CN108584901B - Method for recovering ceramic-grade iron phosphate from polymetallic hazardous wastes - Google Patents
Method for recovering ceramic-grade iron phosphate from polymetallic hazardous wastes Download PDFInfo
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- CN108584901B CN108584901B CN201810541401.6A CN201810541401A CN108584901B CN 108584901 B CN108584901 B CN 108584901B CN 201810541401 A CN201810541401 A CN 201810541401A CN 108584901 B CN108584901 B CN 108584901B
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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
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
Abstract
The invention relates to a method for recovering ceramic-grade ferric phosphate from multi-metal hazardous waste, which comprises the steps of treating sludge containing multi-metal phosphorization wastewater and Fe3+Proportioning the sludge, then carrying out acid leaching, generating iron phosphate precipitate at the pH value of 2.0-2.5, separating the iron phosphate precipitate from other various metals, dissolving and reducing the iron phosphate precipitate, and removing a small amount of copper ions; adjusting the pH to 3.5-3.8 to remove a small amount of chromium in the form of chromium phosphate; finally adding hydrogen peroxide to oxidize into Fe3+Generating iron phosphate with phosphate radical, adjusting the pH value to 2.1-2.5 with diluted acid, stirring, and filtering to obtain a filter cake which is ceramic-grade iron phosphate. The method adopts a full wet process, does not need heating, and has simple equipment and operation method and low cost; the chemical agent has single type and is environment-friendly; the extracted ceramic-grade iron phosphate product has high added value and can be directly used as a raw material in industries such as ceramics, adhesives, pigments, chemical engineering and the like.
Description
Technical Field
The invention belongs to the field of wastewater, sewage or sludge treatment, and relates to a method for recovering ceramic-grade iron phosphate from polymetallic hazardous wastes.
Background
In the industries of machinery, steel and the like, a phosphating surface treatment technology is adopted to manufacture a protective layer of a mechanical part, and a large amount of pickling and phosphating waste liquid is generated in the process. The phosphating wastewater contains a large amount of phosphate radicals, heavy metal ions such as copper, nickel, zinc and the like and acid and alkali substances, is usually treated by a chemical precipitation method, for example, lime milk clarifying solution is added, the pH value is adjusted to be 10-11, most of the phosphate radicals and various heavy metal ions in the wastewater are removed by precipitation, and after filtration, the phosphating wastewater treatment sludge is obtained.
At present, the problem of phosphate pollution in water areas in China is very serious, and the ecological damage range caused by water eutrophication is continuously expanded. Meanwhile, phosphate is an indispensable resource for production, life and life activities, is widely used in chemical fertilizer industry, refractory materials, food industry, battery industry and the like, and China is a country with very short phosphorus resources, so that the phosphate has great significance for recycling the phosphorus resources in the phosphorus-containing wastes. At present, the method for disposing the phosphate radical-containing waste mainly comprises a biological method, a struvite recovery method and a sodium phosphate method. The high-rise philosophy adopts a phosphorus accumulating bacteria biological absorption method to remove phosphorus in sewage, and researches on recovery of phosphate radicals in sewage with medium and low phosphorus content by a magnesium ammonium phosphate crystal (struvite) method. The Liu Ying adopts an adsorption-desorption method to recover phosphorus in the waste activated sludge, namely, the waste activated sludge is digested by adopting a heating and ultrasonic crushing method to release the phosphorus in the sludge into an aqueous solution, and FeCl is used for3Preparing hydrated iron oxide adsorbent, desorbing with sodium hydroxide solution, and condensing, concentrating, crystallizing, high temperature treating and cooling to obtain sodium phosphate product.
The surface treatment phosphatization wastewater treatment sludge contains high phosphate radical content, contains heavy metals such as copper, nickel, zinc and the like, has complex components and great harm, is easy to cause bacterial inactivation by a biological method, needs evaporation and crystallization by a struvite and sodium phosphate method, has high energy consumption, and is difficult to realize the separation and recovery of copper, nickel and zinc.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for recovering ceramic-grade iron phosphate from polymetallic hazardous wastes.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a method for recovering ceramic grade ferric phosphate from polymetallic hazardous waste, the method comprising the steps of:
a. proportioning the multi-metal-containing phosphatized wastewater treatment sludge, adding water for pulping, adding acid for acid leaching, and filtering;
b. adding 3-5 wt% of lime water or calcium carbonate slurry into the filtrate obtained in the step a, adjusting the pH to 2.0-2.5, stirring for 30-60 min, and filtering to obtain a filter cake which is crude iron phosphate;
c. adding water into a filter cake for pulping, adjusting the pH value to be 0.5-1.0 by using acid to dissolve the filter cake, filtering again, adding scrap iron into the filtrate under stirring to reduce ferric iron into ferrous iron completely, and filtering;
d. adding 3-5 wt% of sodium carbonate into the filtrate obtained in the step c to adjust the pH value to 3.5-3.8, removing a small amount of chromium in the rough iron phosphate in the form of chromium phosphate, filtering, and collecting the filtrate;
e. adding hydrogen peroxide into the filtrate under stirring to oxidize Fe2+Is Fe3+To form FePO4Adjusting the pH value to 2.1-2.5 by using dilute sulfuric acid, stirring for 30-60 min, and filtering to obtain a filter cake which is ceramic-grade iron phosphate.
