A Composite Material for Chip Wastewater Treatment and Its Preparation Method

Abstract

This application relates to a composite material for chip wastewater treatment and a preparation method thereof. The preparation method includes: immersing an activated carbon-zirconium loading material with a mass ratio of 1:(4-6) in an alumina sol, and impregnating for 1-1.5 h under magnetic stirring at 450-550 r / min; drying the impregnated system at a temperature of 60-70 °C for 0.5-2 h, and calcining the obtained solid at a temperature of 400-900 °C for 4-6 h to obtain the composite material. The composite material prepared in this application has the characteristics of high adsorption, corrosion resistance, high efficiency of regeneration and environmental protection. Especially when treating chip wastewater with a relatively high fluorine content, it shows high adsorption, greatly improving the defluorination effect, and the recycled composite material still has high-performance fluoride ion adsorption performance.

Description

Technical Field

[0001] This application relates to the technical field of sewage treatment, and particularly to a composite material for treating chip wastewater and a preparation method thereof. Background Art

[0002] Fluorine is an essential element for the human body. Low-concentration fluoride ions are beneficial to preventing dental caries and tooth decay. However, when the fluoride ion concentration is too high, it will cause harm to organisms or humans in water. Currently, the problem of excessive fluoride in water bodies is widespread worldwide, especially in chip wastewater. Fluorine in chip wastewater is characterized by high concentration, strong corrosiveness, and high toxicity, seriously affecting the respiration, growth, and reproduction of aquatic organisms in water, and destroying the ecological balance and species diversity of aquatic organisms.

[0003] Currently, the technologies for removing fluoride from chip wastewater include three categories: precipitation method, adsorption method, and membrane separation method. Among them, the adsorption method is the main application method, and common adsorbents are activated alumina, hydroxyapatite, ion exchange resin, etc. However, such adsorbents have high requirements for the influent water quality, and the preparation cost of the adsorbents is relatively high. In comparison, activated carbon is a material with relatively high cost performance for fluoride adsorption and is also the most widely used material.

[0004] However, the adsorption capacity of activated carbon is limited. Especially for chip wastewater with a relatively high fluoride ion concentration, the fluoride ion removal rate is relatively low; and activated carbon will irreversibly adsorb some pollutants in the sewage during the adsorption process, resulting in a decrease in its adsorption capacity after multiple uses. Therefore, it is necessary to propose a highly efficient and usable composite material that can efficiently remove fluoride and improve the adsorption capacity after recycling. Summary of the Invention

[0005] To solve the above existing problems, this application provides a composite material for treating chip wastewater and a preparation method thereof. This application uses activated carbon loaded with zirconium and alumina to prepare a composite material, which has the characteristics of high adsorption, corrosion resistance, high efficiency in regeneration, and environmental protection. Especially when treating chip wastewater with a relatively high fluorine content, it shows high adsorption, greatly improving the fluoride removal effect, and the recycled composite material still has high fluoride ion adsorption performance.

[0006] In the first aspect, this application provides a preparation method of a composite material for treating chip wastewater, and the preparation method includes:

[0007] Immerse an activated carbon-zirconium loading material with a mass ratio of 1:(4 - 6) in alumina sol, and impregnate it for 1 - 1.5 h under magnetic stirring at 450 - 550 r / min;

[0008] The impregnated system is dried at a temperature of 60 - 70 °C for 0.5 - 2 h, and the obtained solid is calcined at a temperature of 400 - 900 °C for 4 - 6 h to obtain the composite material.

[0009] Optionally, the calcination is carried out in a nitrogen atmosphere, and the flow rate of the nitrogen atmosphere is 8 - 10 L / min.

[0010] Optionally, the temperature during the calcination is between 500 - 700 °C.

[0011] Optionally, the preparation method of the activated carbon - zirconium supported material includes:

[0012] Deionized water and absolute ethanol are mixed to prepare a pre - liquid.

[0013] The activated carbon is pretreated and then added to the pre - liquid, and ultrasonic treatment is carried out for 1 - 2 h to obtain a suspension. Under magnetic stirring, zirconium oxychloride is added to the suspension, and after dissolution, sodium hydroxide is added to adjust the pH to 9 - 11 to obtain a mixed solution.

[0014] The mixed solution is ultrasonically treated for 1 - 2 h, then heated to 175 - 185 °C, and reacted for 0.5 - 2 h. The obtained solid product is cooled and ground to obtain the activated carbon - zirconium supported material.

[0015] Optionally, the mesh number of the grinding is 30 - 40 meshes.

[0016] Optionally, when the activated carbon pretreated is added to the pre - liquid, the pretreatment method includes:

[0017] The activated carbon is placed in a nitric acid solution with a concentration of 0.5 - 1.5 mol / L, shaken at 100 - 140 rpm for 4 - 8 h, then left standing for 1 - 3 h, and washed to obtain the pretreated activated carbon.

[0018] Optionally, the preparation method of the alumina sol includes:

[0019] Deionized water is heated to 83 - 85 °C, and then aluminum isopropoxide is added thereto. Under constant - temperature magnetic stirring for 1.5 - 2.5 h, hydrolysis is carried out to obtain a reaction solution. Nitric acid with a concentration of 0.5 - 1.5 mol / L is added to the reaction solution, and the alumina sol is obtained through reaction.

[0020] Optionally, the molar ratio of aluminum isopropoxide, deionized water and nitric acid is 1:(120 - 130):(0.2 - 0.24).

[0021] In a second aspect, the present application provides a composite material obtained by the preparation method of the composite material for treating chip wastewater described in the first aspect above.

[0022] Thirdly, the present application provides an application of a composite material obtained by the preparation method of the chip wastewater treatment composite material described in the first aspect above in defluorination of chip wastewater. The composite material is used as a fluoride ion adsorbent and is applied to defluorination in chip wastewater treatment;

[0023] When the composite material is saturated, it is recycled after regeneration treatment. The regeneration treatment method includes:

[0024] The saturated composite material is filtered and dried in sequence, then placed in an aluminum sulfate solution, ultrasonically treated for 2 - 3 h, and then filtered and dried in sequence, and the composite material is recycled.

[0025] In summary, the present application includes the following beneficial technical effects:

[0026] The present application uses activated carbon as a substrate material, and loads aluminum and zirconium elements on the activated carbon to prepare an activated carbon-based composite material. The preparation process of this material uses fewer raw materials, which not only effectively reduces the treatment cost, but also reduces waste generation and has environmental protection; moreover, this composite material has a larger specific surface area, can provide a large number of adsorption sites, and has high adsorption performance for fluoride ions; it has good corrosion resistance, can resist the corrosion of wastewater in chip wastewater treatment, and maintains good stability and durability. When the adsorption is saturated, its adsorption performance can be restored by using an aluminum sulfate solution to achieve cyclic use. Description of the Drawings

[0027] Figure 1 is a flowchart of the preparation method of the chip wastewater treatment composite material in the embodiment of the present application;

[0028] Figure 2 is a flowchart of the preparation method of the activated carbon-zirconium loaded material in the embodiment of the present application;

[0029] Figure 3 is a flowchart of the regeneration method of the chip wastewater treatment composite material in the embodiment of the present application;

[0030] Figure 4 is a comparison chart of the defluorination effects of the chip wastewater treatment composite materials prepared in Examples 1 - 5 of the present application under different dosages of the activated carbon-zirconium loaded material;

[0031] Figure 5 is a comparison chart of the defluorination rates of the chip wastewater treatment composite materials prepared in Examples 6 - 10 of the present application under different calcination temperatures;

[0032] Figure 6 is a comparison chart of the defluorination rates of the chip wastewater treatment composite material prepared in Example 3 of the present application under different pH conditions;

[0033] Figure 7 It is a comparison chart of the fluorine removal rate of the chip wastewater treatment composite material prepared in Example 3 of the present application under different dosages;

[0034] Figure 8 It is a comparison chart of the fluorine removal rate of the chip wastewater treatment composite material prepared in Example 3 of the present application under different initial fluoride ion concentrations (5mg / L, 10mg / L, 20mg / L respectively);

[0035] Figure 9 It is a comparison chart of the fluorine removal rate of the chip wastewater treatment composite material, alumina sol, and activated carbon-zirconium loaded material prepared in Example 3 of the present application;

[0036] Figure 10 It is a comparison chart of the fluorine removal rate of the chip wastewater treatment composite material prepared in Example 3 of the present application after multiple regenerations. Detailed implementation manners

[0037] The present application will be further described in detail below in conjunction with embodiments. It should be specifically noted that: for those not specifying specific conditions in the following embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer; the raw materials used in the following embodiments can be obtained from ordinary commercial sources unless otherwise specified.

