CN107047614B - Composite potassium ferrate slow-release disinfectant and preparation method and use method thereof - Google Patents
Composite potassium ferrate slow-release disinfectant and preparation method and use method thereof Download PDFInfo
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Abstract
The invention discloses a composite potassium ferrate slow-release disinfectant, a preparation method and a use method thereof, and belongs to the field of tail water deep treatment.
Description
Technical Field
The invention belongs to the field of advanced treatment of tail water, and particularly relates to a composite potassium ferrate slow-release disinfectant, and a preparation method and a use method thereof.
Background
With the enlargement of industrial scale and industrial type in China, a large amount of industrial wastewater is generated in the production process. Especially in the industries of petroleum, chemical industry, electrolysis, printing and dyeing, textile and the like, the discharge amount of the waste water is large, and the physical and chemical properties of the waste water are complex. Many industrial waste water has high COD and high chroma simultaneously, contains various heavy metals, and the BOD/COD value is very low, which causes poor biodegradability of the waste water, so that the tail water after the conventional treatment method still has certain COD content, the chroma does not reach the standard, and a large amount of pathogenic microorganisms such as bacteria, viruses, amoeba cysts and the like exist, for example, a common biological filter can only remove 80-90 percent of escherichia coli, therefore, the tail water can be discharged after reaching the standard only by urgently needing to be disinfected and decolored.
Potassium ferrate is a novel, efficient and nontoxic multifunctional water treatment agent, has shown its specific advantages in the aspect of water treatment, and is widely applied to the field of water treatment by virtue of its super-strong oxidizing ability and excellent characteristics such as flocculation, decoloration, deodorization, sterilization and the like, which are incomparable with other water treatment agents. The potassium ferrate can not only remove organic and inorganic pollutants in water through oxidation in a broad spectrum manner, and particularly has more remarkable treatment effect on some organic pollutants which are difficult to degrade, but also has remarkable decoloring and sterilizing capabilities.
However, the application of potassium ferrate in water treatment at present has many problems. Due to the oxidizing property of potassium ferrateStrong strength, easy decomposition when being affected with damp and heated, poor stability and larger storage difficulty. In addition, potassium ferrate is also extremely easy to decompose in water, so that the effective time of the potassium ferrate is short, medicaments need to be continuously added, the cost is high, and if Fe exists in the solution3+，Fe3+Has strong catalytic reduction effect on ferrate, and the existence of the ferrate can obviously reduce the stability of the product, and the strength of the effect is stronger than that of Fe3+The concentration of (c) is in a direct proportional relationship. Decomposing ferrate to generate Fe3+This in turn accelerates the decomposition of ferrate. Ferrate decomposes when meeting water and rapidly decomposes to release oxygen under acidic or neutral conditions. Therefore, the stability of the potassium ferrate in preservation is improved, and the control of the decomposition rate of the potassium ferrate in water is the key to the application of the potassium ferrate to the advanced treatment of tail water. The current main method is to coat a layer of inert substance on the surface of potassium ferrate to prevent external moisture and reducing components from contacting the potassium ferrate, so that the potassium ferrate can be stably stored for a long time and can be slowly released in water. For example, as a Chinese patent "a preparation method of a slow-release potassium ferrate clathrate for water treatment" (publication No. 104211157A, publication date: 2014 12, 17), potassium ferrate is coated with ethyl cellulose, so that the stability of potassium ferrate is improved, but a large amount of organic solvents are used in the preparation process, so that the problem of environmental protection exists, and the utilization value is reduced. For another example, in a chinese patent, "polyethylene wax-coated stable potassium ferrate and a preparation method thereof" (publication No. 105061784a, published as 2015, 11/18/10), when polyethylene wax is used to prepare coated stable potassium ferrate, the coating rate and stability of potassium ferrate are greatly improved, the water absorption rate of 10 days is only 2% when the mass of polyethylene wax/potassium ferrate is 5/1, and the coating rate reaches 90%, but the dissolution rate of potassium ferrate is reduced, and the time for releasing 50% of potassium ferrate is 17.7 h. And the cost of the polyethylene wax is higher and is not economical.
