CN106698598B - Anti-hardening iron-carbon-copper ternary electrolytic filler capable of efficiently removing oxytetracycline and preparation and application thereof - Google Patents
Anti-hardening iron-carbon-copper ternary electrolytic filler capable of efficiently removing oxytetracycline and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to an anti-hardening iron-carbon-copper ternary electrolytic filler for efficiently removing oxytetracycline, and preparation and application thereof, wherein the iron-carbon-copper ternary electrolytic filler comprises the following raw material components in parts by weight: 20-30 parts of reduced iron powder of 90-100 meshes; 1-5 parts of 90-100 mesh metal copper powder; 2-15 parts of 90-100 mesh fly ash; 40-50 parts of 90-100 mesh clay; 3-8 parts of a binder solution. The iron-carbon-copper ternary electrolytic filler forms an iron-carbon-copper three-in-one microcell group, so that the number of microcells in the filler is increased, the potential difference of the microcells is increased, the reaction speed is higher, the reaction ratio is controllable, the terramycin removing effect is better, and because iron atoms and copper atoms are not in direct contact, when the terramycin is removed, partial chemical bonds of the terramycin are broken under the action of richer micro-electrolysis, the reaction speed is accelerated, and the terramycin treating effect is improved.
Description
Technical Field
The invention relates to an anti-hardening iron-carbon-copper ternary electrolytic filler for efficiently removing oxytetracycline, and preparation and application thereof, and belongs to the technical field of sewage treatment.
Background
In livestock and poultry production, tetracycline medicaments are widely used as feed additives for preventing and treating common intestinal infection of livestock and poultry, promoting growth and improving the production quality of livestock products, and are also widely applied to aquaculture and other breeding industries for preventing and treating various bacterial diseases. Terramycin belongs to the group of tetracycline antibiotics, also known as oxytetracycline, having the molecular formula C22H24N2O9The relative molecular mass 460.44 is a derivative of a polycyclic carboxyamide parent nucleus, and is a natural product in the tetracycline family found in the 40 th century. The finished product is odorless light yellow crystalline or amorphous powder; darkening in sunlight, alkalineThe solution is easy to destroy and lose efficacy. It is very slightly soluble in water, slightly soluble in ethanol, and easily soluble in sodium hydroxide solution and dilute hydrochloric acid.
Terramycin is used as a broad-spectrum antibacterial drug, and has inhibitory effects on gram-positive bacteria, gram-negative bacteria, spirochetes, rickettsiae, mycoplasma, chlamydia, protozoa and the like. In the livestock breeding industry, the streptomycin can be used as a growth promoter and a medicament for preventing intestinal bacteria and is used as a feed additive. As a feed additive, the terramycin can stimulate the growth of livestock and poultry, improve the survival rate and the feed utilization rate and reduce the breeding cost, thereby being widely used.
China is a large country for the use of antibiotics and also a large country for production. At the same time, however, large amounts of waste water containing residual antibiotics are produced during the production of antibiotics. Due to the bacteriostatic and bactericidal activity of antibiotics, the waste water has poor biodegradability and certain biotoxicity. Therefore, the wastewater with high antibiotic concentration must be greatly reduced before entering the sewage treatment system.
The treatment of tetracycline waste water generally includes photocatalytic oxidation, coagulation, adsorption, chemical oxidation, fenton oxidation, and the like. The photocatalytic oxidation method is the field of research on wastewater treatment, and whether the method is suitable for large-scale treatment of tetracycline wastewater is questioned, because light can only catalyze and degrade antibiotic molecules on the illuminated surface, and industrial application examples are few. The coagulation method and the adsorption method cannot effectively remove tetracycline pollutants, the chemical oxidation method has a certain removal rate on COD, the degradation efficiency on terramycin is not high, and secondary pollution is generated. Although the Fenton oxidation method can oxidize organic wastewater difficult to biodegrade, the Fenton reagent method has the disadvantages of high reagent cost, complex flow, large waste residue generation amount, secondary pollution, requirement for subsequent treatment and the like. Therefore, the development of an efficient, economic and environment-friendly tetracycline wastewater treatment method has important practical significance for the sustainable development and environmental protection of tetracycline production enterprises.