Further, in the step a, Fe is calculated according to the mass ratio after the materials are mixed3+：PO4 3-＝1.2～1.5：1。
Further, the material preparation in the step a is to treat the phosphatized wastewater containing multi-metal treatment sludge and Fe3+And (4) proportioning the sludge.
Further, the acid in step a is concentrated sulfuric acid.
Further, the pH value of acid leaching in the step a is 0.5-1.0.
And further, the water in the step a is 1-5 times of the volume of the sludge.
And furthermore, the water in the step c is 1-3 times of the volume of the sludge.
Further, the acid in step c is concentrated sulfuric acid.
And furthermore, in the step e, the concentration of hydrogen peroxide is 20-30 wt%.
Further, the dilute sulfuric acid in the step e is 10-30 wt% of dilute sulfuric acid.
The invention has the beneficial effects that: the invention discloses a method for recovering ceramic-grade iron phosphate from multi-metal hazardous waste, which is used for recovering phosphate radicals to prepare a ceramic-grade iron phosphate product with high added value by adopting a simple and novel method of acid leaching-rough iron phosphate-dissolving reduction-purification-oxidation acidification aiming at treating sludge of phosphorization wastewater containing copper, nickel, zinc, iron, chromium, cobalt and other multi-metals simultaneously, and can also realize the recovery of copper, nickel, zinc, cobalt and other metals simultaneously. The method adopts a full wet process, does not need heating, and has simple equipment and operation method and low cost; the chemical agent has single type and is environment-friendly; the extracted ceramic-grade iron phosphate product has high added value and can be directly used as a raw material in industries such as ceramics, adhesives, pigments, chemical engineering and the like.
Detailed Description
The following describes in detail preferred embodiments of the present invention. The experimental procedures, in which specific conditions are not specified in the examples, are generally carried out under conventional conditions or under conditions recommended by the manufacturers.
Example 1
(1) Analysis of raw materials
Taking phosphatized wastewater to treat sludge and Fe3+The sludge is calculated by Fe according to mass percentage3+：PO4 3-1.2-1.5, the metal content is analyzed by a flame atomic absorption spectrophotometer, the phosphate radical content is analyzed by a visible spectrophotometry method, the water content is analyzed by a weight reduction method, the result is shown in table 1, and the Fe content in the embodiment is Fe3+：PO4 3-＝1.24。
TABLE 1 sludge composition Table
(2) Acid leaching experiment
And (2) putting 500g of the uniformly mixed sludge into a 2000mL beaker, adding 1000mL of water, mechanically stirring and putting the uniformly mixed sludge into the beaker, adjusting the rotating speed to be 300r/min to enable the sludge to be slurried, then slowly adding 98% sulfuric acid into the slurry, gradually dissolving the sludge in the process, adding the sulfuric acid until the sludge does not react, continuously stirring for 30min, and stabilizing the pH value to be about 0.5 to enable metals in the sludge to be completely leached. Filtering after the leaching reaction is qualified to obtain 1268mL of filtrate.
(3) Crude iron phosphate
And (2) slowly adding 3% lime water into the filtrate after acid leaching under stirring to adjust the pH value to 2.5, stirring for 30min, filtering, washing the filter cake with water with the pH value of 2.5 until the washing water is colorless, wherein 208.75g of the obtained filter cake is crude iron phosphate, and the filtrate and the washing water enter a separation process of copper, zinc, nickel, cobalt and manganese. 10 g of filter cake is taken separately, dried to constant weight at 105 ℃, and after grinding, crude iron phosphate (main component FePO) is analyzed4·2H2O) component (B), the results are shown in Table 2. And 3-5 wt% of lime water or calcium carbonate slurry and other weak alkaline substances can be added into the filtrate after acid leaching to adjust the pH, the concentration cannot be too high, and if the concentration is too high, more impurities exist.
TABLE 2 crude iron phosphate composition Table
(4) Dissolution reduction
198.75g of the crude iron phosphate cake was placed in a 500mL beaker, 400mL of water was added to prepare a slurry, 98% sulfuric acid was added thereto with stirring to adjust the pH to 0.5 to dissolve iron phosphate and impurities, and then filtration was performed. The main component of the obtained filter cake is gypsum which can be used as a building material after being washed. Under the stirring state, adding iron filings into the filtrate to reduce ferric iron completely to ferrous iron, simultaneously separating out a small amount of copper in the rough iron phosphate in the form of copper powder, filtering to obtain 501mL of filtrate, and entering the next process.