The bentonite is a layered aluminosilicate with montmorillonite as main component, and its interlaminar cations are easy to exchange, and has great ion exchange capacity, high adsorption capacity and good decolorizing effect. The predicted resource amount of the Chinese bentonite is more than 80 hundred million tons, which is at the first position in the world, accounts for 60 percent of the total amount in the world, has low price and wide source, and is widely applied to various water treatment technologies. However, the silica structure on the surface of natural bentonite has extremely strong hydrophilicity and hydrolysis of a large number of exchangeable cations between layers, so that unmodified raw soil cannot effectively adsorb hydrophobic organic pollutants. In order to improve the capability of the bentonite for treating sewage and wastewater, the bentonite is often required to be modified when being applied to water treatment. Common modification methods include high-temperature roasting modification, acidification modification, organic modification and the like.
Chinese patent 'a method for treating wastewater by using organically modified bentonite' (publication No. 102367182A, publication date 3, month 3 and day 7 of 2012), through curing and molding the organically modified bentonite, the wastewater is effectively diffused on the bentonite, and the purpose of reaching the standard of pollutants after treatment is realized. However, the bentonite is difficult to achieve the purpose of disinfection by being singly used, has weak treatment capacity on some macromolecular organic matters or aromatic hydrocarbon organic matters which are difficult to degrade, and needs to be combined with other water treatment agents to achieve the effect.
Cyclodextrin (CD) is a generic name for a series of cyclic oligosaccharides produced by amylose under the action of Cyclodextrin glucosyltransferase produced by Bacillus β -Cyclodextrin is a chemical substance with the molecular formula of C42H70O35β -cyclodextrin polymer reserves the cavity structure of cyclodextrin, has a three-dimensional space network structure inside, is loose into a honeycomb shape, has higher water absorption, is nontoxic, has high bioavailability, is commonly used for synthesizing environment-friendly materials, adsorbs pollutants in air and water, and is coated by β -cyclodextrin, so that the stability is greatly improved, and the sustained-release effect is certain.
Chinese patent' adsorption based on cyclodextrin polymer material-KMnO4Method for treating micro-pollutants in water through oxidative coupling (publication No. 102659206A, publication date 9/12/2012) by coupling cyclodextrin polymer material adsorption enrichment and KMnO4Oxidation reductionThe cyclodextrin polymer material and the KMnO are added in sequence simply4So that KMnO is made4The consumption of the method is large, and the economy is not high.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems of poor stability, poor oxidation continuity, large medicament using amount, narrow application range, high cost and the like of the existing potassium ferrate water treatment medicament, the invention aims to provide a composite potassium ferrate slow-release disinfectant, which fully mixes and finishes coating potassium ferrate, modified bentonite and β -cyclodextrin polymer so that the potassium ferrate continuously plays a role in tail water advanced treatment.
The invention aims at solving the problems of weak oxidation performance, easy interference on adsorption performance, easy moisture absorption, difficult regeneration and the like of bentonite in the preparation of an adsorbent, and the other purpose of the invention is to provide a preparation method of the composite potassium ferrate slow-release disinfectant.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the composite potassium ferrate slow-release disinfectant comprises, by mass, 20 parts of sodium hydroxide, 10-15 parts of potassium hydroxide, 10-15 parts of calcium hypochlorite, 15-18 parts of ferric nitrate, 2-4 parts of n-hexane, 1-2 parts of isopropanol, 1-2 parts of diethyl ether, 100-120 parts of calcium bentonite, 100-200 parts of β -cyclodextrin and 10-20 parts of epoxy chloropropane.
Furthermore, when in use, the slow-release disinfectant is combined with 200-400 parts of powdered activated carbon and 20-40 parts of carboxymethyl cellulose to prepare an activated carbon column with the granularity of 5 mm.
Furthermore, the preservation conditions of the slow-release disinfectant are as follows: storing in dark under the dry condition below 35 ℃.
