Adsorbent for recycling cover plate glass thinning liquid, preparation method and application

Abstract

The invention relates to the technical field of glass thinning liquid recovery treatment, in particular to an adsorbent for cover plate glass thinning liquid recovery and a preparation method and application thereof.The preparation method includes the steps that activated carbon is soaked in a metal salt solution to obtain activated carbon carrying metal ions, the activated carbon carrying the metal ions is subjected to high-temperature calcination to obtain the adsorbent, and the adsorbent is placed in cover plate glass thinning waste liquid for adsorption; desorbing the adsorbent loaded with the adsorption substance to obtain a desorption material which can be directly sold as a raw material; and residual waste liquid is filtered and reused in the thinning process. The method is simple, green and environment-friendly, the adsorption process is simple, resource utilization of cover plate glass thinning waste liquid treatment is achieved, the problem of environmental pollution in the cover plate glass industry can be effectively solved, sustainable development of the cover plate glass industry is promoted, and very good economic value is achieved. The problems that in the prior art, the glass thinning liquid recovery treatment process is tedious, and the economical efficiency is poor are solved.

Description

Technical Field

[0001] The present invention relates to the technical field of glass thinning liquid recovery and treatment, and in particular to an adsorbent for recovering cover glass thinning liquid, a preparation method and an application thereof. Background Art

[0002] With the popularization of 5G technology and the popularity of wireless charging, the "double glass structure" of smartphones has ushered in the era. In order to meet people's pursuit of thinner and lighter smartphones, a large number of glass thinning factories have emerged, gradually thinning from the initial 6mm to 0.3mm, or even thinner. Cover glass thinning usually adopts chemical etching, using the principle of hydrofluoric acid (HF) reacting with silicon dioxide (SiO2) to generate fluorinated silicic acid, so that the glass surface is peeled off, achieving the purpose of glass thinning and surface strengthening. As the reaction proceeds, the HF concentration in the thinning liquid gradually decreases, while the fluorinated silicic acid content in the system continues to increase. The increase in the concentration of fluorinated silicic acid not only reduces the etching ability of the system, but also causes uneven etching of the substrate surface, resulting in a decrease in product quality and an increase in etching processing time, so that the thinning liquid cannot continue to be used and waste liquid is discharged. Although chemical etching effectively solves the problem of ultra-thinning in the cover glass industry, the generation of a large amount of fluorine-containing waste liquid has brought inevitable harm to the environment. Therefore, the development of a recovery and treatment technology for cover glass thinning liquid is of great significance to environmental protection and resource utilization.

[0003] The Chinese invention with publication number CN109626646A discloses a method for online recycling and reuse of fluorine-containing glass thinning waste liquid in the glass thinning industry. The method analyzes the content of various acid components in the fluorine-containing glass thinning waste liquid; then, under continuous stirring, organic acid alkali metal salts are added to the fluorine-containing glass thinning waste liquid in a molar ratio for mixing; finally, after precipitation and sedimentation, the precipitate is separated from the bottom, and after washing, dehydration and drying, a fluorosilicate alkali metal salt solid is obtained, and the organic acid and useful acid components are separated to make it meet the content of each component of the etching liquid in the original glass thinning process, and then it is returned to the original process for continued use after microfiltration. This method will not bring anions into the treated recycled liquid, and the reaction process is gentle, safe and reliable. However, the process steps are relatively cumbersome and the treatment process is not economical. Summary of the invention

[0004] In view of the problems in the prior art that the recovery process of glass thinning liquid is complicated and has poor economic efficiency, the present invention provides an adsorbent for recovering cover glass thinning liquid, a preparation method and an application thereof.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] The present invention provides a method for preparing an adsorbent for recovering cover glass thinning liquid, comprising:

[0007] The activated carbon is immersed in a metal salt solution to obtain activated carbon loaded with metal ions;

[0008] The activated carbon loaded with metal ions is calcined at high temperature to obtain an adsorbent.

[0009] Furthermore, the concentration of the metal salt solution is 130-167 g / L.

[0010] Furthermore, the mass ratio of the metal salt to the activated carbon in the metal salt solution is (4-5):6.

[0011] Preferably, the metal salt solution is one or more of a sodium carbonate aqueous solution, a sodium bicarbonate aqueous solution, a potassium carbonate aqueous solution, a potassium bicarbonate aqueous solution, a calcium bicarbonate aqueous solution and a calcium chloride aqueous solution.