[0038] Fluorine is an essential element for the human body. Low concentrations of fluoride ions are beneficial for preventing dental caries and tooth decay. However, when the fluoride ion concentration is too high, it will cause harm to organisms or humans in water. Currently, the problem of excessive fluoride in water bodies is relatively common worldwide. The World Health Organization and the Environmental Protection Agency stipulate that the fluoride ion concentration shall not exceed 1.5mg / L. In China's "Sanitary Standard for Drinking Water (GB5749 - 2006)", the limit value of fluoride concentration is 1mg / L, and in the first-class standard of "Integrated Wastewater Discharge Standard (GB8978~1996)", it is required that the discharge concentration of fluoride during industrial production should be less than 10mg / L.

[0039] Among various types of industrial sewage, fluoride in chip wastewater is characterized by high concentration, strong corrosiveness, and high toxicity. Therefore, it is necessary to propose an effective method to reduce the fluoride ion concentration in chip wastewater and achieve efficient fluorine removal.

[0040] Currently, the technologies commonly used at home and abroad for removing fluoride in water can generally be divided into three categories: precipitation method, adsorption method, and membrane separation method. Among them, the adsorption method is the main method, and the commonly used adsorbents are activated alumina, hydroxyapatite, ion exchange resin, etc. However, such adsorbents have relatively strict requirements for the influent water quality, and the preparation cost of the adsorbents is relatively high, which is a challenge faced by current fluorine removal technologies. In comparison, activated carbon is a material with a relatively high cost performance for adsorption and defluorination, but there are still some problems with activated carbon adsorption:

[0041] First, the adsorption capacity of activated carbon is limited. Although activated carbon has a large specific surface area and a rich pore structure, and has a strong adsorption capacity for pollutants such as fluoride, it does not have a large adsorption capacity. After adsorption saturation, regeneration or replacement is required, which increases the treatment cost and operation complexity.

[0042] Second, since activated carbon will irreversibly adsorb some pollutants during the adsorption process, its adsorption capacity decreases after multiple uses. At present, the main regeneration methods of activated carbon include thermal regeneration, chemical regeneration, and biological regeneration, etc. However, based on the properties of activated carbon materials themselves, these methods all have certain limitations, such as low regeneration efficiency, high energy consumption, complex operation, etc., and it is difficult to achieve high efficiency and environmental protection.

[0043] In addition, the fluoride removal technology of activated carbon is also affected by water quality conditions. Factors such as fluoride concentration, pH value, and temperature in different water qualities will all affect the adsorption effect of activated carbon. For example, high-concentration fluoride will cause activated carbon to reach adsorption saturation, while low pH value will affect the surface charge and adsorption performance of activated carbon.

[0044] Finally, the fluoride removal technology of activated carbon also needs to consider economy and environmental protection. Activated carbon is a material with a relatively high price, and its use cost is high. Therefore, economy and treatment effect need to be comprehensively considered in practical applications. At the same time, environmental protection factors also need to be considered in the regeneration and waste treatment of activated carbon to avoid secondary pollution to the environment.

[0045] Therefore, this application proposes a highly efficient and usable composite material, which can efficiently remove fluoride and be recycled, and avoid causing secondary harm to the environment during the recycling process.

[0046] This application proposes a composite material for treating chip wastewater and a preparation method thereof for fluoride-containing chip wastewater. The specific implementation method is as follows:

[0047] A preparation method of a composite material for treating chip wastewater refers to Figure 1 , and the specific steps include:

[0048] Step S1: Immerse the activated carbon-zirconium loading material with a mass ratio of 1:(4 - 6) in alumina sol, and impregnate it for 1 - 1.5 h under magnetic stirring at 450 - 550 r / min;

[0049] In specific implementation, the impregnation method is used to load aluminum elements on the activated carbon-zirconium loading material, so that the aluminum elements are attached to the surface and pores of the activated carbon-zirconium loading material in the form of compounds, realizing the high dispersion of aluminum elements, and uniformly loading a sufficient amount of aluminum elements on the activated carbon-zirconium loading material.

[0050] In specific implementation, optionally, the mass ratio of activated carbon to zirconium in the activated carbon-zirconium supported material can be 1:4, 1:5 or 1:6.

[0051] Preferably, the mass ratio of activated carbon to zirconium in the activated carbon-zirconium supported material is 1:5.

[0052] In specific implementation, the mass ratio of the activated carbon-zirconium supported material to the alumina sol is 1:5.8. When prepared according to the above mass-volume ratio, the pore structure of the activated carbon-zirconium supported material can be better retained, avoiding excessive filling of pores by the alumina sol, thereby maintaining the high porosity and specific surface area of the composite material.

[0053] The addition of the alumina sol will change the surface charge and polarity of the activated carbon-zirconium supported material, thereby improving the adsorption performance of the composite material.

[0054] In specific implementation, optionally, the rotation speed during magnetic stirring is 450 r / min, 500 r / min or 550 r / min.

[0055] Preferably, the rotation speed during magnetic stirring is 500 r / min, so that the alumina is uniformly attached to the activated carbon-zirconium supported material to improve the homogeneity.

[0056] In specific implementation, optionally, the impregnation time is 1 h, 1.2 h or 1.5 h.

[0057] Preferably, the impregnation time is 1 h, so that the alumina in the alumina sol has sufficient dispersion time and uniformly diffuses to the surface and voids of the activated carbon-zirconium supported material.

[0058] Step S2: Place the impregnated system in an oven and dry it at a temperature of 60-70 °C for 0.5-2 h, and calcine the obtained solid at a temperature of 400-900 °C for 4-6 h to obtain the composite material.

[0059] In specific implementation, optionally, place the impregnated activated carbon-zirconium supported material in an oven and dry it at a temperature of 60 °C, 65 °C or 70 °C.

[0060] Preferably, place the impregnated activated carbon-zirconium supported material in an oven and dry it at a temperature of 60 °C.

[0061] In specific implementation, optionally, dry the impregnated activated carbon-zirconium supported material for 0.5 h, 1 h, 1.5 h or 2 h.

[0062] Preferably, dry the impregnated activated carbon-zirconium supported material for 2 h to fully dry the activated carbon-zirconium supported material, avoid adsorption of other solutions in the material, and retain the maximum adsorption capacity of the material.

[0063] During specific implementation, optionally, the obtained solid is calcined at a temperature of 400 °C, 500 °C, 600 °C, 700 °C, 800 °C or 900 °C.

[0064] Preferably, the obtained solid is placed in a tubular muffle furnace at 600 °C for calcination and compounding, taken out after cooling, and the chip wastewater treatment composite material is prepared.

[0065] During specific implementation, the calcination is carried out in a nitrogen atmosphere to prevent material oxidation and promote phase transformation. The flow rate of the nitrogen atmosphere is 8 - 10 L / min.

[0066] During specific implementation, optionally, the flow rate of the nitrogen atmosphere is 8 L / min, 8.5 L / min, 9 L / min, 9.5 L / min or 10 L / min.