The micro-electrolysis technology (also known as internal electrolysis) is an electrochemical method, and is an effective method for treating high-concentration refractory organic wastewater. It is composed of a base, a cover and a coverUnder the condition of no power supply, the potential difference generated by a micro-electrolysis material filled in the wastewater is utilized to treat the wastewater so as to achieve the purpose of degrading organic pollutants; when the process is used for treating organic wastewater which is difficult to biodegrade and has high chroma, the COD of the wastewater can be greatly reducedCrAnd the chroma, and the biodegradability of the waste water can be greatly improved. Compared with other water treatment technologies, the micro-electrolysis technology has the characteristics of low operation cost, simple process flow, long service life, strong universality and the like, and has wide application prospect. In the traditional micro-electrolysis process, iron scraps and granular carbon are mechanically stirred together to form iron-carbon filler; in the operation process, iron and carbon are in physical contact, so that an isolation layer is easily formed, the electrolytic effect is gradually ineffective, hardening is easy to occur, and further the cost consumption is increased.
Disclosure of Invention
Aiming at the defects of the existing technology for treating the oxytetracycline waste water, the invention provides the hardening-resistant iron-carbon-copper ternary electrolytic filler for efficiently removing the oxytetracycline, and the iron-carbon-copper ternary electrolytic filler has the advantages of good effect on removing the oxytetracycline, high removal efficiency, less shedding after treatment, small loss, low cost, convenient operation and difficult hardening.
The technical scheme of the invention is as follows:
an anti-hardening iron-carbon-copper ternary electrolytic filler for efficiently removing oxytetracycline, which is used for removing the oxytetracycline and has a bulk density of 880-930 kg/m3The apparent density is 1050 to 1100kg/m3The water absorption rate is 35-40 wt%, and the porosity is 10% -20%; the material is prepared by taking reduced iron powder, metal copper powder, fly ash and clay as raw materials, pelletizing and granulating and then sintering in an oxygen-free manner, wherein the sintering temperature is 550-650 ℃; the iron-carbon-copper ternary electrolytic filler comprises the following raw material components in parts by weight: 20-30 parts of reduced iron powder of 90-100 meshes; 1-5 parts of 90-100 mesh metal copper powder; 2-15 parts of 90-100 mesh fly ash; 40-50 parts of 90-100 mesh clay; 3-8 parts of a binder solution.
Preferred in the invention, SiO in fly ash245-50% of Al2O3Content 25-30%, K2O, CaO, MgO, and Na2The total content of O is 5-10%.
In the invention, the iron powder is preferably industrial grade reduced iron powder, and the preferred particle size is 100 meshes.
In the invention, the particle size of the metal copper powder is preferably 100 meshes, and the particle size of the fly ash is preferably 100 meshes.
Preferably, the binder solution is a mixed solution obtained by mixing, heating and fusing polyvinyl alcohol, sodium carboxymethylcellulose, nickel sulfate hexahydrate and water, wherein the mass concentration of the polyvinyl alcohol in the mixed solution is 1-3 wt%, the mass concentration of the nickel sulfate is 8-12 wt%, and the mass concentration of the sodium carboxymethylcellulose is 1-4 wt%.
Preferably, the iron-carbon-copper ternary electrolytic filler comprises the following raw material components in parts by weight: 25-30 parts of reduced iron powder of 90-100 meshes; 2-3 parts of 90-100 mesh metal copper powder; 2.5-5 parts of 90-100 mesh fly ash; 45-50 parts of 90-100 mesh clay; 5-8 parts of a binder solution.
According to the most preferable technical scheme of the invention, the iron-carbon-copper ternary electrolytic filler comprises the following raw materials in parts by weight: 30 parts of reduced iron powder of 90-100 meshes; 3 parts of 90-100 mesh metal copper powder; 50 parts of 90-100 mesh clay; 5 parts of 90-100 mesh fly ash; 8 parts of adhesive diluent.