(5) Purification
Adding 3% sodium carbonate into the filtrate under stirring to adjust pH to 3.8 to obtain Cr3+Precipitation as chromium phosphate removes a small amount of chromium from the crude iron phosphate, under which conditions nickel, zinc, cobalt, manganese do not precipitate. Filtering to obtain 15.46g of filter cake, entering 583mL of filtrate into the next process, and returning the filter cake to pulping for chromium recovery.
(6) Oxidation-acidification
Adding 30% hydrogen peroxide into the filtrate under stirring to oxidize Fe2+Completely precipitating phosphate radical and ferric iron, adjusting the pH value to 2.1 with 30% dilute sulfuric acid, stirring for 30-60 min, filtering to obtain a filter cake which is refined iron phosphate, drying to constant weight at 230 ℃, grinding, and analyzing, wherein the results are shown in Table 3. Content of effective component (main component FePO)4) And the impurity content reaches the quality standard of ceramic-grade iron phosphate. A small amount of nickel, zinc, cobalt and manganese enter the filtrate, and the filtrate is used for pulping and further recovery.
In step c, extra Fe is introduced in the iron reduction process2+And (e) the excess iron is present as ferric hydroxide at a pH of > 2.5 after oxidation in step e, and is acidified to a pH of 2.1-2.5 to convert the excess iron to Fe3+The iron hydroxide exists in the solution instead of entering the filter cake together with the iron phosphate in the form of ferric hydroxide precipitate, so as to ensure the quality of the iron phosphate.
TABLE 3 refined iron phosphate composition Table
Example 2
(1) Analysis of raw materials
Taking phosphatized wastewater to treat sludge and Fe3+The sludge is calculated by Fe according to mass percentage3+：PO4 3-1.2-1.5, mixing uniformly, analyzing the metal content by using a flame atomic absorption spectrophotometer, and analyzing phosphorus by using a visible spectrophotometryAcid radical content, water content by weight loss analysis, the results are shown in Table 4, this example is Fe3+：PO4 3-＝1.45。
TABLE 4 sludge Components Table
(2) Acid leaching experiment
And (2) putting 500g of the uniformly mixed sludge into a 2000mL beaker, adding 1000mL of water, mechanically stirring and putting the uniformly mixed sludge into the beaker, adjusting the rotating speed to be 300r/min to enable the sludge to be slurried, then slowly adding 98% sulfuric acid into the slurry, gradually dissolving the sludge in the process, adding the sulfuric acid until the sludge does not react, continuously stirring for 30min, and stabilizing the pH value to be about 0.6 to enable metals in the sludge to be completely leached. Filtering after the leaching reaction is qualified to obtain 1324mL of filtrate.
(3) Crude iron phosphate
And slowly adding 5% lime water into the filtrate after acid leaching under stirring to adjust the pH value to 2.5, stirring for 30min, filtering, washing the filter cake with water with the pH value of 2.5 until the washing water is colorless, wherein 201.33g of the obtained filter cake is crude iron phosphate, and the filtrate and the washing water enter a separation process of copper, zinc, nickel, cobalt and manganese. 10 g of filter cake is taken separately, dried to constant weight at 105 ℃, and after grinding, crude iron phosphate (main component FePO) is analyzed4·2H2O) component (B), the results are shown in Table 5.
TABLE 5 crude iron phosphate composition Table
(4) Dissolution reduction
191.33g of the crude iron phosphate cake was placed in a 500mL beaker, 400mL of water was added to prepare a slurry, 98% sulfuric acid was added thereto with stirring to adjust the pH to 0.5 to dissolve iron phosphate and impurities, and then filtration was performed. The main component of the obtained filter cake is gypsum which can be used as a building material after being washed. Under the stirring state, adding iron filings into the filtrate to reduce ferric iron completely to ferrous iron, simultaneously separating out a small amount of copper in the rough iron phosphate in the form of copper powder, filtering to obtain 484mL of filtrate, and entering the next process.
(5) Purification
To the filtrate was added 5% sodium carbonate with stirring to adjust the pH to 3.5, and Cr (iii) was precipitated as chromium phosphate to remove a small amount of chromium from the crude iron phosphate, under which condition nickel, zinc, cobalt, manganese did not precipitate. Filtering to obtain 16.05g of filter cake, introducing 568mL of filtrate into the next process, and returning the filter cake to pulping for chromium recovery.
