A resource recovery method for fluorine-containing copper sulfate waste liquid

Abstract

The present invention relates to a resource recovery method of fluorine-containing copper sulfate waste liquid, and the resource recovery method comprises: mixing the fluorine-containing copper sulfate waste liquid and a silicon medium and then electrolyzing to obtain electrolytic copper and a post-electrolysis liquid; distilling the obtained post-electrolysis liquid to obtain fluorosilicic acid and sulfuric acid; the electrolyte used in the electrolysis contains 10-20 mg / L of amino acids and 3-5 mg / L of sodium caseinate. The resource recovery method provided by the present invention realizes efficient recovery of copper resources by introducing silicon medium and the coordination of amino acids and sodium caseinate in the electrolysis process, and the obtained electrolytic copper has finer grains and a dense surface. At the same time, the post-electrolysis liquid is further distilled and treated, and the fluorosilicic acid and sulfuric acid in the solution are recovered.

Description

Technical Field

[0001] The invention relates to the field of sewage treatment, and in particular to a resource recovery method for fluorine-containing copper sulfate waste liquid. Background Art

[0002] Currently, in the semiconductor industry, silicon wafers need to be etched to obtain silicon wafer products with the required performance.

[0003] For example, CN113292999A discloses an additive, an etching system and an etching method for copper-catalyzed etching of silicon wafers, wherein the additive includes: a metal complexing agent, an acidity regulator and water. The acidity regulator is selected from one or more of citric acid, acetic acid or phosphoric acid; the metal complexing agent is selected from one or more of ethylenediaminetetraacetic acid, salicylic acid or hexamethylenetetramine. The etching system is prepared by mixing the additive with the copper-catalyzed etching solution. Compared with the etching solution without the additive, the etching solution obtained by the additive has milder etching reaction conditions, a lower weight loss rate of the silicon wafer, fewer inverted pyramid spikes on the surface of the prepared silicon wafer, a more uniform and smoother structure, and the surface reflectivity of the silicon wafer can be further reduced. It is particularly suitable for the future texturing process of thin-film silicon wafers and has industrial practical value.

[0004] CN108133968A discloses a method for etching a conical array silicon surface using porous copper with a pine wood structure. First, pine wood is sintered in a non-oxidizing atmosphere to obtain porous carbon with a pine wood structure, and then the porous carbon is soaked in a copper nitrate solution, dried, and sintered in an oxygen-free atmosphere to obtain porous copper with a pine wood structure; the porous copper is used as a catalyst, placed on a silicon plane, and the single crystal silicon is immersed in an etchant. Under the catalytic assistance of copper, the silicon surface is corroded, thereby forming a conical array silicon surface with a convex and concave opposite to the porous copper structure. The silicon surface prepared by this scheme has a conical array structure, which topologically describes the microstructure of pine wood, and is highly borrowed from nature, and can obtain excellent hydrophobic properties and photon receiving capabilities; the conical array silicon surface obtained by the present invention has the advantages of a narrower top and a smaller contact area with water, which is more conducive to reducing the adhesion of the silicon surface to water and is conducive to obtaining better hydrophobic properties.

[0005] Therefore, a large amount of fluorine-containing copper sulfate waste liquid will be generated during the etching process. The current treatment methods for this type of waste liquid are mostly incineration or solidification burial, and the valuable components in the waste liquid are not effectively utilized. Summary of the invention

[0006] In view of the problems existing in the prior art, the object of the present invention is to provide a resource recovery method for fluorine-containing copper sulfate waste liquid to solve the problem that valuable components in the current fluorine-containing copper sulfate waste liquid cannot be effectively recovered.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] The present invention provides a resource recovery method for fluorine-containing copper sulfate waste liquid, the resource recovery method comprising:

[0009] The fluorine-containing copper sulfate waste liquid and the silicon medium are mixed and then electrolyzed to obtain electrolytic copper and post-electrolysis liquid;

[0010] The obtained post-electrolysis liquid is distilled to obtain fluorosilicic acid and sulfuric acid;

[0011] The electrolyte used in the electrolysis contains 10-20 mg / L of amino acids and 3-5 mg / L of sodium caseinate.