The preparation method of the anti-hardening iron-carbon-copper ternary electrolytic filler for efficiently removing the oxytetracycline comprises the following steps:
(1) respectively drying reduced iron powder, metal copper powder, clay and fly ash, then crushing and sieving with a 100-mesh sieve, mixing the iron powder, the metal copper powder, the clay and the fly ash according to the proportion, and uniformly stirring to obtain a mixed material;
(2) spraying the adhesive solution onto the surface of the mixed material in a spraying mode, blending into a thick substance, granulating the thick substance by a granulator to obtain raw material balls with the particle size of 4-6mm, and drying the raw material balls for later use;
(3) firing the raw material ball at 550-650 ℃ for 25-35 minutes under the oxygen-free condition, and cooling to prepare the iron-carbon-copper ternary electrolytic filler.
According to the invention, the drying temperature of the reducing iron powder, the metal copper powder, the clay and the fly ash in the step (1) is 105-110 ℃, and the drying time is 3-5 h.
According to the invention, the drying in the step (3) is to place the raw material balls in a fume hood for air drying for more than 24 hours, wherein the temperature of the fume hood is 22-25 ℃.
The filler prepared by the preparation method has high production efficiency, no brittleness and crack of a finished product, good ventilation, no dead knot during combustion, no blockage and no overheating sintering phenomenon, and has comprehensive advantages in the aspects of cost, raw material sources and the like.
The application of the micro-electrolysis particle filler is used for treating oxytetracycline waste water, wherein the oxytetracycline waste water is treated by an iron-carbon-copper ternary electrolysis filler, the hydraulic retention time is 2-8 h, the temperature is 20-30 ℃, the volume ratio of the filler to the oxytetracycline waste water is 4-5: 1, and the concentration of oxytetracycline in the oxytetracycline waste water is 80-120 mg/L.
The terramycin wastewater with the concentration of 100mg/L is treated by the iron-carbon-copper ternary electrolytic particle filler for eight hours, and the removal rate of the terramycin reaches 88 percent.
The micro-electrolysis reaction column for treating the oxytetracycline waste water is provided with the aeration disc, the bearing plate and the packing layer from bottom to top, the side wall of the reaction column is provided with the sampling ports which are uniformly distributed, the top of the reaction column is provided with the water outlet, the water inlet is directly connected with the waste water, and the air inlet is connected with the aeration pump. The reaction column is made of organic glass, the diameter of the reaction column is 180-200 mm, the height of the reaction column is 1.0-1.5 m, the height between the supporting plate and the aeration disc is 15-20 mm, and the filler layer is filled with anti-hardening iron-carbon-copper ternary electrolytic fillers.
The anti-hardening iron-carbon-copper ternary electrolytic filler for efficiently removing the oxytetracycline has the advantages that the reduced iron powder, the metal copper powder, the clay and the fly ash are mixed and then bonded into a sphere under the action of the adhesive, the adhesive forms a mesh in the material, the reduced iron powder, the metal copper powder, the clay and the fly ash are uniformly filled in the mesh-shaped pores, and the adhesive is carbonized through calcination to form an iron-carbon-copper three-in-one microcell group, so that the number of microcells in the filler is increased, the potential difference of the microcells is increased, the reaction speed is higher, the reaction ratio is controllable, the oxytetracycline removing effect is better, and because the iron atoms and the copper atoms are not in direct contact, when the oxytetracycline is removed, the more abundant microelectrolysis causes partial chemical bonds of the oxytetracycline to be broken, the reaction speed is increased, and the oxytetracycline.
The filler prepared by the invention has strong pressure resistance, long service life and good effect of removing terramycin. The anti-hardening iron-carbon-copper ternary electrolytic filler prepared by the invention is prepared by mixing reduced iron powder, metal copper powder, clay and fly ash, and then spraying an adhesive aqueous solution for granulation, so that the raw materials are fully contacted, the filler with the original powder structure is changed into a spherical structure, the specific surface area of the filler is increased, the adhesive forms a woven net shape in the material, the reduced iron powder, the metal copper powder, the clay and the fly ash are filled in the woven net-shaped pores, the material is combined more firmly, the strength of the filler is increased, and meanwhile, the adhesive forms a woven net in the material, so that the filler has good water absorption; the filler prepared by the invention can be continuously used for more than 3 months, has stable property, is not hardened, and has no change in the internal material structure.
