CN117945447A - Harmless treatment and resource utilization method for fluorine-containing waste residues - Google Patents
Harmless treatment and resource utilization method for fluorine-containing waste residues Download PDFInfo
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- CN117945447A CN117945447A CN202410119864.9A CN202410119864A CN117945447A CN 117945447 A CN117945447 A CN 117945447A CN 202410119864 A CN202410119864 A CN 202410119864A CN 117945447 A CN117945447 A CN 117945447A
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- fluorine
- leaching
- containing waste
- calcium fluoride
- recycling
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 57
- 239000011737 fluorine Substances 0.000 title claims abstract description 57
- 239000002699 waste material Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000002386 leaching Methods 0.000 claims abstract description 101
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 76
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 72
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000004343 Calcium peroxide Substances 0.000 claims abstract description 17
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000019402 calcium peroxide Nutrition 0.000 claims abstract description 17
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 238000004064 recycling Methods 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 239000000047 product Substances 0.000 abstract description 28
- 239000006227 byproduct Substances 0.000 abstract description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 14
- 150000003839 salts Chemical class 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000010436 fluorite Substances 0.000 description 4
- 150000004812 organic fluorine compounds Chemical class 0.000 description 4
- 239000003480 eluent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for harmless treatment and resource utilization of fluorine-containing waste residues, which comprises the following steps: (1) Dripping leaching solution containing oxidant and hydrochloric acid into leaching column filled with fluorine-containing waste residue, and performing cyclic leaching oxidation to obtain coarse calcium fluoride product; (2) And uniformly mixing the coarse calcium fluoride product with calcium peroxide, and roasting to obtain a calcium fluoride product. Compared with the prior art, the method can rapidly and effectively remove the organic fluoride in the waste salt and prepare the calcium fluoride byproduct with high purity by means of cyclic leaching oxidation and mixed roasting.
Description
Technical Field
The invention relates to the technical field of solid waste recycling, in particular to a method for harmless treatment and recycling of fluorine-containing waste residues.
Background
A large amount of fluorine-containing wastewater can be generated in the production and use processes of the fluorine chemical products, and a large amount of fluorine-containing waste residues are generated after the fluorine-containing wastewater is subjected to neutralization, precipitation and other steps. With the increasing demand of people for fluoride chemicals, the production of fluoride waste residues is increasing, so that the safe treatment and recycling of fluoride waste residues are urgent. Most of the fluorine-containing waste residues have calcium fluoride content of more than 50%, can be further purified to prepare calcium fluoride byproducts, and have the potential of resource utilization. But has the following problems: on one hand, the current recycling is generally purified until the calcium fluoride content reaches 60-80%, and the research on refining fluorine-containing waste residues into acid fluorite fine powder of a fluoride industry chain is relatively less; on the other hand, the research on recycling of fluorine-containing waste residues is mainly focused on the field of inorganic fluoride industry, and the research on fluorine-containing waste residues in the industry of organic fluoride industry is less. The fluorine-containing waste residues in inorganic fluorine chemical industry such as photovoltaics, integrated circuits and the like are relatively simple in composition, the CaF 2、CaCO3、SiO2 is mainly used, the property is stable, the content of organic matters is low, and the recycling process is relatively easy. For the organofluorine industry, besides inorganic matters such as CaF 2、CaCO3、SiO2, intermediates and byproducts of various fluorine chemicals exist, the organofluorine is difficult to degrade, the environmental ecological hazard is huge, most of the organofluorine is dangerous waste, the treatment difficulty is high, and the fluoride ion leaching risk is high.
Disclosure of Invention
The invention aims to provide a method for harmless treatment and resource utilization of fluorine-containing waste residues.
The aim of the invention can be achieved by the following technical scheme: a method for harmless treatment and resource utilization of fluorine-containing waste residues comprises the following steps:
(1) Dripping leaching solution containing oxidant and hydrochloric acid into leaching column filled with fluorine-containing waste residue, and performing cyclic leaching oxidation to obtain coarse calcium fluoride product;
(2) And uniformly mixing the coarse calcium fluoride product with calcium peroxide, and roasting to obtain a calcium fluoride product.