[0067] Preferably, the flow rate of the nitrogen atmosphere is 10 L / min.

[0068] During specific implementation, the preparation method of the alumina sol includes:

[0069] Heat deionized water to 83 - 85 °C, then add aluminum isopropoxide thereto, stir magnetically at a constant temperature for 1.5 - 2.5 h for hydrolysis to obtain a reaction solution, and add nitric acid with a concentration of 0.5 - 1.5 mol / L to the reaction solution to prepare the alumina sol.

[0070] During specific implementation, put deionized water into a beaker, place the beaker in a constant temperature heating magnetic stirrer, and then heat it to 83 - 85 °C by using the constant temperature heating magnetic stirrer.

[0071] During specific implementation, heat deionized water to 83 °C, 84 °C or 85 °C.

[0072] Preferably, after heating deionized water to 85 °C, keep it at a constant temperature. Heating to 85 °C helps to accelerate the hydrolysis reaction of aluminum isopropoxide, improve production efficiency, shorten the reaction time, and the resulting sol system is more stable and uniform.

[0073] During specific implementation, slowly add aluminum isopropoxide to the heated deionized water. Slowly adding can ensure that the aluminum isopropoxide powder does not aggregate in water and is more completely dispersed.

[0074] During specific implementation, the rotation speed of the constant temperature magnetic stirring is 400 - 500 r / min.

[0075] During specific implementation, optionally, the rotation speed of the constant temperature magnetic stirring is 400 r / min, 450 r / min or 500 r / min.

[0076] Preferably, the rotation speed of the constant temperature magnetic stirring is 500 r / min.

[0077] In specific implementation, optionally, the time of constant-temperature magnetic stirring is 1.5 h, 2 h or 2.5 h.

[0078] In specific implementation, optionally, the concentration of the nitric acid solution is 0.5 mol / L, 1 mol / L or 1.5 mol / L.

[0079] Preferably, the concentration of the nitric acid solution is 1 mol / L.

[0080] In specific implementation, for simplicity of calculation, the molar ratio is adopted. The molar ratio of aluminum isopropoxide, deionized water and nitric acid is 1:(120 - 130):(0.2 - 0.24).

[0081] Preferably, the molar ratio of aluminum isopropoxide to deionized water and nitric acid is 1:130:0.24.

[0082] In specific implementation, the preparation method of the above-mentioned activated carbon-zirconium supported material refers to Figure 2 , including:

[0083] Step S11: Mix deionized water and absolute ethanol to obtain a prefabricated solution;

[0084] Step S12: After the activated carbon is pretreated, add it to the prefabricated solution, and perform ultrasonic treatment for 1 - 2 h to obtain a suspension. Under magnetic stirring, add zirconium oxychloride to the suspension. After dissolution, add sodium hydroxide to adjust the pH to 9 - 11 to obtain a mixed solution;

[0085] Step S13: The mixed solution is ultrasonically treated for 1 - 2 h, then heated to 175 - 185 °C, and reacted for 0.3 - 1 h. The obtained solid product is cooled and ground to obtain the activated carbon-zirconium supported material.

[0086] In specific implementation, when the activated carbon is added to the prefabricated solution after pretreatment, the pretreatment method includes:

[0087] Place the activated carbon in a nitric acid solution with a concentration of 0.5 - 1.5 mol / L, shake it at 100 - 140 rpm for 4 - 8 h, then let it stand for 1 - 3 h, and wash it to obtain the pretreated activated carbon.

[0088] By pretreating the activated carbon, impurities are removed, the internal pores of the activated carbon are enlarged, the area distribution inside and outside the pores is made uniform, the conductivity and hydrophilicity are improved. At the same time, the concentration of oxygen-containing functional groups on the surface of the activated carbon is increased, the hydrophilicity of the activated carbon material is improved, and a more effective electric double-layer capacitor is formed.

[0089] In specific implementation, optionally, place the activated carbon in a nitric acid solution with a concentration of 0.5 mol / L, 1 mol / L or 1.5 mol / L.

[0090] Preferably, the activated carbon is placed in a nitric acid solution with a concentration of 1 mol / L.

[0091] After being treated with nitric acid, more pores can be formed on the surface of the activated carbon, thereby increasing its surface area, enabling the activated carbon to adsorb more impurities and improving its adsorption capacity. At the same time, impurities and blockages on the surface of the activated carbon are removed, making its pore structure more open and facilitating the subsequent loading of zirconium and aluminum elements.

[0092] During specific implementation, optionally, it can be shaken at 100 rpm, 110 rpm, 120 rpm, 130 rpm, or 140 rpm.

[0093] Preferably, it is shaken at 120 rpm.

[0094] During specific implementation, optionally, the shaking time is 4 h, 5 h, 6 h, 7 h, or 8 h.

[0095] Preferably, the shaking time is 6 h.

[0096] During specific implementation, the standing time is 1 h, 2 h, or 3 h.

[0097] Preferably, the standing time is 2 h.

[0098] During specific implementation, the pretreated activated carbon is washed with deionized water until the pH value of the activated carbon no longer changes.

[0099] During specific implementation, deionized water and absolute ethanol are mixed in a ratio of 1:1.

[0100] During specific implementation, optionally, the ultrasonic treatment time is 1 h, 1.5 h, or 2 h.

[0101] Preferably, the ultrasonic treatment time is 2 h to form a uniformly dispersed suspension.

[0102] During specific implementation, the concentration of sodium hydroxide added is 4 mol / L.

[0103] During specific implementation, optionally, the pH is adjusted to 9, 10, or 11.

[0104] Preferably, the pH is adjusted to 10.

[0105] During specific implementation, the mixed solution is ultrasonically treated for 1 h, 1.5 h, or 2 h. Preferably, the mixed solution is ultrasonically treated for 1 h.

[0106] During specific implementation, after the mixed solution is ultrasonically treated, it is then heated to 175 °C, 180 °C, or 185 °C. Preferably, after the mixed solution is ultrasonically treated, it is then heated to 180 °C.

[0107] In specific implementation, the mixed solution is ultrasonically treated for 1 - 2 h, then heated to 175 - 185 °C, and reacted for 0.3 h, 0.4 h, 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h or 1 h. Preferably, the reaction time is 0.5 h.

[0108] In specific implementation, after ultrasonically treating the mixed solution for 1 h, it is placed into a polytetrafluoroethylene inner liner, then loaded into a high-temperature reactor, sealed and placed in an oven, and reacted at 180 °C for 0.5 h. After cooling and grinding, it is sieved through a 30 - 40 mesh sieve.

[0109] Adding a polytetrafluoroethylene inner liner can prevent the inner wall of the reactor from being corroded, prevent substances from adhering to the inner wall of the reactor, and reduce the operation difficulty.

[0110] Preferably, the obtained product is sieved through a 30 - mesh sieve after grinding.

[0111] In the second aspect, the present application provides a composite material prepared by the preparation method of the chip wastewater treatment composite material in the first aspect above.

[0112] In the third aspect, the present application provides an application of the composite material prepared by the preparation method of the chip wastewater treatment composite material in the first aspect above in defluorination of chip wastewater. The composite material is used as a fluoride ion adsorbent and applied to defluorination in chip wastewater treatment.

[0113] When the composite material is saturated, after regeneration treatment, it can be recycled. The regeneration treatment method includes:

[0114] The saturated composite material is filtered and dried in sequence, then placed in an aluminum sulfate solution, ultrasonically treated for 2 - 3 h, and then filtered and dried in sequence, and the composite material is recycled.

[0115] In specific implementation, the regeneration treatment method refers to Figure 3 , and includes:

[0116] Step S21: Filter the saturated composite material with a filtering device of ≥30 meshes, dry it, and then recycle it;

[0117] Step S22: Place the recycled composite material in an aluminum sulfate solution with a concentration of 5 - 8%, ultrasonically treat it for 2 - 3 h, filter it again with a filtering device of ≥30 meshes, and recycle it after drying.