[0012] The resource recovery method provided by the present invention realizes efficient recovery of copper resources by introducing silicon medium and the combination of amino acid and sodium caseinate in the electrolysis process, and the obtained electrolytic copper has finer grains and a dense surface. At the same time, the post-electrolysis liquid is further distilled to recover fluorosilicic acid and sulfuric acid in the solution.

[0013] In the present invention, if the fluorine-containing copper sulfate waste liquid contains insoluble solids such as dust, floccules, etc., it is mixed with a silicon medium to perform a solid-liquid separation operation, which can be specifically performed by conventional solid-liquid separation operations in the art such as filtration, filter pressing, centrifugation, etc.

[0014] In the present invention, the amino acid includes one or a combination of at least two of glycine, alanine, serine, tyrosine, cysteine ​​or phenylalanine.

[0015] In the present invention, the concentration of amino acids in the electrolyte used in the electrolysis is 10-20 mg / L, for example, 10 mg / L, 10.2 mg / L, 10.4 mg / L, 10.6 mg / L, 10.8 mg / L, 11 mg / L, 11.2 mg / L, 11.4 mg / L, 11.6 mg / L, 11.8 mg / L, 12 mg / L, 12.2 mg / L, 12.4 mg / L, 12.6 mg / L, 12.8 mg / L, 13 mg / L, 13.4 mg / L, 13.6 mg / L, 13.8 mg / L, 14 mg / L, 14.2 mg / L, 14.4 mg / L, 14.6 mg / L, 14.8 mg / L, 15 mg / L 20mg / L, but not limited to the listed values, other values ​​not listed in this range are also applicable.

[0016] In the present invention, the concentration of sodium caseinate in the electrolyte used in the electrolysis is 3-5 mg / L, for example, it can be 3 mg / L, 3.1 mg / L, 3.2 mg / L, 3.3 mg / L, 3.4 mg / L, 3.5 mg / L, 3.6 mg / L, 3.7 mg / L, 3.8 mg / L, 3.9 mg / L, 4 mg / L, 4.1 mg / L, 4.2 mg / L, 4.3 mg / L, 4.4 mg / L, 4.5 mg / L, 4.6 mg / L, 4.7 mg / L, 4.8 mg / L, 4.9 mg / L or 5 mg / L, but is not limited to the listed values, and other unlisted values ​​within the range are equally applicable.

[0017] As a preferred technical solution of the present invention, the fluorine-containing copper sulfate waste liquid comprises, by mass percentage, 1-3% copper sulfate, 5-15% hydrofluoric acid, and 10-30% sulfuric acid.

[0018] In the present invention, the copper sulfate in the fluorine-containing copper sulfate waste liquid is 1-3% by mass percentage, for example, it can be 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9% or 3%, etc., but is not limited to the listed values, and other values ​​not listed within the range are also applicable.

[0019] In the present invention, the mass percentage of hydrofluoric acid in the fluorine-containing copper sulfate waste liquid is 5-15%, for example, it can be 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5% or 15%, etc., but is not limited to the listed values, and other values ​​not listed within the range are also applicable.

[0020] In the present invention, the sulfuric acid in the fluorine-containing copper sulfate waste liquid is 10-30% by mass percentage, for example, it can be 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30%, etc., but is not limited to the listed values, and other values ​​not listed within the range are equally applicable.

[0021] As a preferred technical solution of the present invention, the silicon medium includes silicon dioxide and / or silicate.