[0012] Preferably, the activated carbon is immersed in the metal salt solution for 24 to 36 hours at a temperature of 30° C. to 45° C.

[0013] Furthermore, the activated carbon loaded with metal ions is calcined at a high temperature to obtain an adsorbent having a calcination temperature of 450°C to 650°C.

[0014] An adsorbent for recovering cover glass thinning liquid is prepared by the method.

[0015] The application of the above-mentioned adsorbent for recovering cover glass thinning liquid in the recovery process of cover glass thinning liquid.

[0016] Furthermore, the application method includes:

[0017] placing the adsorbent in the cover glass thinning waste liquid, mixing them evenly, and obtaining the adsorbent carrying the adsorbent and the remaining waste liquid;

[0018] placing the adsorbent loaded with the adsorbed substance in an eluent for desorption to obtain a desorbed material;

[0019] The remaining waste liquid is filtered and reused in the thinning process.

[0020] Preferably, the eluent is ethanol and / or water at a temperature of 65°C to 70°C.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The present invention discloses a method for preparing an adsorbent for recovering cover glass thinning liquid. The method comprises the steps of immersing activated carbon in a metal salt solution to obtain activated carbon loaded with metal ions and calcining the activated carbon at a high temperature to obtain the adsorbent. The preparation method is simple, does not require complex reaction equipment, is green, pollution-free, has a high yield, and is suitable for industrialization. The prepared adsorbent can be used for adsorption and recovery of fluorinated silicic acid in the cover glass thinning liquid without using organic solvents, is green and environmentally friendly, and the material desorbed after adsorption can be directly used as an industrial raw material for market sales. The remaining waste liquid after adsorption by the adsorbent can be reused for thinning the cover glass. The process is simple, and the resource utilization of the waste liquid treated from the cover glass thinning process is realized. The environmental pollution problem in the cover glass industry can be effectively improved, and the sustainable development of the cover glass industry can be promoted, which has very good economic value.

[0023] The present invention provides an adsorbent for recovering cover glass thinning liquid, which is prepared by the above method. The adsorbent is green and environmentally friendly, has a simple use method, is low in cost, is easy to recycle, and has good economic efficiency.

[0024] For example, the application of the above-mentioned adsorbent for recovering cover glass thinning liquid in the recovery and treatment of cover glass thinning liquid, when applying it, it is only necessary to place the adsorbent in the cover glass thinning waste liquid, mix it evenly, and obtain the adsorbent carrying the adsorbent and the remaining waste liquid; then, the adsorbent carrying the adsorbent is placed in the eluent for desorption to obtain the desorption material; the desorption material can be directly used as an industrial raw material for market sales to generate economic benefits, and the remaining waste liquid is filtered and treated and can be used again in the thinning process, with high resource utilization, simple process and low investment cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The present invention is a schematic flow chart of a method for preparing an adsorbent for recovering cover glass thinning liquid.

[0026] Figure 2 The present invention is a process diagram of an application method of an adsorbent for recovering cover glass thinning liquid in the recovery process of cover glass thinning liquid. DETAILED DESCRIPTION

[0027] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text are the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definition in this specification shall prevail.

[0028] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0029] Herein, all features such as values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible secondary ranges and individual values ​​within the range (including integers and fractions).

[0030] In this document, unless otherwise specified, “includes,” “including,” “contains,” “has,” or similar terms cover the meanings of “consisting of” and “mainly consisting of,” for example, “A includes a” covers the meanings of “A includes a and other” and “A only includes a.”

[0031] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.

[0032] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0033] The following examples use conventional instruments and equipment in the art. The experimental methods in the following examples where specific conditions are not specified are usually carried out under conventional conditions or under conditions recommended by the manufacturer. The various raw materials used in the following examples are conventional commercial products unless otherwise specified, and their specifications are conventional specifications in the art. In the specification of the present invention and the following examples, unless otherwise specified, "%" means weight percentage, "part" means weight part, and ratio means weight ratio.

[0034] The present invention is further described in detail below in conjunction with specific embodiments, which are intended to explain the present invention rather than to limit it.

