CN112429826A - Cyanogen removal material and preparation method thereof - Google Patents
Cyanogen removal material and preparation method thereof Download PDFInfo
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- CN112429826A CN112429826A CN202011194775.9A CN202011194775A CN112429826A CN 112429826 A CN112429826 A CN 112429826A CN 202011194775 A CN202011194775 A CN 202011194775A CN 112429826 A CN112429826 A CN 112429826A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
Abstract
The invention discloses a preparation method of a cyanogen removal material, which takes foamed aluminum as a load matrix, wherein the surface of the foamed aluminum is sequentially coated with a catalyst layer and a cyanogen removal material layer, and the method comprises the following steps: washing and airing the foamed aluminum for later use; placing a titanium source in water-soluble alcohol, performing ultrasonic dispersion for 14-26 min, adding a ferrous salt solution, uniformly stirring, adding copper hydroxide, performing ultrasonic dispersion for 25-55 min, dropwise adding a sodium hydroxide solution to adjust the pH to 10-11 after the ultrasonic dispersion is finished, uniformly stirring, placing in a hydrothermal kettle, and reacting at the temperature of 120-250 ℃ for 8-24 h to obtain a composite catalyst solution; dissolving a composite metal salt in an organic solvent, adding a thickening agent, stirring until the solution is uniform, keeping the system temperature at 30-40 ℃, adding an adhesive, and stirring uniformly to obtain a decyanation solution; soaking foamed aluminum in the composite catalyst solution overnight, taking out and airing; and soaking in a cyanogen removal solution, recovering the temperature of the system to room temperature, standing overnight, taking out, and airing to obtain the cyanogen removal material.
Description
Technical Field
The invention belongs to the technical field of cyanogen removal materials, and particularly relates to a cyanogen removal material and a preparation method thereof.
Background
The cyanide CN, which is known as CN, is very stable in the form of a covalent bond (C.ident.N) containing a triple bond between a carbon atom and a nitrogen atom, and exists as a whole in the usual chemical reactions. Since CN groups have similar chemical properties to halogens, they are often referred to as pseudohalogens. Cyanide compounds are generally known as inorganic cyanide compounds and are highly toxic. In addition, organic cyanide forms such as propionitrile, acetonitrile, n-butyronitrile and the like can quickly separate out ions in vivo and are also high-toxicity. Many cyanides, which release hydrogen cyanide or cyanide ions after heating or acid exposure or in the air from tissues, have the same highly toxic effect as hydrogen cyanide.
Cyanide exists mainly in industrial production wastewater such as coking wastewater, aluminum electrolysis production wastewater and the like, and because the cyanide has high toxicity, the wastewater containing the cyanide can seriously affect the environment if not treated. Currently, the method for removing cyanogen from cyanide-containing wastewater is mainly determined according to the source, property and water quantity of wastewater, and can be classified into physical method, chemical method, physical-chemical method, biochemical method, advanced oxidation method, and the like.
The physical cyanide removal mainly comprises membrane separation, acid steaming house and the like, and is generally suitable for recycling industrial cyanide. The membrane separation mainly utilizes an electrode membrane method and a reverse osmosis method to separate the high-concentration cyanogen-containing solution to obtain low-concentration cyanogen-containing wastewater and high-concentration cyanogen-containing wastewater, and the latter is used for process recycling. Since the saturated vapor pressure of hydrogen cyanide gas in water is the saturated vapor pressure, gas is formed as the temperature increases or decreases. The evaporation circulation process utilizes the volatility of hydrogen cyanide and absorbs hydrogen cyanide with alkali liquor under the heating condition. The method has the advantages of convenience and quick recovery process; the disadvantage is a poor effect on cyanide.