[0022] As a preferred technical solution of the present invention, the mass ratio of the fluorine-containing copper sulfate waste liquid and the silicon medium in the mixture is (100-1000):1, for example, it can be 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 400:1, 450:1, 500:1, 550:1, 600:1, 650:1, 700:1, 750:1, 800:1, 850:1, 900:1, 950:1 or 1000:1, but is not limited to the listed values, and other unlisted values ​​within the range are equally applicable.

[0023] As a preferred technical solution of the present invention, the current density of the electrolysis is 300-1000A / dm 2 , for example, it can be 300A / dm 2 、320A / dm 2 、340A / dm 2 、360A / dm 2 、380A / dm 2 、400A / dm2 、420A / dm 2 、440A / dm 2 、460A / dm 2 、480A / dm 2 、500A / dm 2 、560A / dm 2 、580A / dm 2 、600A / dm 2 、620A / dm 2 、640A / dm 2 、660A / dm 2 、680A / dm 2 、700A / dm 2 、720A / dm 2 、740A / dm 2 、760A / dm 2 、780A / dm 2 、800A / dm 2 、820A / dm 2 、840A / dm 2 、860A / dm 2 、880A / dm 2 、900A / dm 2 、920A / dm 2 、940A / dm 2 、960A / dm 2 、980A / dm 2 or 1000A / dm 2 The above values ​​are not limited to the above values, and other values ​​not listed in the above values ​​are also applicable.

[0024] Preferably, the electrolysis temperature is 40-70°C, for example, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C or 70°C, etc., but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0025] As a preferred technical solution of the present invention, the anode region and the cathode region in the electrolysis are separated by a cationic membrane.

[0026] As a preferred technical solution of the present invention, the distillation method includes reduced pressure distillation.

[0027] Preferably, the distillation temperature is 100-150°C, for example, it can be 100°C, 102°C, 104°C, 106°C, 108°C, 110°C, 112°C, 114°C, 116°C, 118°C, 120°C, 122°C, 124°C, 126°C, 128°C, 130°C, 132°C, 134°C, 136°C, 138°C, 140°C, 142°C, 144°C, 146°C, 148°C or 150°C, etc., but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0028] As a preferred technical solution of the present invention, the fluorosilicic acid is treated with alkali.

[0029] Preferably, the mass ratio of fluorosilicic acid to the alkali treatment agent in the alkali treatment is (5-10):1, for example, it can be 5:1, 5.2:1, 5.4:1, 5.6:1, 5.8:1, 6:1, 6.2:1, 6.4:1, 6.6:1, 6.8:1, 7:1, 7.2:1, 7.4:1, 7.6:1, 7.8:1, 8:1, 8.2:1, 8.4:1, 8.6:1, 8.8:1, 9:1, 9.2:1, 9.4:1, 9.6:1, 9.8:1 or 10:1, but is not limited to the listed values, and other unlisted values ​​within this range are equally applicable.

[0030] Preferably, the alkaline treatment agent comprises aqueous ammonia. The mass concentration of aqueous ammonia can be 5-15%, for example, 5%, 5.2%, 5.4%, 5.6%, 5.8%, 6%, 6.2%, 6.4%, 6.6%, 6.8%, 7%, 7.2%, 7.4%, 7.6%, 7.8%, 8%, 8.2%, 8.4%, 8.6%, 8.8%, 9%, 9.2%, 9.4%, 9.6%, 9.8%, 10%, 10.2%, 10.4%, 10.6%, 10.7%, 10.8%, 10.9%, 10.1%, 10.2%, 10.4%, 10.6%, 10.7%, 10.8%, 10.9%, 10.1%, 10.2%, 10.4%, 10.6%, 10.8%, 10.9%, 10.1%, 10.2%, 10.4%, 10.6%, 10.8%, 10.8%, 10.9%, 10.2%, 10.4%, 10.6%, 10.8 ... .6%, 10.8%, 11%, 11.2%, 11.4%, 11.6%, 11.8%, 12%, 12.2%, 12.4%, 12.6%, 12.8%, 13%, 13.2%, 13.4%, 13.6%, 13.8%, 14%, 14.2%, 14.4%, 14.6%, 14.8% or 15%, etc., but not limited to the listed values, other values ​​not listed in the range are also applicable.