Preferably, the leaching solution in the step (1) is formed by mixing an oxidant and a hydrochloric acid aqueous solution.
Further preferably, the oxidizing agent comprises one or more of calcium nitrate, nitric acid.
Still more preferably, the oxidizing agent is calcium nitrate, and the mass ratio of the calcium nitrate to the hydrochloric acid aqueous solution is 1:1 to 30.
Still more preferably, the oxidizing agent is nitric acid, and the mass ratio of nitric acid to hydrochloric acid aqueous solution is 1:1 to 50.
Still more preferably, the oxidizing agent is a mixture of calcium nitrate and nitric acid, and the mass ratio of the calcium nitrate, the nitric acid and the hydrochloric acid aqueous solution is 1:0.5:1 to 100.
Further preferably, the aqueous hydrochloric acid solution contains 10 to 37wt% hydrochloric acid.
Preferably, the mass of the leaching solution in the step (1) is 1-5 times that of the fluorine-containing waste residue, the leaching rate is 1-20 ml/s, and the leaching is circularly carried out for 1-5 times.
Preferably, the calcium peroxide in the step (2) accounts for 0.1-5% of the mass of the crude calcium fluoride.
Preferably, the roasting temperature in the step (2) is 400-800 ℃ and the time is 0.5-5 h.
Preferably, the method for harmless treatment and resource utilization of the fluorine-containing waste residues comprises the following steps:
s1: preparing leaching solution, wherein the leaching solution is prepared by mixing an oxidant and hydrochloric acid solution.
S2: and adding the fluorine-containing waste residues into a leaching column.
S3: slowly dripping the prepared leaching solution into a leaching column through a peristaltic pump, and performing cyclic leaching oxidation to obtain a crude calcium fluoride product.
S4: and (3) uniformly mixing the crude calcium fluoride product subjected to cyclic leaching oxidation treatment with calcium peroxide, and placing the mixture in a roasting furnace for high-temperature roasting to prepare a calcium fluoride product of the high-purity fluoride raw material.
Preferably, the fluorine-containing waste residue is organic waste water generated in the synthesis process of fluorine-containing compound precursor substances, and the solid waste residue is generated by neutralization and precipitation and contains organic fluoride.
Compared with the prior art, the invention has the following beneficial effects:
1. The method can carry out high-value utilization on fluorine-containing waste residues, and purify and prepare a fluoride raw material grade calcium fluoride product;
2. the invention adopts the combination of cyclic leaching oxidation and high-temperature roasting, realizes the removal of organic fluoride in fluorine-containing waste residues, can obtain high-purity calcium fluoride byproducts after the treatment of the fluorine-containing waste residues, has the purity of more than 97 percent, can be used as acid-grade fluorite fine powder, and has higher added value;
3. the method can rapidly and effectively remove the organic fluoride in the waste salt and reduce the harmful factors in the waste salt, thereby being beneficial to the safe utilization of the resource product and preparing the calcium fluoride byproduct with high purity;
4. The invention can fix hydrogen fluoride generated by decomposing organic fluoride to generate calcium fluoride, thereby further improving the purity of the calcium fluoride, and can be used as a byproduct of calcium fluoride of a fluoride raw material grade through refining and purification;
5. The invention can treat fluorine-containing waste residues in the organofluorine industry, firstly remove organic components in the fluorine-containing waste residues through innocent treatment, and then carry out resource utilization through refining and purification.
Detailed Description
The following examples of the present invention are described in detail, and are given by way of illustration of the present invention, but the scope of the present invention is not limited to the following examples.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified. Wherein the fluorine-containing waste residue is generated in the hexafluoropropylene production process, the water content is 52wt%, the calcium fluoride content (dry basis) is 53.2wt%, and the total organic matter content (dry basis) is 2.3wt%.