Chemical method mainly uses chemical oxidation to remove toxic cyanideAnd the waste water is processed into non-toxic carbon dioxide, nitrogen and the like. At present, the most popular method for breaking cyanogen is to add chemical oxidant, i.e. chemical method, such as ozone method, hydrogen peroxide method, alkaline chlorine oxidation method, chlorine method, sulfur dioxide air method, etc. The ozone method is a method that ozone can oxidize cyanide into nontoxic nitrogen under alkaline conditions, but the ozone method has limited industrial application, has a prospect which is not as good as that of the alkaline chlorine oxidation method, and has poor effect on SAD method. The hydrogen peroxide process is H2O2Under the conditions of normal temperature, alkalinity and catalyst, cyanide can be oxidized to generate CNO-、NH4 +Etc., the treatment process is simple but due to H2O2The price is expensive, so that the treatment cost is high, and certain danger is also caused in the aspects of transportation and use. The alkaline chlorine oxidation method is a method for decomposing chlorine cyanide into low-toxicity or non-toxicity by using chlorine cyanide, is a mature method for treating cyanide in wastewater, but residual chlorine exists after treatment, CNCl is easily generated in the treatment process to pollute the operation environment, equipment is seriously corroded, the operation cost is higher, and the SAD cyanide effect is poorer. The sulfur dioxide air method is to oxidize cyanide in waste water to generate carbonate and ammonium radical with sulfur dioxide and air as oxidant and copper ion as catalyst. The method has the advantages of quick reaction, wide medicament source and low treatment cost, but SCN is difficult to oxidize-And SCN-CN can be dissociated later-Therefore, it is not suitable for treating SCN-containing-High cyanide-containing waste water.
The physical and chemical method mainly takes activated carbon, resin and extractant to absorb cyanide, but the amount of cyanide recovered by the activated carbon or the resin is smaller, so the method is suitable for advanced treatment. The biochemical method is to treat cyanide-containing waste water by using microorganisms. The method can save a certain cost, and particularly has a better treatment effect on low-concentration simple cyanide. The advanced oxidation method is characterized in that hydroxyl free radicals with strong oxidizing capability are generated, and under the reaction conditions of high temperature and high pressure, electricity, sound, light irradiation, catalysts and the like, organic matters with high molecular weight and difficult degradation are oxidized into low-toxicity or non-toxic micromolecular substances. However, this method is very expensive to handle and requires a very small amount of water to be treated.
The foamed aluminum is a novel structure and functional material which integrates multiple advantages of light weight, high strength, sound absorption, sound insulation, energy absorption, heat insulation, shock absorption, damping, electromagnetic shielding and the like, and can be widely applied to the fields of machinery, electronics, buildings, environmental protection, metallurgy, transportation, aerospace, national defense and military industry and the like. At present, foamed aluminum is mainly used for sound insulation, and is not seen in a water treatment process.
Although various methods are currently used for cyanide removal from wastewater, each method has its own disadvantages. The inventor of the application can effectively improve the removal effect of cyanide by coating a chemical substance capable of combining cyanide on the basis of the property of foamed aluminum and taking the foamed aluminum as a carrier matrix.
Disclosure of Invention
The invention mainly aims to solve the problem that the existing cyanogen removing material is poor in effect, and provides a cyanogen removing material and a preparation method thereof. The cyanogen removing material has good cyanogen removing effect and can be recycled for multiple times.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme.
The invention provides a preparation method of a cyanogen removal material, which is characterized in that the cyanogen removal material takes foamed aluminum as a load matrix, the surface of the foamed aluminum is coated with a catalyst layer and a cyanogen removal material layer in sequence, and the method comprises the following steps:
washing and airing commercially available foamed aluminum for later use;
placing a titanium source in water-soluble alcohol for ultrasonic dispersion for 14-26 min, then adding a ferrous salt solution, uniformly stirring, then adding copper hydroxide for ultrasonic dispersion for 25-55 min, dropwise adding a sodium hydroxide solution after the ultrasonic dispersion is finished, adjusting the pH to 10-11, uniformly stirring, then placing in a hydrothermal kettle for reaction, wherein the temperature of solvothermal reaction is 120-250 ℃, and the reaction time is 8-24 h, so as to obtain the magnetic nano Cu-Fe3O4/TiO2Compounding a catalyst solution;
dissolving a composite metal salt in an organic solvent, adding a thickening agent, stirring until the solution is uniform, keeping the system temperature at 30-40 ℃, adding an adhesive into the cyanogen-removing solution, and stirring uniformly to obtain a cyanogen-removing solution;
soaking the foamed aluminum in magnetic nano Cu-Fe3O4/TiO2Taking out and airing the composite catalyst solution after the composite catalyst solution is over night; and soaking in the cyanogen removal solution, recovering the temperature of the system to room temperature, standing overnight, taking out, and airing to obtain the cyanogen removal material.