[0031] As a preferred technical solution of the present invention, the alkali treatment obtains silicon dioxide and ammonium bifluoride solution.

[0032] Preferably, silicon dioxide is used as the silicon medium.

[0033] As a preferred technical solution of the present invention, the resource recovery method comprises:

[0034] The fluorine-containing copper sulfate waste liquid and the silicon medium are mixed and then electrolyzed to obtain electrolytic copper and post-electrolysis liquid;

[0035] The obtained post-electrolysis liquid is distilled to obtain fluorosilicic acid and sulfuric acid;

[0036] The fluorine-containing copper sulfate waste liquid comprises, by mass percentage, 1-3% copper sulfate, 5-15% hydrofluoric acid, and 10-30% sulfuric acid; the silicon medium comprises silicon dioxide and / or silicate; the mass ratio of the fluorine-containing copper sulfate waste liquid to the silicon medium in the mixture is (100-1000):1;

[0037] The electrolyte used in the electrolysis contains 10-20 mg / L of amino acids and 3-5 mg / L of sodium caseinate; the current density of the electrolysis is 300-1000 A / dm 2 ; The electrolysis temperature is 40-70°C; the anode region and the cathode region in the electrolysis are separated by a cationic membrane;

[0038] The distillation method includes reduced pressure distillation; the distillation temperature is 100-150°C;

[0039] The fluorosilicic acid is subjected to alkali treatment; the mass ratio of fluorosilicic acid to alkali treatment reagent in the alkali treatment is (5-10):1; the alkali treatment reagent includes ammonia water; the alkali treatment obtains silicon dioxide and ammonium bifluoride solution; the silicon dioxide serves as the silicon medium.

[0040] Compared with the prior art solutions, the present invention has the following beneficial effects:

[0041] (1) The present invention mainly solves the problem of copper recovery in fluorine-containing sulfuric acid. Fluorine is highly corrosive, and an ion membrane is used to block anions. Since the fluoride ion radius is small, it is easy to pass through the cation exchange membrane, so it is necessary to adjust the copper ion concentration in the electrolysis system to ensure that the fluoride ions exist in the form of fluorine-copper complex ions and do not pass through the cation exchange membrane, and use silicon carbide corrosion-resistant material as the cathode. At the same time, in order to fix the release of fluoride ions caused by copper migration, it is necessary to add silicon dioxide and sulfuric acid in the anode chamber to ensure that fluorine is converted into fluorosilicic acid. The migration of fluoride ions is avoided, ensuring the smooth recovery of copper by electrolysis.

[0042] (2) In order to ensure full utilization of various resources under low-carbon conditions, the present invention simultaneously converts fluorine into a high value-added ammonium bifluoride product. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 It is a flow chart of a resource utilization method provided by an embodiment of the present invention.

[0044] The present invention is further described in detail below. However, the following examples are only simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims. DETAILED DESCRIPTION

[0045] To better illustrate the present invention and facilitate understanding of the technical solution of the present invention, typical but non-limiting embodiments of the present invention are as follows:

[0046] Specific as Figure 1 As shown in the figure, it can be seen that the fluorine-containing copper sulfate waste liquid is first filtered to remove insoluble particles and flocs in the waste liquid, and then mixed with a silicon medium and electrolyzed to obtain electrolytic copper and post-electrolysis liquid. The post-electrolysis liquid can be distilled to obtain a fluorosilicic acid product and a sulfuric acid product, wherein the fluorosilicic acid product can be further treated with alkali to obtain silicon dioxide and ammonium bifluoride, and the obtained silicon dioxide can be reused as a silicon medium.