[0118] In specific implementation, the concentration of the aluminum sulfate solution can be 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or 8%.

[0119] In specific implementation, the ultrasonication time can be 2 h, 2.5 h or 3 h.

[0120] It should be noted that the value ranges of the above substances and the value ranges of the various parameters are only the preferred solutions of the present invention. The present invention does not limit the values, and any value ranges applicable to the present invention are feasible.

[0121] To enable those skilled in the art to better understand the present application, the following describes the preparation method of the chip wastewater treatment composite material provided by the present application through multiple specific examples.

[0122] Example 1

[0123] A preparation method of a chip wastewater treatment composite material

[0124] Step 1: Measure 100 mL of deionized water and add it to a beaker, and place it in a thermostatic heating magnetic stirrer to heat to 85 °C; weigh 8.7 g of aluminum isopropoxide powder with an electronic balance, slowly add it to 100 mL of heated deionized water and stir for 2 h; slowly add 10 mL of 1 mol / L HNO3 solution to the hydrolysis solution of aluminum isopropoxide, and continue to stir for 1 h. The molar ratio of the added aluminum isopropoxide to water and nitric acid is 1:130:0.24, and finally a transparent and stable alumina sol is prepared.

[0125] Step 2: Take 60 g of activated carbon and place it in 30 ml of a 1% nitric acid solution, shake it in a shaking box at 25 °C and 120 rpm for 6 h, let it stand for 2 h, and then wash it with deionized water until the pH no longer changes.

[0126] Step 3: Mix deionized water and absolute ethanol in a volume ratio of 1:1 to make 30 ml of a prefabricated solution. Place the prefabricated solution in a 50 ml glassware, add 100 mg of pretreated activated carbon powder, and ultrasonically treat it for 2 h to modify the activated carbon powder and form a uniformly dispersed suspension. Under the action of magnetic stirring, add 500 mg of zirconium hydroxide solid. After the solid is dissolved, add 4 mol / L NaOH solution until the pH of the mixed solution is 10. After the mixed solution is ultrasonically treated for 1 h, put it into a polytetrafluoroethylene inner liner, then put it into a high-temperature reaction kettle, seal it and place it in an oven, and react at 180 °C for 0.5 h. The obtained solid product is cooled, ground and sieved through a 30-mesh sieve to obtain an activated carbon-zirconium loaded material.

[0127] Step 4: Weigh 1.00 g of the activated carbon-zirconium loaded material, add it to the above-prepared alumina sol, impregnate it under magnetic stirring at 500 r / min for 1 h, and then place the impregnated system in a drying oven and dry it at 60 °C for 2 h; put the above-obtained solid into a tubular muffle furnace, calcine it at 600 °C for 5 h in a nitrogen environment, and the nitrogen flow rate is 10 L / min to obtain a chip wastewater treatment composite material. Wait for it to cool, take it out, and store it for standby.

[0128] Example 2

[0129] Preparation Method of a Composite Material for Chip Wastewater Treatment

[0130] The difference between Example 2 and Example 1 lies in: the different mass of the activated carbon-zirconium loaded material (dosage) and the different rotation speed of magnetic stirring in Step 4.

[0131] Step 1: Measure 100 mL of deionized water and add it to a beaker, and heat it to 85 °C in a constant temperature heating magnetic stirrer; weigh 8.7 g of aluminum isopropoxide powder with an electronic balance, slowly add it to 100 mL of heated deionized water and stir for 2 h; slowly add 10 mL of 1 mol / L HNO3 solution to the hydrolysis solution of aluminum isopropoxide, and continue to stir for 1 h. The molar ratio of the added aluminum isopropoxide to water and nitric acid is 1:130:0.24, and finally a transparent and stable alumina sol is prepared.

[0132] Step 2: Take 60 g of activated carbon and place it in 30 ml of nitric acid solution with a concentration of 1%, shake it in a shaking box at 25 °C and 120 rpm for 6 h, let it stand for 2 h, and then wash it with deionized water until the pH no longer changes.

[0133] Step 3: Mix deionized water and absolute ethanol according to a volume ratio of 1:1 to make 30 ml of a prefabricated solution. Place the prefabricated solution in a 50 ml glassware, add 100 mg of pretreated activated carbon powder, and ultrasonically treat it for 2 h to modify the activated carbon powder and form a uniformly dispersed suspension. Under the action of magnetic stirring, add 500 mg of zirconium hydroxide solid. After the solid is dissolved, add 4 mol / L NaOH solution until the pH of the mixed solution is 10. After the mixed solution is ultrasonically treated for 1 h, put it into a polytetrafluoroethylene inner liner, then install it into a high-temperature reaction kettle, seal it and place it in an oven, and react at 180 °C for 0.5 h. The obtained solid product is cooled, ground and sieved through a 30-mesh sieve to obtain the activated carbon-zirconium loaded material.

[0134] Step 4: Weigh 1.25 g of the activated carbon-zirconium loaded material, add it to the above-prepared alumina sol, impregnate it for 1 h under magnetic stirring at 550 r / min, and then put the impregnated system into a drying oven and dry it at 60 °C for 2 h; put the above-obtained solid into a tubular muffle furnace, calcine it at 600 °C for 5 h in a nitrogen environment, and the nitrogen flow rate is 10 L / min to obtain the composite material. Wait for it to cool, take it out and store it for later use.

[0135] Example 3

[0136] Preparation Method of a Composite Material for Chip Wastewater Treatment

[0137] The difference between Example 3 and Example 1 lies in: the different mass of the activated carbon-zirconium loaded material (dosage) and the different impregnation time in Step 4.

[0138] Step 1: Measure 100 mL of deionized water and add it to a beaker, then place it in a thermostatic heating magnetic stirrer and heat it to 85 °C. Weigh 8.7 g of aluminum isopropoxide powder with an electronic balance, slowly add it to the 100 mL of heated deionized water and stir for 2 h. Slowly add 10 mL of 1 mol / L HNO3 solution to the hydrolysis solution of aluminum isopropoxide, and continue to stir for 1 h. The molar ratio of the added aluminum isopropoxide to water and nitric acid is 1:130:0.24, and finally a transparent and stable alumina sol is prepared.

[0139] Step 2: Take 60 g of activated carbon and place it in 30 mL of 1% nitric acid solution. Shake it in a shaking box at 25 °C and 120 rpm for 6 h, let it stand for 2 h, and then wash it with deionized water until the pH no longer changes.

[0140] Step 3: Mix deionized water and absolute ethanol in a volume ratio of 1:1 to make 30 mL of a prefabricated solution. Place the prefabricated solution in a 50 mL glassware, add 100 mg of pretreated activated carbon powder, and ultrasonically treat it for 2 h to modify the activated carbon powder and form a uniformly dispersed suspension. Under the action of magnetic stirring, add 500 mg of zirconium hydroxide solid. After the solid is dissolved, add 4 mol / L NaOH solution until the pH of the mixed solution is 10. After ultrasonically treating the mixed solution for 1 h, put it into a polytetrafluoroethylene inner liner, then install it in a high-temperature reaction kettle, seal it and place it in an oven, and react at 180 °C for 0.5 h. Cool the obtained solid product, grind it, and pass it through a 30-mesh sieve to obtain an activated carbon-zirconium supported material.

[0141] Step 4: Weigh 1.50 g of the activated carbon-zirconium supported material and add it to the above-prepared alumina sol. Immerse it under magnetic stirring at 500 r / min for 1.5 h, and then place the immersed system in a drying oven and dry it at 60 °C for 2 h. Put the obtained solid into a tubular muffle furnace and calcine it at 600 °C for 5 h in a nitrogen environment, with a nitrogen flow rate of 10 L / min, to obtain a composite material for treating chip wastewater. Wait for it to cool, take it out, and store it for standby.