The circulating leaching equipment adopts a common leaching device and comprises a leaching column, a leaching solution collecting tank, a leaching solution recovery pump, a leaching solution storage tank and a leaching pump. And the eluent in the storage tank is slowly dripped into the leaching column from the upper part of the leaching column through the leaching pump, leaching is started, the eluent flows into the collecting tank, and the eluent in the collecting tank enters the storage tank for recycling through the recycling pump.
Example 1
5Kg of fluorine-containing waste residues are placed in a leaching column, 20kg of leaching solution is prepared by mixing calcium nitrate and 30wt% of hydrochloric acid aqueous solution according to the mass ratio of 1:20, 5ml/s of leaching solution is slowly dripped into the leaching column, and leaching is circularly carried out for 3 times, so that a crude calcium fluoride product is obtained.
100G of calcium peroxide and the crude calcium fluoride are added and mixed uniformly, and the mixture is placed in a roasting furnace for high-temperature roasting at 400 ℃ for 4 hours, and then cooled to obtain the calcium fluoride byproduct 1.
Example 2
10Kg of fluorine-containing waste residues are placed in a leaching column, nitric acid and 20wt% hydrochloric acid aqueous solution are mixed according to the mass ratio of 1:50 to prepare 30kg of leaching solution, 3ml/s of leaching solution is slowly dripped into the leaching column, and leaching is circularly carried out for 2 times, so that a crude calcium fluoride product is obtained.
150G of calcium peroxide and the crude calcium fluoride are added and mixed uniformly, and the mixture is placed in a roasting furnace for high-temperature roasting at 600 ℃ for 2 hours, and then cooled to obtain the calcium fluoride byproduct 2.
Example 3
20Kg of fluorine-containing waste residues are placed in a leaching column, and calcium nitrate, nitric acid and 10wt% hydrochloric acid aqueous solution are prepared according to the following steps of 1:0.5:20, mixing and preparing 100kg of leaching solution, slowly dripping 10ml/s into a leaching column, and circularly leaching for 1 time to obtain a crude calcium fluoride product.
Adding 300g of calcium peroxide and the crude calcium fluoride, uniformly mixing, placing the mixture in a roasting furnace, roasting at a high temperature of 800 ℃ for 0.5h, and cooling to obtain the calcium fluoride byproduct 3.
Example 4
5Kg of fluorine-containing waste residues are placed in a leaching column, 20kg of leaching solution is prepared by mixing calcium nitrate and 30wt% of hydrochloric acid aqueous solution according to the mass ratio of 1:30, 1ml/s of leaching solution is slowly dripped into the leaching column, and leaching is circularly carried out for 5 times, so that a crude calcium fluoride product is obtained.
Adding 50g of calcium peroxide and the crude calcium fluoride, uniformly mixing, placing the mixture in a roasting furnace, roasting at a high temperature of 500 ℃ for 3 hours, and cooling to obtain the calcium fluoride byproduct 4.
Example 5
5Kg of fluorine-containing waste residues are placed in a leaching column, 25kg of leaching solution is prepared by mixing calcium nitrate and 30wt% of hydrochloric acid aqueous solution according to the mass ratio of 1:1, 1ml/s of leaching solution is slowly dripped into the leaching column, leaching is circularly carried out for 5 times, and a crude calcium fluoride product is obtained.
Adding 50g of calcium peroxide and the crude calcium fluoride, uniformly mixing, placing the mixture in a roasting furnace, roasting at a high temperature of 500 ℃ for 2 hours, and cooling to obtain the calcium fluoride byproduct 5.
Example 6
5Kg of fluorine-containing waste residues are placed in a leaching column, 25kg of leaching solution is prepared by mixing calcium nitrate and 30wt% of hydrochloric acid aqueous solution according to the mass ratio of 1:20, 20ml/s of leaching solution is slowly dripped into the leaching column, and leaching is circularly carried out for 3 times, so that a crude calcium fluoride product is obtained.