[0035] See also Figure 1 The present invention discloses a method for preparing an adsorbent for recovering cover glass thinning liquid, which is characterized by comprising:

[0036] S1: Immersing activated carbon in a metal salt solution to obtain activated carbon loaded with metal ions, specifically:

[0037] The metal salt is dissolved into a metal salt solution, and the metal ions are immersed in the activated carbon by an impregnation method at a temperature of 30°C to 45°C for 24 to 36 hours to obtain activated carbon loaded with metal ions; the metal salt solution is one or more of a sodium carbonate aqueous solution, a sodium bicarbonate aqueous solution, a potassium carbonate aqueous solution, a potassium bicarbonate aqueous solution, a calcium bicarbonate aqueous solution and a calcium chloride aqueous solution; the concentration of the metal salt solution is 130 to 167 g / L; the mass ratio of the metal salt in the metal salt solution to the activated carbon is (4 to 5):6;

[0038] S2: calcining the activated carbon loaded with metal ions at high temperature to obtain an adsorbent, specifically:

[0039] The activated carbon loaded with metal ions is calcined at a temperature of 450°C to 650°C for 5 to 6 hours to obtain an adsorbent.

[0040] Example 1

[0041] 10 g of Na2CO3, 10 g of K2CO3, and 5 g of CaCl2 were weighed separately and dissolved in 150 mL of deionized water to obtain a metal salt solution. Subsequently, 30 g of activated carbon was immersed in the metal salt solution and ultrasonically oscillated in a 35°C water bath constant temperature oscillator for 30 hours. After the activated carbon was fully impregnated, it was taken out and aged in an oven at 60°C for 12 hours. Finally, the sample was calcined at 450°C in an argon-protected tubular muffle furnace for 5 hours to obtain an adsorbent.

[0042] Example 2

[0043] 10 g of NaHCO3, 10 g of KHCO3, and 5 g of CaCl2 were weighed separately and dissolved in 150 mL of deionized water to obtain a metal salt solution. Subsequently, 30 g of activated carbon was immersed in the metal salt solution and ultrasonically oscillated in a 35°C water bath constant temperature oscillator for 30 hours. After the activated carbon was fully impregnated, it was taken out and aged in an oven at 60°C for 12 hours. Finally, the sample was calcined at 550°C in an argon-protected tubular muffle furnace for 5 hours to obtain an adsorbent.

[0044] Example 3

[0045] 10 g of Na2CO3, 10 g of KHCO3, and 5 g of CaCl2 were weighed separately and dissolved in 150 mL of deionized water to obtain a metal salt solution. Subsequently, 30 g of activated carbon was immersed in the metal salt solution and ultrasonically oscillated in a 35°C water bath constant temperature oscillator for 30 hours. After the activated carbon was fully impregnated, it was taken out and aged in an oven at 60°C for 12 hours. Finally, the sample was calcined at 450°C in an argon-protected tubular muffle furnace for 6 hours to obtain an adsorbent.

[0046] Example 4

[0047] 10 g of NaHCO3, 10 g of K2CO3, and 5 g of CaCl2 were weighed separately and dissolved in 150 mL of deionized water to obtain a metal salt solution. Subsequently, 30 g of activated carbon was immersed in the metal salt solution and ultrasonically oscillated in a 35°C water bath constant temperature oscillator for 24 hours. After the activated carbon was fully impregnated, it was taken out and aged in an oven at 60°C for 12 hours. Finally, the sample was calcined at 450°C in an argon-protected tubular muffle furnace for 5 hours to obtain an adsorbent.

[0048] Example 5

[0049] 10 g of NaHCO3 and 10 g of KHCO3 were weighed separately and dissolved in 150 mL of deionized water to obtain a metal salt solution. Subsequently, 30 g of activated carbon was immersed in the metal salt solution and ultrasonically oscillated in a water bath constant temperature oscillator at 45 ° C for 24 hours. After the activated carbon was fully impregnated, it was taken out and aged in an oven at 60 ° C for 12 hours. Finally, the sample was calcined at 450 ° C for 5 hours in an argon-protected tubular muffle furnace to obtain an adsorbent.

[0050] Example 6

[0051] 10 g of Ca(HCO3)2 and 12 g of KHCO3 were weighed separately and dissolved in 150 mL of deionized water to obtain a metal salt solution. Subsequently, 30 g of activated carbon was immersed in the metal salt solution and ultrasonically oscillated in a water bath constant temperature oscillator at 45°C for 24 hours. After the activated carbon was fully impregnated, it was taken out and aged in an oven at 60°C for 12 hours. Finally, the sample was calcined at 500°C for 6 hours in an argon-protected tubular muffle furnace to obtain an adsorbent.