[0142] Example 4

[0143] A preparation method of a composite material for treating chip wastewater

[0144] The difference between Example 4 and Example 1 lies in: the mass of the activated carbon-zirconium supported material (dosage) is different and the nitrogen flow rate is different.

[0145] Step 1: Measure 100 mL of deionized water and add it to a beaker, then place it in a thermostatic heating magnetic stirrer and heat it to 85 °C; weigh 8.7 g of aluminum isopropoxide powder with an electronic balance, slowly add it to the 100 mL of heated deionized water and stir for 2 h; slowly add 10 mL of 1 mol / L HNO3 solution to the hydrolysis solution of aluminum isopropoxide, continue to stir for 1 h. The molar ratio of the added aluminum isopropoxide to water and nitric acid is 1:130:0.24, and finally a transparent and stable alumina sol is prepared.

[0146] Step 2: Take 60 g of activated carbon and place it in 30 mL of 1% nitric acid solution, shake it in a shaking box at 25 °C and 120 rpm for 6 h, let it stand for 2 h, and then wash it with deionized water until the pH no longer changes.

[0147] Step 3: Mix deionized water and absolute ethanol in a volume ratio of 1:1 to make 30 mL of a prefabricated solution. Place the prefabricated solution in a 50 mL glassware, add 100 mg of pretreated activated carbon powder, and ultrasonically treat it for 2 h to modify the activated carbon powder and form a uniformly dispersed suspension. Under the action of magnetic stirring, add 500 mg of zirconium hydroxide solid. After the solid dissolves, add 4 mol / L NaOH solution until the pH of the mixed solution is 10. After ultrasonically treating the mixed solution for 1 h, put it into a polytetrafluoroethylene inner liner, then install it in a high-temperature reaction kettle, seal it and place it in an oven, and react at 180 °C for 0.5 h. Cool the obtained solid product, grind it, and pass it through a 30-mesh sieve to obtain an activated carbon-zirconium supported material.

[0148] Step 4: Weigh 1.75 g of the activated carbon-zirconium supported material, add it to the above-prepared alumina sol, impregnate it under magnetic stirring at 500 r / min for 1 h, and then place the impregnated system in a drying oven and dry it at 60 °C for 2 h; put the above-obtained solid into a tubular muffle furnace, calcine it at 600 °C for 5 h in a nitrogen environment, and the nitrogen flow rate is 9 L / min to obtain a composite material for treating chip wastewater. Wait for it to cool, take it out, and store it for standby.

[0149] Example 5

[0150] A preparation method of a composite material for treating chip wastewater

[0151] The difference between Example 5 and Example 1 lies in: the mass of the activated carbon-zirconium supported material (dosage) is different and the nitrogen flow rate is different.

[0152] Step 1: Measure 100 mL of deionized water and add it to a beaker, then place it in a thermostatic heating magnetic stirrer and heat it to 85 °C; weigh 8.7 g of aluminum isopropoxide powder with an electronic balance, slowly add it to the 100 mL of heated deionized water and stir for 2 h; slowly add 10 mL of 1 mol / L HNO3 solution to the hydrolysis solution of aluminum isopropoxide, continue to stir for 1 h. The molar ratio of the added aluminum isopropoxide to water and nitric acid is 1:130:0.24, and finally a transparent and stable alumina sol is prepared.

[0153] Step 2: Take 60 g of activated carbon and place it in 30 ml of a 1% nitric acid solution, shake it in a shaking box at 25 °C and 120 rpm for 6 h, let it stand for 2 h, and then wash it with deionized water until the pH no longer changes.

[0154] Step 3: Mix deionized water and absolute ethanol in a volume ratio of 1:1 to make 30 ml of a pre-prepared solution. Place the pre-prepared solution in a 50 ml glassware, add 100 mg of pretreated activated carbon powder, and ultrasonically treat it for 2 h to modify the activated carbon powder and form a uniformly dispersed suspension. Under the action of magnetic stirring, add 500 mg of zirconium hydroxide solid. After the solid dissolves, add 4 mol / L NaOH solution until the pH of the mixed solution is 10. After ultrasonically treating the mixed solution for 1 h, put it into a polytetrafluoroethylene inner liner, then install it into a high-temperature reaction kettle, seal it and place it in an oven, and react at 180 °C for 0.5 h. Cool the obtained solid product, grind it, and sieve it through a 30-mesh sieve to obtain an activated carbon-zirconium loaded material.

[0155] Step 4: Weigh 2.00 g of the activated carbon-zirconium loaded material, add it to the above-prepared alumina sol, impregnate it under magnetic stirring at 500 r / min for 1 h, and then place the impregnated system in a drying oven and dry it at 60 °C for 2 h; put the above-obtained solid into a tubular muffle furnace, calcine it at 600 °C for 5 h in a nitrogen environment, and the nitrogen flow rate is 8 L / min to obtain a composite material for treating chip wastewater. Wait for it to cool, take it out, and store it for standby.

[0156] Example 6

[0157] A preparation method of a composite material for treating chip wastewater

[0158] The difference between Example 6 and Example 1 is only that: the mass of the activated carbon-zirconium loaded material is different and the temperature during the calcination of the obtained solid is different.

[0159] Step 1: Measure 100 mL of deionized water and add it to a beaker, then place it in a thermostatic heating magnetic stirrer and heat it to 85 °C. Weigh 8.7 g of aluminum isopropoxide powder with an electronic balance, slowly add it to the 100 mL of heated deionized water and stir for 2 h. Slowly add 10 mL of 1 mol / L HNO3 solution to the hydrolysis solution of aluminum isopropoxide, and continue to stir for 1 h. The molar ratio of the added aluminum isopropoxide to water and nitric acid is 1:130:0.24, and finally a transparent and stable alumina sol is prepared.

[0160] Step 2: Take 60 g of activated carbon and place it in 30 mL of a 1% nitric acid solution. Shake it in a shaker at 25 °C and 120 rpm for 6 h, let it stand for 2 h, and then wash it with deionized water until the pH no longer changes.

[0161] Step 3: Mix deionized water and absolute ethanol in a volume ratio of 1:1 to make 30 mL of a prefabricated solution. Place the prefabricated solution in a 50 mL glassware, add 100 mg of pretreated activated carbon powder, and ultrasonically treat it for 2 h to modify the activated carbon powder and form a uniformly dispersed suspension. Under the action of magnetic stirring, add 500 mg of zirconium oxychloride solid. After the solid dissolves, add 4 mol / L NaOH solution until the pH of the mixed solution is 10. After ultrasonically treating the mixed solution for 1 h, place it in a polytetrafluoroethylene inner liner, then put it into a high-temperature reaction kettle, seal it and place it in an oven, and react at 180 °C for 0.5 h. Cool the obtained solid product, grind it, and pass it through a 30-mesh sieve to obtain an activated carbon-zirconium supported material.

[0162] Step 4: Weigh 2.00 g of the activated carbon-zirconium supported material, add it to the alumina sol prepared above, impregnate it under magnetic stirring at 500 r / min for 1 h, and then place the impregnated system in a drying oven and dry it at 60 °C for 2 h. Place the obtained solid in a tubular muffle furnace, calcine it at 400 °C for 5 h in a nitrogen environment, with a nitrogen flow rate of 10 L / min, to obtain a composite material for treating chip wastewater. Wait for it to cool, take it out, and store it for later use.

[0163] Example 7

[0164] A preparation method of a composite material for treating chip wastewater

[0165] The difference between Example 7 and Example 1 lies in: the mass of the activated carbon-zirconium supported material is different, the temperature during the calcination of the obtained solid is different, the rotation speed of the magnetic stirring in Step 4 is different, and the impregnation time is different.