Adding 50g of calcium peroxide and the crude calcium fluoride, uniformly mixing, placing the mixture in a roasting furnace, roasting at a high temperature of 700 ℃ for 1h, and cooling to obtain the calcium fluoride byproduct 6.
Example 7
10Kg of fluorine-containing waste residues are placed in a leaching column, nitric acid and 20wt% hydrochloric acid aqueous solution are mixed according to the mass ratio of 1:30 to prepare 20kg of leaching solution, 2ml/s of leaching solution is slowly dripped into the leaching column, and leaching is circularly carried out for 2 times, so that a crude calcium fluoride product is obtained.
Adding 500g of calcium peroxide and the crude calcium fluoride, uniformly mixing, placing the mixture in a roasting furnace, roasting at a high temperature of 600 ℃ for 2 hours, and cooling to obtain the calcium fluoride byproduct 7.
Example 8
10Kg of fluorine-containing waste residues are placed in a leaching column, nitric acid and 20wt% hydrochloric acid aqueous solution are mixed according to the mass ratio of 1:50 to prepare 10kg of leaching solution, 1ml/s of leaching solution is slowly dripped into the leaching column, leaching is circularly carried out for 5 times, and a crude calcium fluoride product is obtained.
Adding 500g of calcium peroxide and the crude calcium fluoride, uniformly mixing, placing the mixture in a roasting furnace, roasting at a high temperature of 800 ℃ for 1h, and cooling to obtain the calcium fluoride byproduct 8.
Example 9
20Kg of fluorine-containing waste residues are placed in a leaching column, and calcium nitrate, nitric acid and 10wt% hydrochloric acid aqueous solution are prepared according to the following steps of 1:0.5:10, mixing and preparing 50kg of leaching solution, slowly dripping the leaching solution into a leaching column at a ratio of 5ml/s, and circularly leaching for 2 times to obtain a crude calcium fluoride product.
100G of calcium peroxide and the crude calcium fluoride are added and mixed uniformly, and the mixture is placed in a roasting furnace for high-temperature roasting at 700 ℃ for 1.5 hours, and then cooled to obtain the calcium fluoride byproduct 9.
Example 10
20Kg of fluorine-containing waste residues are placed in a leaching column, and calcium nitrate, nitric acid and 10wt% hydrochloric acid aqueous solution are prepared according to the following steps of 1:0.5:50, mixing and preparing 80kg of leaching solution, slowly dripping 10ml/s into a leaching column, and circularly leaching for 5 times to obtain a crude calcium fluoride product.
Adding 200g of calcium peroxide and the crude calcium fluoride, uniformly mixing, placing the mixture in a roasting furnace, roasting at a high temperature of 500 ℃ for 2 hours, and cooling to obtain the calcium fluoride byproduct 10.
Comparative example 1
20Kg of fluorine-containing waste residues are placed in a leaching column, 100kg of clear water is used as leaching liquor, and 10ml/s of the leaching liquor is slowly dripped into the leaching column to obtain a crude calcium fluoride product. Roasting at 800 deg.c for 0.5 hr, and cooling to obtain calcium fluoride byproduct 11.
Comparative example 2
20Kg of fluorine-containing waste residue is placed in a leaching column, 100kg of 10wt% hydrochloric acid aqueous solution is added, and the mixture is slowly dripped into the leaching column at the rate of 10ml/s, so as to obtain a crude calcium fluoride product. Roasting at 800 deg.c for 0.5 hr, and cooling to obtain calcium fluoride byproduct 12.
Comparative example 3
20Kg of fluorine-containing waste residue is placed in a leaching column, 100kg of 10wt% hydrochloric acid aqueous solution is added, the mixture is slowly dripped into the leaching column at the speed of 10ml/s, and leaching is circularly carried out for 1 time, so as to obtain a crude calcium fluoride product. Roasting at 800 deg.c for 0.5 hr, and cooling to obtain calcium fluoride byproduct 13.
