluorinated dearsenified phosphoric acid and calcium powder to the semi-finished product is 6.2:3.8: 1.
4. The method for recycling the ultra-low concentration phosphorus-containing wastewater according to claim 1, wherein in the step (4), the drying time is 1-2h, and the drying temperature is 80-100 ℃.
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Citations (8)
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| CN1463916A (en) * | 2002-06-28 | 2003-12-31 | 李光明 | Process for production of fodder level di-calcium phosphate |
| CN1463917A (en) * | 2002-06-28 | 2003-12-31 | 李光明 | Process for increasing fodder/ fertilizer ratio of fodder level calcium hydrogen phosphate |
| CN102815681A (en) * | 2012-06-21 | 2012-12-12 | 中化云龙有限公司 | Method for producing feed-grade calcium dihydrogen phosphate from wet-process phosphoric acid |
| CN103864042A (en) * | 2014-02-28 | 2014-06-18 | 昆明川金诺化工股份有限公司 | Method for lowering free acid of feed grade monocalcium phosphate |
| CN104445730A (en) * | 2014-11-21 | 2015-03-25 | 贵阳中化开磷化肥有限公司 | Comprehensive utilization method of wastewater containing phosphorus and fluorine |
| WO2018032911A1 (en) * | 2016-08-15 | 2018-02-22 | 东江环保股份有限公司 | Method for preparing feed grade calcium hydrophosphate from waste liquid comprising phosphoric acid |
| CN108946691A (en) * | 2018-08-03 | 2018-12-07 | 禄丰天宝磷化工有限公司 | A kind of technique producing feed-level calcium biphosphate |
| CN110078039A (en) * | 2019-06-04 | 2019-08-02 | 瓮福（集团）有限责任公司 | A kind of low-concentration phosphorus-containing wastewater step produces the method and device of calcium hydrophosphate fodder |
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- 2022-07-14 CN CN202210823076.9A patent/CN115108541A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1463916A (en) * | 2002-06-28 | 2003-12-31 | 李光明 | Process for production of fodder level di-calcium phosphate |
| CN1463917A (en) * | 2002-06-28 | 2003-12-31 | 李光明 | Process for increasing fodder/ fertilizer ratio of fodder level calcium hydrogen phosphate |
| CN102815681A (en) * | 2012-06-21 | 2012-12-12 | 中化云龙有限公司 | Method for producing feed-grade calcium dihydrogen phosphate from wet-process phosphoric acid |
| CN103864042A (en) * | 2014-02-28 | 2014-06-18 | 昆明川金诺化工股份有限公司 | Method for lowering free acid of feed grade monocalcium phosphate |
| CN104445730A (en) * | 2014-11-21 | 2015-03-25 | 贵阳中化开磷化肥有限公司 | Comprehensive utilization method of wastewater containing phosphorus and fluorine |
| WO2018032911A1 (en) * | 2016-08-15 | 2018-02-22 | 东江环保股份有限公司 | Method for preparing feed grade calcium hydrophosphate from waste liquid comprising phosphoric acid |
| CN108946691A (en) * | 2018-08-03 | 2018-12-07 | 禄丰天宝磷化工有限公司 | A kind of technique producing feed-level calcium biphosphate |
| CN110078039A (en) * | 2019-06-04 | 2019-08-02 | 瓮福（集团）有限责任公司 | A kind of low-concentration phosphorus-containing wastewater step produces the method and device of calcium hydrophosphate fodder |
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