[0052] The present invention provides an adsorbent for recovering cover glass thinning liquid, which is prepared by the above method. The adsorbent can be used for adsorption and recovery of fluorinated silicic acid in the cover glass thinning liquid, without using organic solvents, and is green and environmentally friendly. The material desorbed after adsorption can be directly used as an industrial raw material for market sales, and the remaining waste liquid after adsorption by the adsorbent can be reused for thinning the cover glass. The process is simple, and the resource utilization of the waste liquid treated by the cover glass thinning is realized, which can effectively improve the environmental pollution problem of the cover glass industry, promote the sustainable development of the cover glass industry, and has very good economic value.

[0053] For example, the application of the above-mentioned adsorbent for recovering cover glass thinning liquid in the recovery and treatment of cover glass thinning liquid, see Figure 2 , methods include:

[0054] S1: placing the adsorbent in the waste liquid of cover glass thinning and mixing them evenly to obtain the adsorbent carrying the adsorbent and the remaining waste liquid; during the mixing process, the metal ions on the adsorbent are mixed with the BF4 in the waste liquid of cover glass thinning. - and SiF6 -The plasma is fully combined. The mass percentage of the adsorbent and the cover glass thinning waste liquid is 0.1% to 1.0%.

[0055] S2: placing the adsorbent loaded with the adsorbent in an eluent for desorption to obtain a desorption material; the eluent is ethanol or water at a temperature of 65°C to 70°C. The analytical material is a desorption material such as Na2SiF6 and KBF4.

[0056] S3: Filter the remaining waste liquid for reuse in the thinning process. The remaining waste liquid contains unreacted HF and a large amount of inorganic acid and organic acid. After adsorption treatment, H2SiF6, HBF4 and other substances in the waste liquid have been removed. The remaining waste liquid can be recycled and reused by the thinning plant after filtering and other treatments.

[0057] Example 7

[0058] 10 g of the adsorbent prepared in Example 1 was placed in 1000 mL of cover glass waste liquid, and ultrasonically oscillated in a water bath constant temperature oscillator at 35° C. for 6 h to obtain an adsorbent loaded with adsorbent and residual waste liquid;

[0059] The adsorbent loaded with the adsorbed substance was placed in 50 mL of 65°C ethanol and washed three times, then washed three times with 70°C hot water, and dried to obtain a desorbed material, which was directly sold as a raw material.

[0060] The remaining waste liquid is filtered several times and reused in the thinning process.

[0061] Example 8

[0062] 6 g of the adsorbent prepared in Example 2 was placed in 1000 mL of cover glass waste liquid, and ultrasonically oscillated in a water bath constant temperature oscillator at 35° C. for 6 h to obtain an adsorbent loaded with adsorbent and residual waste liquid;

[0063] The adsorbent loaded with the adsorbed substance was placed in 50 mL of 65°C ethanol and washed three times, then washed three times with 70°C hot water, and dried to obtain a desorbed material, which was directly sold as a raw material.

[0064] The remaining waste liquid is filtered several times and reused in the thinning process.

[0065] Example 9

[0066] 8 g of the adsorbent prepared in Example 3 was placed in 1000 mL of cover glass waste liquid, and ultrasonically oscillated in a water bath constant temperature oscillator at 35° C. for 6 h to obtain an adsorbent loaded with adsorbent and residual waste liquid;

[0067] The adsorbent loaded with the adsorbed substance was placed in 50 mL of 65°C ethanol and washed three times, then washed three times with 65°C hot water, and dried to obtain a desorbed material, which was directly sold as a raw material.

[0068] The remaining waste liquid is filtered several times and reused in the thinning process.

[0069] Example 10

[0070] 5 g of the adsorbent prepared in Example 4 was placed in 1000 mL of cover glass waste liquid, and ultrasonically oscillated in a water bath constant temperature oscillator at 35° C. for 6 h to obtain an adsorbent loaded with adsorbent and residual waste liquid;

[0071] The adsorbent loaded with the adsorbed substance was placed in 50 mL of 65°C ethanol and washed three times, then washed three times with 65°C hot water, and dried to obtain a desorbed material, which was directly sold as a raw material.

[0072] The remaining waste liquid is filtered several times and reused in the thinning process.

[0073] Embodiment 11

[0074] 7 g of the adsorbent prepared in Example 5 was placed in 1000 mL of cover glass waste liquid, and ultrasonically oscillated in a water bath constant temperature oscillator at 35° C. for 6 h to obtain an adsorbent loaded with adsorbent and residual waste liquid;

[0075] The adsorbent loaded with the adsorbed substance was placed in 50 mL of 65°C ethanol, washed several times, and dried to obtain a desorbed material, which was directly sold as a raw material.