The preparation method is characterized in that the titanium source is one or a mixture of any more of butyl titanate, ethyl titanate, propyl titanate, titanium tetrachloride and titanyl sulfate.
The above production method is characterized in that the ferrous salt is a chloride, nitrate or sulfate of iron.
The preparation method is characterized in that the titanium source, the ferrous salt and the copper hydroxide are added according to the mass ratio of 1:1 (0.5-1).
The preparation method is characterized in that the composite metal salt is selected from one or more of lithium tetracyanophosphate, sodium tetracyanoborate, potassium perchlorate, lithium hexacyanoarsenate (V), magnesium dioxalate borate, sodium dicyanodilate and lithium tricyanomethanesulfonate.
The preparation method is characterized in that the organic solvent is one or more selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, methyl acetate, N-methyl pyrrolidone, tetrahydrofuran and dimethyl ether.
The above-mentioned production method is characterized in that the thickener is any one selected from the group consisting of gelatin, carboxymethyl cellulose, xanthan gum and agar.
The above-described production method is characterized in that the binder is any one selected from polyvinyl alcohol, polyethylene glycol, and triethanolamine.
The preparation method is characterized in that the composite metal salt, the thickener and the adhesive are mixed according to a mass ratio of 1: (0.1-0.5): (0.1-0.5) in an amount.
By the technical scheme, the invention at least has the following advantages: the invention uses foamThe aluminum is used as a loading matrix, and the catalyst layer and the cyanide removal material layer are loaded on the surface of the foamed aluminum, so that the contact area of the foamed aluminum and cyanide-containing wastewater can be increased due to the porous nature of the foamed aluminum, and the removal rate of cyanide in the wastewater is improved. The invention relates to a method for preparing magnetic nano Cu-Fe3O4/TiO2The composite catalyst is coated on the surface of the foamed aluminum and has synergistic effect with the cyanogen removing material, so that the cyanogen removing efficiency is effectively improved. The cyanide removing material takes the composite metal salt as a main active substance, and active ions are loaded on the surface of the foamed aluminum under the action of the thickening agent and the adhesive, so that on one hand, the loading strength can be increased, the surface substance of the foamed aluminum can be kept in a stable state in the actual water treatment process, and on the other hand, the cyanide-containing substance can be firmly combined on the foamed aluminum, and secondary pollution is avoided. In addition, compared with other materials, the foamed aluminum used in the invention has the advantages of light weight, good stability, more and uniform distributed gaps and large surface area, so that the foamed aluminum is convenient to carry and is obviously superior to other existing materials in removal effect.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
And (3) washing commercially available foamed aluminum with the size of 5 multiplied by 3cm for 2-3 times by using an ethanol solution, and then naturally airing under a ventilation condition for later use. Putting 100 parts of butyl titanate in ethanol solution for ultrasonic treatmentDispersing for 20min, then adding 100 parts of ferrous sulfate solution, uniformly stirring, then adding 50 parts of copper hydroxide, performing ultrasonic dispersion for 40min, dropwise adding sodium hydroxide solution after the ultrasonic dispersion is finished, adjusting the pH to 10-11, uniformly stirring, then placing in a hydrothermal kettle for reaction, wherein the temperature of solvothermal reaction is 185 ℃, and the reaction time is 16h, thus obtaining the magnetic nano Cu-Fe3O4/TiO2Compounding the catalyst solution. Dissolving 100 parts of lithium tetracyanophosphate in tetrahydrofuran, adding 20 parts of gelatin, stirring until the solution is uniform, keeping the system temperature at 35 ℃, adding 30 parts of polyvinyl alcohol into the decyanation solution, and stirring uniformly to obtain the decyanation solution. Soaking the foamed aluminum in the obtained magnetic nano Cu-Fe3O4/TiO2The composite catalyst solution is taken out and dried overnight. And soaking in the cyanogen removal solution, recovering the temperature of the system to room temperature, standing overnight, taking out, and airing to obtain the cyanogen removal material.