The invention has the following advantages:
(1) the invention is prepared by using reducing iron powder, metal copper powder and fly ash, and has low cost.
(2) The method utilizes the micro-electrolysis technology, can effectively remove the terramycin content in the wastewater, and improves the biodegradability of the wastewater.
(3) Compared with the prior method for treating the oxytetracycline waste water, the application method of the invention is more convenient to use, saves more time and is easier to control.
Drawings
FIG. 1 is a schematic structural diagram of a micro-electrolysis reaction column for treating oxytetracycline wastewater by using anti-hardening iron-carbon-copper ternary electrolysis particle fillers;
in the figure 1, 1 is simulated waste water, 2 is a water inlet pump, 3 is an aeration disc, 4 is a gas inlet pump, 5 is a sampling port, 6 is a water outlet, 7 is a packing layer, and 8 is a bearing plate.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention is further described below with reference to the accompanying drawings and embodiments. The specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
SiO in fly ash in examples245-50% of Al2O3Content 25-30%, K2O, CaO, MgO, and Na2The total content of O is 5-10%; all the components are mass percent, and the fly ash is purchased from a certain power plant in the south of China; the reducing iron powder and the metallic copper powder are purchased from Tianjin Mao chemical reagent factory; clay was purchased from Zibo brick factory, Shandong province.
Example 1
An anti-hardening iron-carbon-copper ternary electrolytic filler for efficiently removing oxytetracycline is used for removing oxytetracycline and is prepared by taking reducing iron powder, metallic copper powder, fly ash and clay as raw materials, pelletizing, granulating and then sintering in an oxygen-free manner; the iron-carbon-copper ternary electrolytic filler comprises the following raw material components in parts by weight: 25 parts of 100-mesh reduced iron powder; 2 parts of 100-mesh metal copper powder; 2.5 parts of 100-mesh fly ash; 45 parts of 100-mesh clay; 5 parts of adhesive solution. The adhesive solution is a mixed solution obtained by mixing, heating and fusing polyvinyl alcohol, sodium carboxymethylcellulose, nickel sulfate hexahydrate and water, wherein the mass concentration of the polyvinyl alcohol in the mixed solution is 2 wt%, the mass concentration of the nickel sulfate is 10 wt%, and the mass concentration of the sodium carboxymethylcellulose is 3 wt%.
The preparation method comprises the following steps:
(1) respectively drying reduced iron powder, metal copper powder, clay and fly ash for 3 hours at the temperature of 110 ℃, and then grinding and sieving by a 100-mesh sieve;
(2) uniformly mixing the reducing iron powder, the metal copper powder, the clay and the fly ash according to the weight ratio, spraying an adhesive solution onto the surface of the mixed material in a spraying mode to prepare a thick substance, granulating the thick substance by a granulator to prepare raw material balls with the particle size of 4-6mm, and carrying out air drying treatment in a fume hood for 24 hours at the temperature of 25 ℃ to obtain the raw material balls;
(3) drying the raw material balls, then placing the dried raw material balls in an anaerobic condition, firing the raw material balls for 25 minutes at 600 ℃, and cooling the raw material balls to obtain the iron-carbon-copper ternary electrolytic filler.
The bulk density of the prepared micro-electrolysis particle filler is 990kg/m3The apparent density is 1080kg/m3The water absorption was 38 wt% and the porosity was 16%.
Example 2
The anti-hardening iron-carbon-copper ternary electrolytic filler for efficiently removing the terramycin is prepared by taking reductive iron powder, metallic copper powder, fly ash and clay as raw materials, pelletizing, granulating and then sintering in an oxygen-free manner, wherein the iron-carbon-copper ternary electrolytic filler comprises the following raw materials in parts by weight: 30 parts of 100-mesh reduced iron powder; 3 parts of 100-mesh metal copper powder; 5 parts of 100-mesh fly ash; 50 parts of 100-mesh clay; 8 parts of a binder solution. The adhesive solution is a mixed solution obtained by mixing, heating and fusing polyvinyl alcohol, sodium carboxymethylcellulose, nickel sulfate hexahydrate and water, wherein the mass concentration of the polyvinyl alcohol in the mixed solution is 3 wt%, the mass concentration of the nickel sulfate is 12 wt%, and the mass concentration of the sodium carboxymethylcellulose is 4 wt%.