[0166] Step 1: Measure 100 mL of deionized water and add it to a beaker, then place it in a thermostatic heating magnetic stirrer and heat it to 85 °C; weigh 8.7 g of aluminum isopropoxide powder with an electronic balance, slowly add it to the 100 mL of heated deionized water and stir for 2 h; slowly add 10 mL of 1 mol / L HNO3 solution to the hydrolysis solution of aluminum isopropoxide, continue to stir for 1 h. The molar ratio of the added aluminum isopropoxide to water and nitric acid is 1:130:0.24, and finally a transparent and stable alumina sol is prepared.

[0167] Step 2: Take 60 g of activated carbon and place it in 30 ml of a 1% nitric acid solution. Shake it in a shaker at 25 °C and 120 rpm for 6 h, let it stand for 2 h, and then wash it with deionized water until the pH no longer changes.

[0168] Step 3: Mix deionized water and absolute ethanol at a volume ratio of 1:1 to make 30 ml of a pre-prepared solution. Place the pre-prepared solution in a 50 ml glassware, add 100 mg of pretreated activated carbon powder, and ultrasonically treat it for 2 h to modify the activated carbon powder and form a uniformly dispersed suspension. Under the action of magnetic stirring, add 500 mg of zirconium hydroxide solid. After the solid is dissolved, add 4 mol / L NaOH solution until the pH of the mixed solution is 10. After the mixed solution is ultrasonically treated for 1 h, put it into a polytetrafluoroethylene inner liner, then load it into a high-temperature reaction kettle, seal it and place it in an oven, and react at 180 °C for 0.5 h. The obtained solid product is cooled, ground and sieved through a 30-mesh sieve to obtain an activated carbon-zirconium supported material.

[0169] Step 4: Weigh 2.00 g of the activated carbon-zirconium supported material, add it to the above-prepared alumina sol, impregnate it under magnetic stirring at 450 r / min for 1.5 h, and then put the impregnated system into a drying oven and dry it at 60 °C for 2 h; put the above-obtained solid in a tubular muffle furnace, calcine it at 500 °C for 5 h in a nitrogen environment, and the nitrogen flow rate is 10 L / min to obtain a composite material for treating chip wastewater. Wait for it to cool, take it out and store it for later use.

[0170] Example 8

[0171] A preparation method of a composite material for treating chip wastewater

[0172] The difference between Example 8 and Example 1 is only that: the mass of the activated carbon-zirconium supported material is different and the temperature during the calcination of the obtained solid is different.

[0173] Step 1: Measure 100 mL of deionized water and add it to a beaker, then place it in a thermostatic heating magnetic stirrer and heat it to 85 °C; weigh 8.7 g of aluminum isopropoxide powder with an electronic balance, slowly add it to the 100 mL of heated deionized water and stir for 2 h; slowly add 10 mL of 1 mol / L HNO3 solution to the hydrolysis solution of aluminum isopropoxide, continue to stir for 1 h. The molar ratio of the added aluminum isopropoxide to water and nitric acid is 1:130:0.24, and finally a transparent and stable alumina sol is prepared.

[0174] Step 2: Take 60 g of activated carbon and place it in 30 ml of nitric acid solution with a concentration of 1%, shake it in a shaking box at 25 °C and 120 rpm for 6 h, let it stand for 2 h, and then wash it with deionized water until the pH no longer changes.

[0175] Step 3: Mix deionized water and absolute ethanol in a volume ratio of 1:1 to make 30 ml of a prefabricated solution. Place the prefabricated solution in a 50 ml glassware, add 100 mg of pretreated activated carbon powder, and ultrasonically treat it for 2 h to modify the activated carbon powder and form a uniformly dispersed suspension. Under the action of magnetic stirring, add 500 mg of zirconium hydroxide solid. After the solid is dissolved, add 4 mol / L NaOH solution until the pH of the mixed solution is 10. After ultrasonically treating the mixed solution for 1 h, put it into a polytetrafluoroethylene inner liner, then install it in a high-temperature reaction kettle, seal it and place it in an oven, and react at 180 °C for 0.5 h. Cool the obtained solid product, grind it, and pass it through a 30-mesh sieve to obtain an activated carbon-zirconium supported material.

[0176] Step 4: Weigh 2.00 g of the activated carbon-zirconium supported material, add it to the above-prepared alumina sol, impregnate it under magnetic stirring at 500 r / min for 1 h, and then place the impregnated system in a drying oven and dry it at 60 °C for 2 h; put the above-obtained solid into a tubular muffle furnace, calcine it at 700 °C for 5 h in a nitrogen environment, and the nitrogen flow rate is 10 L / min to obtain a composite material for treating chip wastewater. Wait for it to cool, take it out, and store it for standby.

[0177] Example 9

[0178] A preparation method of a composite material for treating chip wastewater

[0179] The difference between Example 9 and Example 1 lies in: the mass of the activated carbon-zirconium supported material is different, the temperature during the calcination of the obtained solid is different, and the temperature and time for drying the impregnated system in Step 4 are different.

[0180] Step 1: Measure 100 mL of deionized water and add it to a beaker, then place it in a thermostatic heating magnetic stirrer and heat it to 85 °C. Weigh 8.7 g of aluminum isopropoxide powder with an electronic balance, slowly add it to the 100 mL of heated deionized water and stir for 2 h. Slowly add 10 mL of 1 mol / L HNO3 solution to the hydrolysis solution of aluminum isopropoxide, and continue to stir for 1 h. The molar ratio of the added aluminum isopropoxide to water and nitric acid is 1:130:0.24, and finally a transparent and stable alumina sol is prepared.

[0181] Step 2: Take 60 g of activated carbon and place it in 30 ml of a 1% nitric acid solution. Shake it in a shaker at 25 °C and 120 rpm for 6 h, let it stand for 2 h, and then wash it with deionized water until the pH no longer changes.

[0182] Step 3: Mix deionized water and absolute ethanol at a volume ratio of 1:1 to make 30 ml of a prefabricated solution. Place the prefabricated solution in a 50 ml glassware, add 100 mg of pretreated activated carbon powder, and ultrasonically treat it for 2 h to modify the activated carbon powder and form a uniformly dispersed suspension. Under the action of magnetic stirring, add 500 mg of zirconium hydroxide solid. After the solid dissolves, add 4 mol / L NaOH solution until the pH of the mixed solution is 10. After ultrasonically treating the mixed solution for 1 h, put it into a polytetrafluoroethylene inner liner, then install it in a high-temperature reaction kettle, seal it and place it in an oven, and react at 180 °C for 0.5 h. Cool the obtained solid product, grind it and pass it through a 30-mesh sieve to obtain an activated carbon-zirconium supported material.

[0183] Step 4: Weigh 2.00 g of the activated carbon-zirconium supported material, add it to the above-prepared alumina sol, impregnate it under magnetic stirring at 500 r / min for 1 h, and then place the impregnated system in a drying oven and dry it at 70 °C for 1 h. Put the above-obtained solid into a tubular muffle furnace, calcine it at 800 °C for 5 h in a nitrogen atmosphere, with a nitrogen flow rate of 10 L / min, to obtain a composite material for treating chip wastewater. Wait for it to cool, take it out, and store it for standby.

[0184] Example 10

[0185] A preparation method of a composite material for treating chip wastewater

[0186] The difference between Example 10 and Example 1 lies in: the different mass of the activated carbon-zirconium supported material, the different temperature during the calcination of the obtained solid, and the different temperature and time for drying the impregnated system in Step 4.

[0187] Step 1: Measure 100 mL of deionized water and add it to a beaker, then place it in a thermostatic heating magnetic stirrer and heat it to 85 °C; weigh 8.7 g of aluminum isopropoxide powder with an electronic balance, slowly add it to the 100 mL of heated deionized water and stir for 2 h; slowly add 10 mL of 1 mol / L HNO3 solution to the hydrolysis solution of aluminum isopropoxide, continue to stir for 1 h. The molar ratio of the added aluminum isopropoxide to water and nitric acid is 1:130:0.24, and finally a transparent and stable alumina sol is prepared.