The cyanogen removal material obtained by the method takes foamed aluminum as a load matrix, and the surface of the foamed aluminum is coated with a catalyst layer and a cyanogen removal material layer in sequence.
Example 2
And (3) washing commercially available foamed aluminum with the size of 5 multiplied by 3cm for 2-3 times by using an ethanol solution, and then naturally airing under a ventilation condition for later use. Placing 100 parts of ethyl titanate in an ethanol solution for ultrasonic dispersion for 26min, then adding 100 parts of a ferrous nitrate solution, uniformly stirring, then adding 80 parts of copper hydroxide for ultrasonic dispersion for 25min, dropwise adding a sodium hydroxide solution after the ultrasonic dispersion is finished, adjusting the pH to 10-11, uniformly stirring, then placing in a hydrothermal kettle for reaction, wherein the temperature of the solvothermal reaction is 120 ℃, and the reaction time is 24h, so as to obtain the magnetic nano Cu-Fe3O4/TiO2Compounding the catalyst solution. Dissolving 100 parts of sodium tetracyanoborate in N-methylpyrrolidone, adding 30 parts of gelatin, stirring until the solution is uniform, keeping the system temperature at 40 ℃, adding 20 parts of triethanolamine into the cyanogen removing solution, and stirring uniformly to obtain the cyanogen removing solution. Soaking the foamed aluminum in the obtained magnetic nano Cu-Fe3O4/TiO2The composite catalyst solution is taken out and dried overnight. Then soaking in the above cyanogen removing solutionAnd (4) recovering the temperature of the system to room temperature in the solution, standing overnight, taking out and airing to obtain the cyanogen removal material.
The cyanogen removal material obtained by the method takes foamed aluminum as a load matrix, and the surface of the foamed aluminum is coated with a catalyst layer and a cyanogen removal material layer in sequence.
Example 3
And (3) washing commercially available foamed aluminum with the size of 5 multiplied by 3cm for 2-3 times by using a methanol solution, and then naturally airing under a ventilation condition for later use. Placing 100 parts of propyl titanate in an ethanol solution for ultrasonic dispersion for 23min, then adding 100 parts of ferrous chloride solution, uniformly stirring, then adding 100 parts of copper hydroxide for ultrasonic dispersion for 45min, dropwise adding a sodium hydroxide solution to adjust the pH value to 10-11 after the ultrasonic dispersion is finished, placing the mixture in a hydrothermal kettle for reaction after the uniform stirring, wherein the temperature of the solvothermal reaction is 200 ℃, and the reaction time is 12h, so as to obtain the magnetic nano Cu-Fe3O4/TiO2Compounding the catalyst solution. Dissolving 100 parts of potassium perchlorate in methyl acetate, adding 30 parts of carboxymethyl cellulose, stirring until the solution is uniform, keeping the system temperature at 30 ℃, adding 10 parts of triethanolamine into the cyanogen-removing solution, and stirring uniformly to obtain the cyanogen-removing solution. Soaking the foamed aluminum in the obtained magnetic nano Cu-Fe3O4/TiO2The composite catalyst solution is taken out and dried overnight. And soaking in the cyanogen removal solution, recovering the temperature of the system to room temperature, standing overnight, taking out, and airing to obtain the cyanogen removal material.
The cyanogen removal material obtained by the method takes foamed aluminum as a load matrix, and the surface of the foamed aluminum is coated with a catalyst layer and a cyanogen removal material layer in sequence.