[0047] Example 1

[0048] This embodiment provides a method for recycling fluorine-containing copper sulfate waste liquid, and the method comprises:

[0049] The fluorine-containing copper sulfate waste liquid and the silicon medium are mixed and then electrolyzed to obtain electrolytic copper and post-electrolysis liquid;

[0050] The obtained post-electrolysis liquid is distilled to obtain fluorosilicic acid and sulfuric acid;

[0051] The fluorine-containing copper sulfate waste liquid comprises, by mass percentage, 2% copper sulfate, 10% hydrofluoric acid, and 25% sulfuric acid; the silicon medium is silicon dioxide; the mass ratio of the fluorine-containing copper sulfate waste liquid to the silicon medium in the mixture is 500:1;

[0052] The electrolyte used in the electrolysis contains 15 mg / L of amino acids and 4 mg / L of sodium caseinate; the current density of the electrolysis is 600 A / dm 2 ; The electrolysis temperature is 55°C; the anode region and the cathode region in the electrolysis are separated by a cationic membrane;

[0053] The distillation method includes reduced pressure distillation; the distillation temperature is 120°C;

[0054] The fluorosilicic acid is subjected to alkali treatment; the mass ratio of fluorosilicic acid to alkali treatment reagent in the alkali treatment is 7:1; the alkali treatment reagent is ammonia water (mass concentration is 12%); the alkali treatment obtains silicon dioxide and ammonium bifluoride solution; the silicon dioxide serves as the silicon medium.

[0055] The indicators of the obtained products are shown in Table 1.

[0056] Example 2

[0057] This embodiment provides a method for recycling fluorine-containing copper sulfate waste liquid, and the method comprises:

[0058] The fluorine-containing copper sulfate waste liquid and the silicon medium are mixed and then electrolyzed to obtain electrolytic copper and post-electrolysis liquid;

[0059] The obtained post-electrolysis liquid is distilled to obtain fluorosilicic acid and sulfuric acid;

[0060] The fluorine-containing copper sulfate waste liquid comprises, by mass percentage, 1% copper sulfate, 15% hydrofluoric acid, and 10% sulfuric acid; the silicon medium is sodium silicate; the mass ratio of the fluorine-containing copper sulfate waste liquid to the silicon medium in the mixture is 1000:1;

[0061] The electrolyte used in the electrolysis contains 20 mg / L of amino acids and 3 mg / L of sodium caseinate; the current density of the electrolysis is 1000 A / dm 2 ; The electrolysis temperature is 40°C; the anode region and the cathode region in the electrolysis are separated by a cationic membrane;

[0062] The distillation method includes reduced pressure distillation; the distillation temperature is 150°C;

[0063] The fluorosilicic acid is subjected to alkali treatment; the mass ratio of fluorosilicic acid to the alkali treatment reagent in the alkali treatment is 5:1; the alkali treatment reagent is ammonia water (mass concentration is 8%); the alkali treatment obtains silicon dioxide and ammonium bifluoride solution; the silicon dioxide serves as the silicon medium.

[0064] The indicators of the obtained products are shown in Table 1.

[0065] Example 3

[0066] This embodiment provides a method for recycling fluorine-containing copper sulfate waste liquid, and the method comprises:

[0067] The fluorine-containing copper sulfate waste liquid and the silicon medium are mixed and then electrolyzed to obtain electrolytic copper and post-electrolysis liquid;

[0068] The obtained post-electrolysis liquid is distilled to obtain fluorosilicic acid and sulfuric acid;

[0069] The fluorine-containing copper sulfate waste liquid comprises, by mass percentage, 3% copper sulfate, 5% hydrofluoric acid, and 30% sulfuric acid; the silicon medium is potassium silicate; the mass ratio of the fluorine-containing copper sulfate waste liquid to the silicon medium in the mixture is 100:1;

[0070] The electrolyte used in the electrolysis contains 10 mg / L of amino acids and 5 mg / L of sodium caseinate; the current density of the electrolysis is 300 A / dm2 ; The electrolysis temperature is 70°C; the anode region and the cathode region in the electrolysis are separated by a cationic membrane;

[0071] The distillation method includes reduced pressure distillation; the distillation temperature is 100°C;

[0072] The fluorosilicic acid is subjected to alkali treatment; the mass ratio of fluorosilicic acid to alkali treatment reagent in the alkali treatment is 10:1; the alkali treatment reagent is ammonia water (mass concentration is 5%); the alkali treatment obtains silicon dioxide and ammonium bifluoride solution; the silicon dioxide serves as the silicon medium.