The preparation method comprises the following steps:
(1) respectively drying reduced iron powder, metal copper powder, clay and fly ash at the temperature of 110 ℃ for 4 hours, and then grinding and sieving by a 100-mesh sieve;
(2) uniformly mixing reduced iron powder, metal copper powder, clay and fly ash according to the weight ratio, spraying an adhesive solution onto the surface of the mixed material in a spraying mode to prepare a thick substance, granulating the thick substance by a granulator to prepare raw material balls with the particle size of 4-6mm, and carrying out air drying treatment in a fume hood for 24 hours at the temperature of 25 ℃ to obtain the raw material balls;
(3) drying the raw material balls, then placing the dried raw material balls in an anaerobic condition, firing the raw material balls for 25 minutes at 650 ℃, and cooling the raw material balls to obtain the iron-carbon-copper ternary electrolytic filler.
The bulk density of the prepared micro-electrolysis particle filler is 9500kg/m3The apparent density is 1050kg/m3The water absorption was 30 wt%, and the porosity was 15%.
Example 3
The hardening-resistant iron-carbon-copper ternary electrolytic filler for efficiently removing the oxytetracycline is the same as the filler in example 1, except that:
the iron-carbon-copper ternary electrolytic filler comprises the following raw material components in parts by weight: 20 parts of 90-mesh reduced iron powder; 1 part of 90-mesh metal copper powder; 10 parts of 90-mesh fly ash; 40 parts of 90-mesh clay; 3 parts of adhesive solution. The adhesive solution is a mixed solution obtained by mixing, heating and fusing polyvinyl alcohol, sodium carboxymethylcellulose, nickel sulfate hexahydrate and water, wherein in the mixed solution, the mass concentration of the polyvinyl alcohol is 1 wt%, the mass concentration of the nickel sulfate is 8 wt%, and the mass concentration of the sodium carboxymethylcellulose is 2 wt%.
Application Experimental example
Firstly, the anti-hardening iron-carbon-copper ternary electrolytic fillers prepared in the embodiment 1 and the embodiment 2 are respectively filled in the micro-electrolytic reaction column to carry out the application test of the fillers. The structure of the micro-electrolysis reaction column for treating the oxytetracycline waste water is shown in figure 1, an aeration disc 3, a bearing plate 8 and a packing layer 7 are arranged from bottom to top, the side wall of the reaction column is provided with sampling ports 5 which are uniformly distributed, the top of the reaction column is provided with a water outlet 6, the water inlet is directly connected with the waste water, and the air inlet is connected with an aeration pump. The reaction column is made of organic glass, the diameter of the reaction column is 180-200 mm, the height of the reaction column is 1.0-1.5 m, the height between the supporting plate and the aeration disc is 15-20 mm, and the filler layer is filled with anti-hardening iron-carbon-copper ternary electrolytic fillers.
1. The filler of example 1 treats the oxytetracycline waste water with the concentration of 100mg/L, and the oxytetracycline removal rate can reach 80% under the conditions that the inlet water pH is 3, the flow rate ratio A/L is 5 and HRT (hydraulic retention time) is 4 h.
The reactor is continuously operated for 6 months, no obvious hardening phenomenon is found, and the wastewater treatment efficiency is stable. The average grain diameter of the filler after wastewater treatment is 5 mm.
2. The filler of example 2 treats the oxytetracycline waste water with the concentration of 100mg/L, and the oxytetracycline removal rate can reach 88% under the conditions that the inlet water pH is 3, the flow rate ratio A/L is 5 and HRT (hydraulic retention time) is 4 h.
The changes in properties of the microelectrolytic particulate fillers prepared in examples 1 and 2 and after use are shown in table 1:
TABLE 1
Comparative example 1
Chinese patent document CN102583659A discloses a granular anti-hardening acid-base dual-purpose ternary micro-electrolysis filler.