Comparative example 4
20Kg of fluorine-containing waste residue is placed in a leaching column, 100kg of 10wt% hydrochloric acid aqueous solution is added, the mixture is slowly dripped into the leaching column at the speed of 10ml/s, and leaching is circularly carried out for 1 time, so as to obtain a crude calcium fluoride product. Adding 300g of calcium oxide and the crude calcium fluoride, uniformly mixing, placing the mixture in a roasting furnace, roasting at a high temperature of 800 ℃ for 0.5h, and cooling to obtain the calcium fluoride byproduct 14.
Comparative example 5
20Kg of fluorine-containing waste residue is placed in a leaching column, 100kg of 10wt% hydrochloric acid aqueous solution is added, the mixture is slowly dripped into the leaching column at the speed of 10ml/s, and leaching is circularly carried out for 1 time, so as to obtain a crude calcium fluoride product. Adding 300g of calcium peroxide and the crude calcium fluoride, uniformly mixing, placing in a roasting furnace, roasting at a high temperature of 800 ℃ for 0.5h, and cooling to obtain the calcium fluoride byproduct 15.
The quality of the calcium fluoride by-product is measured by referring to the national standard GB/T5195.1-2017 determination EDTA titration method and distillation-potentiometric titration method of the content of fluorite calcium fluoride, the related data are shown in the table 1, the index purity of the calcium fluoride of the related embodiment is more than 97%, and the content of the calcium fluoride accords with the special first-grade quality standard in GB 8216-87 fluorite ore.
Table 1 calcium fluoride product detection
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The harmless treatment and recycling method for the fluorine-containing waste residues is characterized by comprising the following steps of:
(1) Dripping leaching solution containing oxidant and hydrochloric acid into leaching column filled with fluorine-containing waste residue, and performing cyclic leaching oxidation to obtain coarse calcium fluoride product;
(2) And uniformly mixing the coarse calcium fluoride product with calcium peroxide, and roasting to obtain a calcium fluoride product.
2. The method for innocent treatment and recycling of fluorine-containing waste residue according to claim 1, wherein the leaching solution in the step (1) is formed by mixing an oxidant and an aqueous hydrochloric acid solution.
3. The method for innocent treatment and recycling of fluorine-containing waste residue according to claim 2, wherein the oxidizing agent comprises one or more of calcium nitrate and nitric acid.
4. The method for harmless treatment and recycling of fluorine-containing waste residues according to claim 3, wherein the oxidant is calcium nitrate, and the mass ratio of the calcium nitrate to the aqueous solution of hydrochloric acid is 1:1 to 30.
5. The method for harmless treatment and recycling of fluorine-containing waste residues according to claim 3, wherein the oxidant is nitric acid, and the mass ratio of nitric acid to hydrochloric acid aqueous solution is 1:1 to 50.
6. The method for harmless treatment and recycling of fluorine-containing waste residues according to claim 3, wherein the oxidant is a mixture of calcium nitrate and nitric acid, and the mass ratio of the calcium nitrate to the nitric acid to the hydrochloric acid aqueous solution is 1:0.5:1 to 100.
7. The method for innocent treatment and recycling of fluorine-containing waste residue according to claim 2, wherein the aqueous hydrochloric acid solution contains 10 to 37wt% of hydrochloric acid.
8. The method for harmless treatment and recycling of fluorine-containing waste residues according to claim 1, wherein the leaching solution in the step (1) is 1-5 times of the fluorine-containing waste residues in mass, the leaching rate is 1-20 ml/s, and the leaching is circularly carried out for 1-5 times.
9. The method for harmless treatment and recycling of fluorine-containing waste residues according to claim 1, wherein the calcium peroxide in the step (2) accounts for 0.1-5% of the mass of the crude calcium fluoride.
10. The method for harmless treatment and recycling of fluorine-containing waste residue according to claim 1, wherein the roasting temperature in the step (2) is 400-800 ℃ for 0.5-5 h.
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