[0073] The indicators of the obtained products are shown in Table 1.

[0074] Example 4

[0075] This embodiment provides a method for recycling fluorine-containing copper sulfate waste liquid, and the method comprises:

[0076] The fluorine-containing copper sulfate waste liquid and the silicon medium are mixed and then electrolyzed to obtain electrolytic copper and post-electrolysis liquid;

[0077] The obtained post-electrolysis liquid is distilled to obtain fluorosilicic acid and sulfuric acid;

[0078] The fluorine-containing copper sulfate waste liquid comprises, by mass percentage, 3% copper sulfate, 12% hydrofluoric acid, and 18% sulfuric acid; the silicon medium is silicon dioxide; the mass ratio of the fluorine-containing copper sulfate waste liquid to the silicon medium in the mixture is 800:1;

[0079] The electrolyte used in the electrolysis contains 18 mg / L of amino acids and 5 mg / L of sodium caseinate; the current density of the electrolysis is 800 A / dm 2 ; The electrolysis temperature is 65°C; the anode region and the cathode region in the electrolysis are separated by a cationic membrane;

[0080] The distillation method includes reduced pressure distillation; the distillation temperature is 135°C;

[0081] The fluorosilicic acid is subjected to alkali treatment; the mass ratio of fluorosilicic acid to alkali treatment reagent in the alkali treatment is 8.5:1; the alkali treatment reagent is ammonia water (mass concentration is 15%); the alkali treatment obtains silicon dioxide and ammonium bifluoride solution; the silicon dioxide serves as the silicon medium.

[0082] The indicators of the obtained products are shown in Table 1.

[0083] Example 5

[0084] The only difference from Example 1 is that no amino acid (serine) is added to the electrolyte. The indicators of the obtained product are shown in Table 1.

[0085] Example 6

[0086] The only difference from Example 1 is that sodium caseinate is not added to the electrolyte. The indicators of the obtained product are shown in Table 1.

[0087] Example 7

[0088] The only difference from Example 1 is that the amino acid (serine) in the electrolyte is replaced by acetic acid of equal concentration. The indexes of the obtained product are shown in Table 1.

[0089] Example 8

[0090] The only difference from Example 1 is that the amino acid (serine) in the electrolyte is replaced by thiourea of ​​equal concentration. The indexes of the obtained product are shown in Table 1.

[0091] Example 9

[0092] The only difference from Example 1 is that the amino acid (serine) in the electrolyte is replaced by polyethylene glycol (molecular weight 400) of equal concentration. The indexes of the obtained product are shown in Table 1.

[0093] Embodiment 11

[0094] The only difference from Example 1 is that the sodium caseinate in the electrolyte is replaced by sodium dodecylbenzene sulfonate of equal concentration. The indexes of the obtained product are shown in Table 1.

[0095] Example 12

[0096] The only difference from Example 1 is that sodium caseinate in the electrolyte is replaced by thiourea of ​​equal concentration. The indexes of the obtained product are shown in Table 1.

[0097] Table 1

[0098]

[0099]

[0100] The results of the above examples show that the resource recovery method provided by the present invention achieves efficient recovery of copper resources by introducing silicon medium and the combination of amino acid and sodium caseinate in the electrolysis process, and the obtained electrolytic copper has good density and small grain size. At the same time, the post-electrolysis liquid is further distilled to recover the fluorosilicic acid and sulfuric acid in the solution.