Example 4
And (3) washing commercially available foamed aluminum with the size of 5 multiplied by 3cm for 2-3 times by using deionized water, and then naturally airing under a ventilation condition for later use. Placing 100 parts of titanium tetrachloride in an ethanol solution for ultrasonic dispersion for 14min, then adding 100 parts of ferrous sulfate solution, uniformly stirring, then adding 50 parts of copper hydroxide for ultrasonic dispersion for 30min, dropwise adding a sodium hydroxide solution after the ultrasonic dispersion is finished, adjusting the pH value to 10-11, uniformly stirring, and then placingReacting in a hydrothermal kettle at 150 ℃ for 20h to obtain magnetic nano Cu-Fe3O4/TiO2Compounding the catalyst solution. Dissolving 100 parts of lithium hexacyanoarsenate (V) in methyl propyl carbonate, adding 50 parts of xanthan gum, stirring until the solution is uniform, keeping the system temperature at 30 ℃, adding 20 parts of polyethylene glycol into the cyanogen-removing solution, and stirring uniformly to obtain the cyanogen-removing solution. Soaking the foamed aluminum in the obtained magnetic nano Cu-Fe3O4/TiO2The composite catalyst solution is taken out and dried overnight. And soaking in the cyanogen removal solution, recovering the temperature of the system to room temperature, standing overnight, taking out, and airing to obtain the cyanogen removal material.
The cyanogen removal material obtained by the method takes foamed aluminum as a load matrix, and the surface of the foamed aluminum is coated with a catalyst layer and a cyanogen removal material layer in sequence.
Example 5
And (3) washing commercially available foamed aluminum with the size of 5 multiplied by 3cm for 2-3 times by using an ethanol solution, and then naturally airing under a ventilation condition for later use. Placing 100 parts of titanyl sulfate in an ethanol solution for ultrasonic dispersion for 21min, then adding 100 parts of ferrous nitrate solution, uniformly stirring, then adding 80 parts of copper hydroxide for ultrasonic dispersion for 35min, dropwise adding a sodium hydroxide solution to adjust the pH value to 10-11 after the ultrasonic dispersion is finished, uniformly stirring, placing in a hydrothermal kettle for reaction, controlling the temperature of solvothermal reaction to be 120 ℃ and the reaction time to be 18h, and obtaining the magnetic nano Cu-Fe3O4/TiO2Compounding the catalyst solution. Dissolving 100 parts of magnesium dioxalate borate in dimethyl carbonate, adding 10 parts of agar, stirring until the solution is uniform, keeping the system temperature at 35 ℃, adding 50 parts of triethanolamine into the cyanogen-removing solution, and stirring uniformly to obtain the cyanogen-removing solution. Soaking the foamed aluminum in the obtained magnetic nano Cu-Fe3O4/TiO2The composite catalyst solution is taken out and dried overnight. And soaking in the cyanogen removal solution, recovering the temperature of the system to room temperature, standing overnight, taking out, and airing to obtain the cyanogen removal material.
The cyanogen removal material obtained by the method takes foamed aluminum as a load matrix, and the surface of the foamed aluminum is coated with a catalyst layer and a cyanogen removal material layer in sequence.
Example 6
And (3) washing commercially available foamed aluminum with the size of 5 multiplied by 3cm for 2-3 times by using deionized water, and then naturally airing under a ventilation condition for later use. Placing 100 parts of butyl titanate in an ethanol solution for ultrasonic dispersion for 14min, then adding 100 parts of ferrous chloride solution, uniformly stirring, then adding 80 parts of copper hydroxide for ultrasonic dispersion for 25min, dropwise adding a sodium hydroxide solution after the ultrasonic dispersion is finished to adjust the pH value to 10-11, uniformly stirring, then placing in a hydrothermal kettle for reaction, wherein the temperature of the solvothermal reaction is 250 ℃, and the reaction time is 24h, so as to obtain the magnetic nano Cu-Fe3O4/TiO2Compounding the catalyst solution. Dissolving 100 parts of sodium dicyanodioxalato in ethylene carbonate, adding 20 parts of xanthan gum, stirring until the solution is uniform, keeping the system temperature at 40 ℃, adding 30 parts of polyethylene glycol into the cyanogen removing solution, and stirring uniformly to obtain the cyanogen removing solution. Soaking the foamed aluminum in the obtained magnetic nano Cu-Fe3O4/TiO2The composite catalyst solution is taken out and dried overnight. And soaking in the cyanogen removal solution, recovering the temperature of the system to room temperature, standing overnight, taking out, and airing to obtain the cyanogen removal material.