[0188] Step 2: Take 60 g of activated carbon and place it in 30 ml of a 1% nitric acid solution, shake it in a shaking box at 25 °C and 120 rpm for 6 h, let it stand for 2 h, and then wash it with deionized water until the pH no longer changes.

[0189] Step 3: Mix deionized water and absolute ethanol at a volume ratio of 1:1 to make 30 ml of a pre-prepared solution. Place the pre-prepared solution in a 50 ml glassware, add 100 mg of pretreated activated carbon powder, and ultrasonically treat it for 2 h to modify the activated carbon powder and form a uniformly dispersed suspension. Under the action of magnetic stirring, add 500 mg of zirconium hydroxide solid. After the solid dissolves, add 4 mol / L NaOH solution until the pH of the mixed solution is 10. After ultrasonically treating the mixed solution for 1 h, put it into a polytetrafluoroethylene inner liner, then install it in a high-temperature reaction kettle, seal it and place it in an oven, and react at 180 °C for 0.5 h. Cool the obtained solid product, grind it and sieve it through a 30-mesh sieve to obtain an activated carbon-zirconium supported material.

[0190] Step 4: Weigh 2.00 g of the activated carbon-zirconium supported material, add it to the above-prepared alumina sol, impregnate it under magnetic stirring at 500 r / min for 1 h, and then put the impregnated system into a drying oven and dry it at 65 °C for 1.5 h; put the above-obtained solid into a tubular muffle furnace, calcine it at 900 °C for 5 h in a nitrogen environment, and the nitrogen flow rate is 10 L / min to obtain a composite material for treating chip wastewater. Wait for it to cool, take it out, and store it for standby.

[0191] Example 11

[0192] A preparation method of a composite material for treating chip wastewater

[0193] The difference between Example 11 and Example 1 is that the mass of the used activated carbon-zirconium supported material is different and a regeneration step is added.

[0194] Step 1: Measure 100 mL of deionized water and add it to a beaker, then place it in a thermostatic heating magnetic stirrer and heat it to 85 °C. Weigh 8.7 g of aluminum isopropoxide powder with an electronic balance, slowly add it to the 100 mL of heated deionized water and stir for 2 h. Slowly add 10 mL of 1 mol / L HNO3 solution to the hydrolysis solution of aluminum isopropoxide, and continue to stir for 1 h. The molar ratio of the added aluminum isopropoxide to water and nitric acid is 1:130:0.24, and finally a transparent and stable alumina sol is prepared.

[0195] Step 2: Take 60 g of activated carbon and place it in 30 ml of a 1% nitric acid solution. Shake it in a shaker at 25 °C and 120 rpm for 6 h, let it stand for 2 h, and then wash it with deionized water until the pH no longer changes.

[0196] Step 3: Mix deionized water and absolute ethanol at a volume ratio of 1:1 to make 30 ml of a pre-prepared solution. Place the pre-prepared solution in a 50 ml glassware, add 100 mg of pretreated activated carbon powder, and ultrasonically treat it for 2 h to modify the activated carbon powder and form a uniformly dispersed suspension. Under the action of magnetic stirring, add 500 mg of zirconium hydroxide solid. After the solid dissolves, add 4 mol / L NaOH solution until the pH of the mixed solution is 10. After ultrasonically treating the mixed solution for 1 h, put it into a polytetrafluoroethylene inner liner, then install it in a high-temperature reaction kettle, seal it and place it in an oven, and react at 180 °C for 0.5 h. Cool the obtained solid product, grind it, and sieve it through a 30-mesh sieve to obtain an activated carbon-zirconium supported material.

[0197] Step 4: Weigh 1.50 g of the activated carbon-zirconium supported material and add it to the above-prepared alumina sol. Immerse it under magnetic stirring at 500 r / min for 1 h, and then place the immersed system in a drying oven and dry it at 60 °C for 2 h. Put the above-obtained solid into a tubular muffle furnace and calcine it at 900 °C for 5 h in a nitrogen environment, with a nitrogen flow rate of 10 L / min, to obtain a composite material for treating chip wastewater. Wait for it to cool, take it out, and store it for standby.

[0198] Step 5: After the composite material is saturated in adsorption, filter it with a 40-mesh filter device and dry it. Then put the dried composite material into a 5% concentration aluminum sulfate solution for regeneration. After regeneration, filter and dry it, and recycle the obtained composite material.

[0199] Performance test method

[0200] Test method: Use the fluoride ion selective electrode method (GB7484-87) to measure the fluoride ion concentration in the aqueous solution.

[0201] The determination method includes:

[0202] Put the fluoride ion selective electrode and the reference electrode (calomel electrode) together into the fluoride-containing solution to be measured. The potential difference between the selective electrode and the reference electrode, that is, the electromotive force E of the electrode, has a linear relationship with the logarithm of the fluoride ion concentration, that is, it follows the Nernst equation. Before each measurement, 10 mL of TISAB I, that is, the total ion strength adjustment buffer solution, should be added to the sample.

[0203] The preparation method of TISAB I is as follows: Weigh 58.8 g of sodium citrate dihydrate and 85 g of sodium nitrate, dissolve them in water, then adjust the pH value to between 5 and 6 with hydrochloric acid, transfer it to a 1000 mL volumetric flask, and make up the volume to obtain TISAB I. The purpose of adding TISAB I is to prevent the influence of other ions existing in the water sample to be measured on the test results.

[0204] The fluoride ion-containing solution used in the experiment is a simulated fluoride-containing chip wastewater prepared by adding analytical pure sodium fluoride to deionized water.

[0205] First, dry 0.2210 g of NaF at 105 - 110 °C for 2 h, then add it to deionized water to dissolve and transfer it to a 1000 mL volumetric flask, make up the volume, and store it in a polyethylene bottle to obtain a fluoride standard stock solution with a fluoride ion concentration of 100 μg / mL. Then, different concentrations of fluoride-containing solutions to be measured can be prepared from the fluoride standard stock solution, specifically including the solutions to be measured with a fluoride content similar to that in the chip wastewater, which are used for the simulated fluoride-containing wastewater experiment.

[0206] In the embodiments of the present application, the chip wastewater treatment composite material is used as an adsorbent and put into a conical flask containing NaF solution. Then, place the conical flask in a thermostatic heating magnetic stirrer with heat collection, set the temperature to 25 °C, and the stirring speed to 500 r / min. After the reaction, take a certain amount of the solution, centrifuge the reaction solution with a centrifuge, and take the supernatant to measure the fluoride ion concentration, and calculate the removal rate of fluoride ions by this adsorbent.

[0207] Performance test results

[0208] Figure 4 It is a comparison chart of the defluorination effects of the chip wastewater treatment composite materials prepared in Examples 1 - 5 of the present application under different dosages of activated carbon-zirconium loading materials. The test results are the defluorination rate and the remaining fluoride ion concentration of the chip wastewater treatment composite materials after 150 min when the dosage of activated carbon-zirconium loading materials is 1 - 2.0 g / L. According to Figure 4 It can be obtained that the addition amount of 1.50 g of activated carbon-zirconium loading material is the most suitable, and the adsorption performance of the obtained chip wastewater treatment composite material is the best.

[0209] Figure 5 It is a comparison chart of the defluorination rates of the chip wastewater treatment composite materials prepared in Examples 6 - 10 of the present application under different calcination temperatures.Figure 5 In it, "●" represents the final remaining concentration of fluoride ions, and "■" represents the fluoride ion removal rate. The test results are the fluoride ion removal rate and the remaining concentration of fluoride ions after 150 minutes of the composite material under the conditions that the dosage of the composite material is 2.0 g / L, the initial concentration of fluoride ions is 5 mg / L, and the pH is 6.90 ± 0.20. According to Figure 5 It can be seen that when the calcination temperature is 600 °C, the obtained composite material has the best performance and the best fluoride removal effect.