[0101] It is stated that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must rely on the above detailed structural features to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the components selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0102] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0103] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0104] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A method for recycling fluorine-containing copper sulfate waste liquid, characterized in that: The resource utilization method comprises: The fluorine-containing copper sulfate waste liquid and the silicon medium are mixed and then electrolyzed to obtain electrolytic copper and post-electrolysis liquid; The obtained post-electrolysis liquid is distilled to obtain fluorosilicic acid and sulfuric acid; The electrolyte used in the electrolysis contains 10-20 mg / L of amino acids and 3-5 mg / L of sodium caseinate.

2. The resource recovery method according to claim 1, characterized in that: The fluorine-containing copper sulfate waste liquid comprises, by mass percentage, 1-3% copper sulfate, 5-15% hydrofluoric acid, and 10-30% sulfuric acid.

3. The resource recovery method according to claim 1, characterized in that: The silicon medium includes silicon dioxide and / or silicate.

4. The resource recovery method according to claim 1, characterized in that: The mass ratio of the fluorine-containing copper sulfate waste liquid to the silicon medium in the mixture is (100-1000):

1.

5. The resource recovery method according to claim 1, characterized in that: The current density of the electrolysis is 300-1000A / dm 2 .

6. The resource recovery method according to claim 1, characterized in that: The temperature of the electrolysis is 40-70°C.

7. The resource recovery method according to claim 1, characterized in that: In the electrolysis, the anode region and the cathode region are separated by a cationic membrane.

8. The resource recovery method according to claim 1, characterized in that: The distillation method includes reduced pressure distillation.

9. The resource recovery method according to claim 1, characterized in that: The vacuum degree of the distillation is 0.01-0.08Mpa.

10. The resource recovery method according to claim 1, characterized in that: The distillation temperature is 100-150°C.

11. The resource recovery method according to claim 1, characterized in that: The fluorosilicic acid is subjected to an alkali treatment.

12. The resource recovery method according to claim 11, characterized in that: The mass ratio of fluorosilicic acid to the alkali treatment agent in the alkali treatment is (5-10):

1.

13. The resource recovery method according to claim 12, characterized in that: The alkaline treatment agent includes aqueous ammonia.

14. The resource recovery method according to claim 11, characterized in that: The alkaline treatment yields silica and ammonium bifluoride solution.

15. The resource recovery method according to claim 14, characterized in that: The silicon dioxide serves as the silicon medium.

16. The resource recovery method according to claim 1, characterized in that: The resource utilization method comprises: The fluorine-containing copper sulfate waste liquid and the silicon medium are mixed and then electrolyzed to obtain electrolytic copper and post-electrolysis liquid; The obtained post-electrolysis liquid is distilled to obtain fluorosilicic acid and sulfuric acid; The fluorine-containing copper sulfate waste liquid comprises, by mass percentage, 1-3% copper sulfate, 5-15% hydrofluoric acid, and 10-30% sulfuric acid; the silicon medium comprises silicon dioxide and / or silicate; the mass ratio of the fluorine-containing copper sulfate waste liquid to the silicon medium in the mixture is (100-1000):1; The electrolyte used in the electrolysis contains 10-20 mg / L of amino acids and 3-5 mg / L of sodium caseinate; the current density of the electrolysis is 300-1000 A / dm 2 ; The electrolysis temperature is 40-70°C; the anode region and the cathode region in the electrolysis are separated by a cationic membrane; The distillation method includes reduced pressure distillation; the distillation temperature is 100-150°C; The fluorosilicic acid is subjected to alkali treatment; the mass ratio of fluorosilicic acid to alkali treatment reagent in the alkali treatment is (5-10):1; the alkali treatment reagent includes ammonia water; the alkali treatment obtains silicon dioxide and ammonium bifluoride solution; the silicon dioxide serves as the silicon medium.

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