The cyanogen removal material obtained by the method takes foamed aluminum as a load matrix, and the surface of the foamed aluminum is coated with a catalyst layer and a cyanogen removal material layer in sequence.
Comparative example 1
And (3) washing commercially available foamed aluminum with the size of 5 multiplied by 3cm for 2-3 times by using an ethanol solution, and then naturally airing under a ventilation condition for later use. Placing 100 parts of butyl titanate in an ethanol solution for ultrasonic dispersion for 20min, then adding 100 parts of ferrous sulfate solution, uniformly stirring, then adding 50 parts of copper hydroxide for ultrasonic dispersion for 40min, dropwise adding a sodium hydroxide solution after the ultrasonic dispersion is finished to adjust the pH value to 10-11, uniformly stirring, then placing in a hydrothermal kettle for reaction, wherein the temperature of the solvothermal reaction is 185 ℃, and the reaction time is 16h, so as to obtain the magnetic nano Cu-Fe3O4/TiO2Compounding the catalyst solution.Soaking the foamed aluminum in the obtained magnetic nano Cu-Fe3O4/TiO2Taking out and airing the composite catalyst solution after the night to obtain the cyanogen removing material.
The cyanogen removing material obtained by the method takes foamed aluminum as a load matrix, and the surface of the foamed aluminum is coated with a catalyst layer.
Comparative example 2
And (3) washing commercially available foamed aluminum with the size of 5 multiplied by 3cm for 2-3 times by using an ethanol solution, and then naturally airing under a ventilation condition for later use. Dissolving 100 parts of lithium tetracyanophosphate in tetrahydrofuran, adding 20 parts of gelatin, stirring until the solution is uniform, keeping the system temperature at 35 ℃, adding 30 parts of polyvinyl alcohol into the decyanation solution, and stirring uniformly to obtain the decyanation solution. And soaking the foamed aluminum in the cyanogen removal solution, recovering the system temperature to room temperature, standing overnight, taking out, and airing to obtain the cyanogen removal material.
The cyanogen removal material obtained by the method takes foamed aluminum as a load matrix, and the surface of the foamed aluminum is coated with a cyanogen removal material layer.
Test example 1 test of cyanogen removing Effect of cyanogen removing Material
Treating wastewater of a certain metal concentrating mill, wherein the concentration of cyanide ions is 2054mg/L before treatment, adding a plurality of cyanogen removing materials into the wastewater, stirring for 15min, standing, taking out the cyanogen removing materials, and measuring the cyanogen removing rate for one time; then, the used cyanogen removal material is used for treating wastewater with the radical ion concentration of 1892mg/L again for 15min, and then the secondary cyanogen removal rate is calculated; the second time used cyanogen removal material was used again for treating wastewater with a radical ion concentration of 2001mg/L for 15min, and the third time cyanogen removal rate was calculated, and the results are shown in Table 1.