Second, the electrolytic filler described in the above examples 1-2 is: experiments on the aspects of potential difference of the microcell, reaction speed (oxytetracycline removal speed), contact proportion with the microcell, oxytetracycline removal efficiency (%) and the like are carried out and compared with the electrolytic filler of comparative example 1, and other conditions are the same, and the results are shown in the following table 2:
TABLE 2
As can be seen from the comparison of the above table, compared with the filler of comparative example 1, the potential difference of the anti-hardening iron-carbon-copper ternary electrolytic filler microcell of the invention is higher than that of comparative example 1, the oxytetracycline removal speed and the oxytetracycline removal efficiency are far higher than that of comparative example 1, therefore, the iron-carbon-copper ternary electrolytic filler of the invention has better effect on treating oxytetracycline, and is more targeted, the iron-carbon-copper ternary electrolytic filler of the invention forms an iron-carbon-copper three-in-one microcell group, so that the number of microcells in the filler is increased, the potential difference of the microcells is increased, the reaction speed is faster, the reaction ratio is controllable, the oxytetracycline removal effect is better, and because the iron atoms and the copper atoms are not directly contacted, when the oxytetracycline is removed, partial chemical bonds of the oxytetracycline are broken under the action of more abundant micro-electrolysis, so that the reaction speed is increased, and the oxytetracycline treatment effect is improved.
Claims (2)
1. An anti-hardening iron-carbon-copper ternary electrolytic filler for efficiently removing terramycin, which is used for removing terramycin and has a bulk density of 880 ~ 930kg/m3The apparent density was 1050 ~ 1100kg/m3Water absorption of 35 ~ 40wt% and porosity of 10% ~ 20, wherein the iron-carbon-copper ternary electrolytic filler is prepared by taking reduced iron powder, metal copper powder, fly ash and clay as raw materials, pelletizing and granulating the raw materials, and then sintering the raw materials in an oxygen-free manner, wherein the sintering temperature is 550-650 ℃, the raw materials of the iron-carbon-copper ternary electrolytic filler comprise, by weight, 30 parts of reduced iron powder with the mesh of 90-100, 3 parts of metal copper powder with the mesh of 90-100, 50 parts of clay with the mesh of 90-100, 5 parts of fly ash with the mesh of 90-100 and 8 parts of adhesive solution, the adhesive solution is mixed solution obtained by mixing, heating and dissolving polyvinyl alcohol, sodium carboxymethylcellulose, nickel sulfate hexahydrate and water, the mass concentration of the polyvinyl alcohol is 1-3 wt%, the mass concentration of the nickel sulfate is 8-12 wt% and the mass concentration of the sodium carboxymethylcellulose is 1-4 wt% in the fly ash, and245-50% of Al2O3Content 25-30%, K2O, CaO, MgO, and Na2The total content of O is 5-10%; the iron powder is industrial grade reduced iron powder with the particle size of 100 meshes;
the preparation method comprises the following steps:
(1) respectively drying reduced iron powder, metal copper powder, clay and fly ash, then crushing and sieving with a 100-mesh sieve, mixing the iron powder, the metal copper powder, the clay and the fly ash according to the proportion, and uniformly stirring to obtain a mixed material; drying the reducing iron powder, the metal copper powder, the clay and the fly ash at 105-110 ℃ for 3-5 h;
(2) spraying the adhesive solution onto the surface of the mixed material in a spraying mode, blending into a thick substance, granulating the thick substance by using a granulator to prepare raw material balls with the particle size of 4-6mm, and placing the raw material balls in a fume hood for air drying for more than 24 hours at the temperature of 22-25 ℃ for later use;
(3) firing the raw material ball at 550-650 ℃ for 25-35 minutes under the oxygen-free condition, and cooling to prepare the iron-carbon-copper ternary electrolytic filler.
2. The application of the hardening-resistant iron-carbon-copper ternary electrolytic filler for efficiently removing the oxytetracycline of claim 1 to the treatment of oxytetracycline waste water, wherein the oxytetracycline waste water is treated by the iron-carbon-copper ternary electrolytic filler, the hydraulic retention time is 2-8 h, the temperature is 20-30 ℃, the volume ratio of the filler to the oxytetracycline waste water is 4-5: 1, and the oxytetracycline concentration in the oxytetracycline waste water is 80-120 mg/L.
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