[0210] Figure 6 It is a comparison chart of the fluoride ion removal rates of the chip wastewater treatment composite material prepared in Example 3 of this application under different pH conditions. The test results are the fluoride ion removal rates of the composite material at 150 minutes under the conditions that the dosage of the composite material is 2.0 g / L and the initial concentration of fluoride ions is 5 mg / L. According to Figure 6 It can be seen that when the pH is in the range of 6.90 ± 0.20, the obtained composite material has the best adsorption performance.

[0211] Figure 7 It is a comparison chart of the fluoride ion removal rates of the chip wastewater treatment composite material prepared in Example 3 of this application under different dosages. The test results are the fluoride ion removal rates of the chip wastewater treatment composite material after 150 minutes under the conditions that the initial concentration of fluoride ions is 5 mg / L and the pH is 6.90 ± 0.20. According to Figure 7 It can be seen that when the initial dosage of the activated carbon composite material is 2.0 g / L, its dosage has the best cost performance.

[0212] Figure 8 It is a comparison chart of the fluoride ion removal rates of the chip wastewater treatment composite material prepared in Example 3 of this application under different initial fluoride ion concentrations (5 mg / L, 10 mg / L, and 20 mg / L respectively), Figure 8 in which "■" is the initial concentration of fluoride ions of 5 mg / L, "●" is the initial concentration of fluoride ions of 10 mg / L, and "▲" is the initial concentration of fluoride ions of 20 mg / L. The test results are the change of the fluoride ion removal rate of the composite material with time under the conditions that the dosage of the chip wastewater treatment composite material is 2.0 g / L and the pH is 6.90 ± 0.20. According to Figure 8 It can be seen that when the initial concentration of fluoride ions is 5 mg / L, the fluoride ion removal rate can reach 90% after 150 minutes. When it is 10 mg / L and 20 mg / L, the fluoride ion removal rate decreases, but still has a good fluoride removal effect.

[0213] Figure 9 It is a comparison chart of the fluoride ion removal rates of the chip wastewater treatment composite material, alumina sol, and activated carbon-zirconium supported material prepared in Example 3 of this application. The test results are the fluoride ion removal rates of different materials after 150 minutes under the conditions that the initial concentration of fluoride ions is 5 mg / L, the dosage of each material is 2.0 g / L, and the pH is 6.90 ± 0.20. According toFigure 9 It can be seen that the activated carbon-zirconium supported material has good adsorption performance. After being compounded with alumina sol, the adsorption performance of the obtained composite material is further improved.

[0214] Figure 10 This is a comparison chart of the fluoride removal rate of the chip wastewater treatment composite material prepared in Example 3 of this application after multiple regenerations. The test results show the change in the fluoride removal rate of the composite material under the conditions of an initial fluoride ion concentration of 5 mg / L, a dosage of 2.0 g / L, and a pH of 6.90 ± 0.20. According to Figure 10 It can be seen that within 5 regeneration times of the composite material, the adsorption performance of the material does not decrease significantly.

[0215] In summary: A chip wastewater treatment composite material and its preparation method provided by this application achieve the uniform loading of zirconium and aluminum elements on the surface of activated carbon, thereby preparing a chip wastewater treatment composite material with excellent fluoride removal performance. This material has a large specific surface area, an appropriate pore size distribution, and a stable alumina loading amount, enabling it to have excellent adsorption capacity and selectivity, thereby achieving the efficient removal of fluoride ions in chip wastewater. Moreover, the preparation cost of this material is low, and it has more excellent renewable performance.

[0216] For the method embodiments, for simplicity of description, they are all expressed as a series of action combinations. However, those skilled in the art should know that the present invention is not limited by the described action sequence, because according to the present invention, certain steps can be performed in other sequences or simultaneously. Secondly, those skilled in the art should also know that the embodiments described in the specification are all preferred embodiments, and the actions and components involved are not necessarily essential to the present invention.

[0217] The above has introduced in detail a chip wastewater treatment composite material and its preparation method provided by the present invention. Specific examples are used in this article to elaborate on the principle and implementation manner of the present invention. The description of the above embodiments is only used to help understand the method and its core idea of the present invention; at the same time, for those of ordinary skill in the art, according to the idea of the present invention, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation to the present invention.

Claims

1. A preparation method of a composite material for chip wastewater treatment, characterized in that, The preparation method includes: Submerge the activated carbon-zirconium supported material with a mass ratio of 1:(4 - 6) in the alumina sol, and impregnate it for 1 - 1.5 h under magnetic stirring at 450 - 550 r / min; the mass ratio of the activated carbon-zirconium supported material to the alumina sol is 1:5.8; Place the impregnated system at a temperature of 60 - 70 °C and dry it for 0.5 - 2 h, and then calcine the obtained solid at a temperature of 400 - 900 °C for 4 - 6 h to obtain the composite material; the calcination is carried out in a nitrogen atmosphere, and the flow rate of the nitrogen atmosphere is 8 - 10 L / min; The preparation method of the activated carbon-zirconium supported material includes: Mix deionized water and absolute ethanol to obtain a prefabricated solution; After the activated carbon is pretreated, add it to the prefabricated solution, and perform ultrasonic treatment for 1 - 2 h to obtain a suspension. Under magnetic stirring, add zirconium oxychloride to the suspension, and after dissolution, add sodium hydroxide to adjust the pH to 9 - 11 to obtain a mixed solution; The mixed solution is ultrasonically treated for 1 - 2 h, then heated to 175 - 185 °C, and reacted for 0.5 - 2 h. The obtained solid product is cooled and ground to obtain the activated carbon-zirconium supported material; The composite material is used as a fluoride ion adsorbent and applied to chip wastewater treatment for defluorination. Among them, the dosage of the activated carbon-zirconium supported material is 1.00 g / L, 1.25 g / L, 1.50 g / L, 1.75 g / L or 2.0 g / L.

2. The preparation method of the composite material for chip wastewater treatment according to claim 1, wherein The temperature during the calcination is between 500 - 700 °C.

3. The preparation method of the composite material for chip wastewater treatment according to claim 1, characterized in that, The mesh number of the grinding is 30 - 40 meshes.

4. The preparation method of the chip wastewater treatment composite material according to claim 1, characterized in that When the activated carbon is added to the prefabricated solution after pretreatment, the pretreatment method includes: Place the activated carbon in a nitric acid solution with a concentration of 0.5 - 1.5 mol / L, shake it at 100 - 140 rpm for 4 - 8 h, then let it stand for 1 - 3 h, and wash to obtain the pretreated activated carbon.

5. The preparation method of the composite material for treating chip wastewater according to claim 1, wherein, The preparation method of the alumina sol includes: Heat the deionized water to 83 - 85 °C, then add aluminum isopropoxide to it, and perform constant-temperature magnetic stirring for 1.5 - 2.5 h to hydrolyze to obtain a reaction solution. Add nitric acid with a concentration of 0.5 - 1.5 mol / L to the reaction solution to react to obtain the alumina sol.

6. The preparation method of the composite material for chip wastewater treatment according to claim 5, characterized in that The molar ratio of aluminum isopropoxide, deionized water and nitric acid is 1:(120 - 130):(0.2 - 0.24).

7. A composite material obtained by the preparation method of the chip wastewater treatment composite material according to any one of claims 1 to 6, characterized in that, The composite material is used as a fluoride ion adsorbent and applied to chip wastewater treatment for defluorination; When the composite material is saturated, after regeneration treatment, it is recycled. The regeneration treatment method includes: Filter and dry the saturated composite material in sequence, then place it in an aluminum sulfate solution, perform ultrasonic treatment for 2 - 3 h, and then filter and dry it in sequence to recycle the composite material.

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