[0076] The remaining waste liquid is filtered several times and reused in the thinning process.

[0077] Example 12

[0078] 1 g of the adsorbent prepared in Example 6 was placed in 1000 mL of cover glass waste liquid, and ultrasonically oscillated in a water bath constant temperature oscillator at 35° C. for 6 h to obtain an adsorbent loaded with adsorbent and residual waste liquid;

[0079] The adsorbent loaded with the adsorbed substance was placed in 50 mL of 65°C ethanol and washed three times, then washed three times with 65°C hot water, and dried to obtain a desorbed material, which was directly sold as a raw material.

[0080] The remaining waste liquid is filtered several times and reused in the thinning process.

[0081] The adsorption rates of Examples 7 to 12 are shown in the following table:

[0082]

[0083] In summary, the present invention provides an adsorbent for recovering cover glass thinning liquid, a preparation method and an application. Activated carbon is immersed in a metal salt solution to obtain activated carbon loaded with metal ions and then calcined at high temperature to obtain an adsorbent. The preparation method is simple, does not require complex reaction equipment, is green, pollution-free, has high yield, and is suitable for industrialization. The prepared adsorbent can be used for adsorption and recovery of fluorinated silicic acid in the cover glass thinning liquid, does not use organic solvents, is green and environmentally friendly, and the material desorbed after adsorption can be directly used as an industrial raw material for market sales. The remaining waste liquid after adsorption by the adsorbent can be reused for thinning the cover glass. The process is simple, and the resource utilization of the waste liquid treatment of cover glass thinning is realized, which can effectively improve the environmental pollution problem of the cover glass industry, promote the sustainable development of the cover glass industry, and has very good economic value.

[0084] The above description is only a preferred embodiment of the present invention and is not intended to impose any limitation on the technical solution of the present invention. Those skilled in the art should understand that, without departing from the spirit and principles of the present invention, the technical solution can also be subjected to several simple modifications and substitutions, and these modifications and substitutions are also within the scope of protection covered by the claims.

Claims

1. A method for preparing an adsorbent for recovering cover glass thinning liquid, characterized in that: include: The activated carbon is immersed in a metal salt solution to obtain activated carbon loaded with metal ions; The activated carbon loaded with metal ions is calcined at high temperature to obtain an adsorbent.

2. The method for preparing an adsorbent for recovering cover glass thinning liquid according to claim 1, characterized in that: The concentration of the metal salt solution is 130-167 g / L.

3. The method for preparing an adsorbent for recovering cover glass thinning liquid according to claim 1, characterized in that: The mass ratio of the metal salt to the activated carbon in the metal salt solution is (4-5):

6.

4. The method for preparing an adsorbent for recovering cover glass thinning liquid according to claim 1, characterized in that: The metal salt solution is one or more of a sodium carbonate aqueous solution, a sodium bicarbonate aqueous solution, a potassium carbonate aqueous solution, a potassium bicarbonate aqueous solution, a calcium bicarbonate aqueous solution and a calcium chloride aqueous solution.

5. The method for preparing an adsorbent for recovering cover glass thinning liquid according to claim 1, characterized in that: The activated carbon is immersed in the metal salt solution for 24 to 36 hours at a temperature of 30°C to 45°C.

6. The method for preparing an adsorbent for recovering cover glass thinning liquid according to claim 1, characterized in that: The activated carbon loaded with metal ions is calcined at a high temperature to obtain an adsorbent at a calcination temperature of 450°C to 650°C.

7. An adsorbent for recovering cover glass thinning liquid, characterized in that: Prepared by the method described in any one of claims 1 to 6.

8. Use of the adsorbent for recovering cover glass thinning liquid as claimed in claim 7 in the recovery process of cover glass thinning liquid.

9. Use of the adsorbent for recovering cover glass thinning liquid according to claim 8 in recovering cover glass thinning liquid, characterized in that: include: placing the adsorbent in the cover glass thinning waste liquid, mixing them evenly, and obtaining the adsorbent carrying the adsorbent and the remaining waste liquid; placing the adsorbent loaded with the adsorbed substance in an eluent for desorption to obtain a desorbed material; The remaining waste liquid is filtered and reused in the thinning process.

10. The use of the cover glass thinning liquid recovery adsorbent according to claim 9 in the recovery and treatment of the cover glass thinning liquid, characterized in that: The eluent is ethanol and / or water at a temperature of 65°C to 70°C.

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