TABLE 1 comparison of the cyanogen removal rates
| Numbering | First order cyanogen removal (%) | Secondary cyanogen removal rate (%) | Third order cyanogen removal (%) |
| Example 1 | 99.99 | 99.99 | 99.98 |
| Example 2 | 99.98 | 99.98 | 99.98 |
| Example 3 | 99.89 | 99.88 | 99.79 |
| Example 4 | 99.97 | 99.98 | 99.98 |
| Example 5 | 99.99 | 99.98 | 99.98 |
| Example 6 | 99.98 | 99.98 | 99.97 |
| Comparative example 1 | 14.52 | 5.11 | 3.43 |
| Comparative example 2 | 31.25 | 15.84 | 3.51 |
As can be seen from the results of Table 1, the cyanogen removing effect of the cyanogen removing material of the present invention is significantly superior to that of comparative examples 1 and 2. Therefore, the composite catalyst and the cyanogen removal material have a synergistic effect by using the foamed aluminum as a loading matrix, the cyanogen removal rate of the wastewater is effectively improved, and the cyanogen removal effect is still good after the cyanogen removal material is used for multiple times. Therefore, the cyanogen removing material can be used for multiple times, saves the cost and has environmental protection significance.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. The preparation method of the cyanogen removal material is characterized in that the cyanogen removal material takes foamed aluminum as a load matrix, and a catalyst layer and a cyanogen removal material layer are sequentially coated on the surface of the foamed aluminum, and the method comprises the following steps:
washing and airing commercially available foamed aluminum for later use;
placing a titanium source in water-soluble alcohol for ultrasonic dispersion for 14-26 min, then adding a ferrous salt solution, uniformly stirring, then adding copper hydroxide for ultrasonic dispersion for 25-55 min, dropwise adding a sodium hydroxide solution after the ultrasonic dispersion is finished, adjusting the pH to 10-11, uniformly stirring, then placing in a hydrothermal kettle for reaction, wherein the temperature of solvothermal reaction is 120-250 ℃, and the reaction time is 8-24 h, so as to obtain the magnetic nano Cu-Fe3O4/TiO2Compounding a catalyst solution;
dissolving a composite metal salt in an organic solvent, adding a thickening agent, stirring until the solution is uniform, keeping the system temperature at 30-40 ℃, adding an adhesive into the cyanogen-removing solution, and stirring uniformly to obtain a cyanogen-removing solution;
soaking the foamed aluminum in magnetic nano Cu-Fe3O4/TiO2Taking out and airing the composite catalyst solution after the composite catalyst solution is over night; and soaking in the cyanogen removal solution, recovering the temperature of the system to room temperature, standing overnight, taking out, and airing to obtain the cyanogen removal material.
2. The preparation method according to claim 1, wherein the titanium source is one or a mixture of any of butyl titanate, ethyl titanate, propyl titanate, titanium tetrachloride and titanyl sulfate.
3. The method of claim 1, wherein the ferrous salt is a chloride, nitrate or sulfate of iron.
4. The preparation method according to claim 1, wherein the titanium source, the ferrous salt and the copper hydroxide are added in a mass ratio of 1:1 (0.5-1).
5. The method according to claim 1, wherein the complex metal salt is selected from one or more of lithium tetracyanophosphate, sodium tetracyanoborate, potassium perchlorate, lithium hexacyanoarsenate (V), magnesium dioxalate borate, sodium dicyanodilate, lithium tricyanomethanesulfonate.
6. The method according to claim 1, wherein the organic solvent is one or more selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, methyl acetate, N-methylpyrrolidone, tetrahydrofuran, and dimethyl ether.
7. The method according to claim 1, wherein the thickener is any one selected from gelatin, carboxymethyl cellulose, xanthan gum, and agar.
8. The method according to claim 1, wherein the binder is selected from any one of polyvinyl alcohol, polyethylene glycol, and triethanolamine.
9. The production method according to claim 1, wherein the composite metal salt, the thickener, and the binder are mixed in a mass ratio of 1: (0.1-0.5): (0.1-0.5) in an amount.
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| CN102921422A (en) * | 2012-11-06 | 2013-02-13 | 常州大学 | Preparation of magnetic nano Cu-Fe3O4/grapheme composite catalyst and application of composite catalyst in reduction of nitro-compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921422A (en) * | 2012-11-06 | 2013-02-13 | 常州大学 | Preparation of magnetic nano Cu-Fe3O4/grapheme composite catalyst and application of composite catalyst in reduction of nitro-compounds |
Non-Patent Citations (2)
| Title |
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| 乌云等: "《煤炭气化工艺与操作》", 31 May 2013, 北京理工大学出版社 * |
| 海关总署关税征管司编著: "《危险化学品归类指南 下》", 31 August 2017, 中国海关出版社 * |
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