(6) Oxidation-acidification
Adding 20% hydrogen peroxide into the filtrate under stirring to oxidize Fe2+Completely precipitating phosphate radical and ferric iron, adjusting pH to 2.5 with 20% dilute sulfuric acid, stirring for 60min, filtering to obtain refined iron phosphate as filter cake, drying at 230 deg.C to constant weight, grinding, and analyzing, the results are shown in Table 6. Content of effective component (main component FePO)4) And the impurity content reaches the quality standard of ceramic-grade iron phosphate. A small amount of nickel, zinc, cobalt and manganese enter the filtrate, and the filtrate is used for pulping and further recovery.
TABLE 6 refined iron phosphate composition Table
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. A method for recovering ceramic-grade iron phosphate from polymetallic hazardous waste, characterized in that it comprises the following preparation steps:
a. proportioning the multi-metal-containing phosphatized wastewater treatment sludge, adding water for pulping, adding acid for acid leaching, and filtering;
b. adding 3-5 wt% of lime water or calcium carbonate slurry into the filtrate obtained in the step a, adjusting the pH to 2.0-2.5, stirring for 30-60 min, and filtering to obtain a filter cake which is crude iron phosphate;
c. adding water into a filter cake for pulping, adjusting the pH value to be 0.5-1.0 by using acid to dissolve the filter cake, then pressing and filtering, adding scrap iron into filtrate under stirring to reduce ferric iron into ferrous iron completely, and filtering;
d. adding 3-5 wt% of sodium carbonate into the filtrate obtained in the step c to adjust the pH value to 3.5-3.8, removing a small amount of chromium in the rough iron phosphate in the form of chromium phosphate, filtering, and collecting the filtrate;
e. adding hydrogen peroxide into the filtrate under stirring to oxidize Fe2+Is Fe3+To form FePO4Then adjusting the pH value to 2.1-2.5 with dilute sulfuric acid, stirring for 30-60 min, and filtering to obtain a filter cake which is ceramic-grade iron phosphate.
2. The method of claim 1, wherein in step a, Fe is added in a mass ratio after the compounding3+：PO4 3-＝1.2～1.5：1。
3. The method according to claim 1 or 2, wherein the material preparation in step a is the mixing of the phosphorus containing wastewater treatment sludge containing multiple metals with Fe3+And (4) proportioning the sludge.
4. The method of claim 1, wherein the acid in step a is concentrated sulfuric acid.
5. The method of claim 1, wherein the pH of the acid leaching in step a is 0.5 to 1.0.
6. The method according to claim 1, wherein the water in step a is 1-5 times the volume of the sludge.
7. The method according to claim 1, wherein the water in step c is 1-3 times the volume of the sludge.
8. The method of claim 1, wherein the acid in step c is concentrated sulfuric acid.
9. The method according to claim 1, wherein the concentration of hydrogen peroxide in step e is 20-30 wt%.
10. The method of claim 1, wherein the dilute sulfuric acid in step e is 10-30 wt% dilute sulfuric acid.
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| CN110357058A (en) * | 2019-08-12 | 2019-10-22 | 江苏荣信环保科技有限公司 | The method that ferric phosphate is made in phosphorous metal sludge and spent acid |
| CN112142030A (en) * | 2020-08-31 | 2020-12-29 | 合肥国轩高科动力能源有限公司 | Preparation method of low-cost low-temperature lithium iron phosphate |
| CN113105054A (en) * | 2021-04-09 | 2021-07-13 | 瀚蓝工业服务(嘉兴)有限公司 | Method for comprehensively recycling phosphorus-containing waste acid and iron-containing etching waste liquid |
| CN114778265A (en) * | 2022-04-28 | 2022-07-22 | 中国第一重型机械股份公司 | Heating-free digestion method and device for chemical analysis sample |
| CN115784188A (en) * | 2023-02-07 | 2023-03-14 | 锂源(深圳)科学研究有限公司 | Method for recycling and preparing battery-grade iron phosphate |
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| CN101871046A (en) * | 2010-06-29 | 2010-10-27 | 青川县天运金属开发有限公司 | Method for recycling heavy metal pollution wastes |
| CN104141044A (en) * | 2014-07-02 | 2014-11-12 | 西华师范大学 | Method for recycling and refining nickel and cadmium in solid hazardous wastes |
| CN107324303A (en) * | 2017-09-04 | 2017-11-07 | 青川县天运金属开发有限公司 | A kind of method of separation and purification iron, chromium from many metal hazardous wastes |
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| CN101871046A (en) * | 2010-06-29 | 2010-10-27 | 青川县天运金属开发有限公司 | Method for recycling heavy metal pollution wastes |
| CN104141044A (en) * | 2014-07-02 | 2014-11-12 | 西华师范大学 | Method for recycling and refining nickel and cadmium in solid hazardous wastes |
| CN107324303A (en) * | 2017-09-04 | 2017-11-07 | 青川县天运金属开发有限公司 | A kind of method of separation and purification iron, chromium from many metal hazardous wastes |
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