The preparation method of the composite potassium ferrate slow-release disinfectant comprises the following steps:
(1) weighing the components according to the proportion, and roasting and modifying the calcium bentonite for later use;
(2) synthesizing β -cyclodextrin polymer, namely dissolving β -cyclodextrin in sodium hydroxide aqueous solution, slightly heating to dissolve β -cyclodextrin, heating to 50-70 ℃, dripping epoxy chloropropane under the condition of full stirring, continuously keeping the temperature and stirring for reaction, gradually increasing the viscosity of the mixture until the reaction is stopped when gel solid appears, cleaning a reaction product, drying to obtain white solid, namely β -cyclodextrin polymer, and grinding and sieving for later use;
(3) preparing a saturated potassium hydroxide solution by using 6-8 parts of potassium hydroxide, adding calcium hypochlorite powder, uniformly stirring, standing, slowly adding ferric nitrate solid, stirring, precipitating a large amount of purple black precipitate, and performing suction filtration to obtain a crude product of potassium ferrate;
(4) dissolving the potassium ferrate crude product obtained in the step (3) by using 1-2 parts of potassium hydroxide solution, stirring, and adding the modified bentonite obtained in the step (1) and the β -cyclodextrin polymer obtained in the step (2) into the solution;
(5) adding 3-5 parts of potassium hydroxide solid into the solution obtained in the step (4), stirring, precipitating for 10-15 min, and performing suction filtration to obtain a filter cake;
(6) and (4) removing water and impurities from the filter cake in the step (4), and drying in vacuum at room temperature to obtain the composite potassium ferrate slow-release disinfectant.
Furthermore, the conditions for roasting and modifying the calcium bentonite in the step (1) are as follows: and roasting in a muffle furnace at 450-550 ℃ for 2h for modification.
Furthermore, the mass concentration of the sodium hydroxide aqueous solution in the step (2) is 10-20%; dripping the epoxy chloropropane within 10-30 min; the reaction product was washed alternately with water and acetone.
Furthermore, the concentration of the potassium hydroxide solution in the step (4) is 2-4 mol/L.
Further, after adding the potassium hydroxide solid in the step (5), cooling the reaction; washing the filter cake with n-hexane, isopropanol and diethyl ether in sequence to remove water and KNO3KCl, KOH, etc.
The use method of the composite potassium ferrate slow-release disinfectant comprises the following steps:
(1) weighing the components according to the proportion, adding 40-60 parts of water, and fully stirring and mixing to prepare an active carbon mixture for later use;
(2) extrusion molding: extruding the active carbon mixture prepared in the step (1) into a columnar shape under high pressure;
(3) curing and drying: drying the formed columnar activated carbon to obtain a finished product, wherein water is fed from the lower part of the columnar activated carbon and discharged from the upper part of the columnar activated carbon when the columnar activated carbon is used.
Furthermore, the drying temperature in the step (3) is 105-120 ℃.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention utilizes the good coating performance of the bentonite and the cyclodextrin to coat the potassium ferrate which is a powerful oxidant, maximally isolates the interference of the external environment to the potassium ferrate, and simultaneously enables the medicament to slowly and continuously release the effective components of the potassium ferrate in water to achieve the functions of disinfection and decoloration;
(2) according to the invention, the bentonite and the cyclodextrin can only play a role after being specially treated, and the bentonite loses surface adsorption water, crystal water in a structural framework and impurities in gaps successively after being roasted and modified at high temperature, so that the adsorption resistance of a water film to pollutants is reduced, the hydrophilicity of the bentonite is reduced, the porosity and the specific surface area of the bentonite are increased, and the overall adsorption performance of the bentonite is improved;
(3) in order to reduce the cost for preparing the potassium ferrate, the potassium ferrate composite is prepared by replacing sodium hypochlorite with higher cost with cheap and easily-obtained calcium hypochlorite powder, so that the side reaction between impurities and various raw materials is effectively avoided, the good performance of the potassium ferrate composite is ensured, and the effect of reducing the cost is achieved;
(4) in order to solve the problems of recycling and continuous utilization of the medicament, the composite potassium ferrate slow-release disinfectant is prepared into an activated carbon column with the diameter of 5mm by using powdered activated carbon, so that the medicament is fixed, is not easy to run off under the scouring condition of water flow, and is convenient to detect and replace the medicament regularly;
(5) according to the invention, bentonite which is harmless to the environment and low in cost is used as a framework material, so that potassium ferrate crystals are uniformly generated in interlayer gaps of the bentonite and are slowly released in the water treatment process, the defects that the potassium ferrate is unstable in the air and the utilization efficiency is low in one-time adding are overcome, and the purposes of stability and slow release are achieved;
(6) in the invention, β -cyclodextrin polymer which is harmless to the environment, cheap and easy to obtain is taken as a coating of potassium ferrate, so that the stability of the potassium ferrate is greatly improved, the storage difficulty of a potassium ferrate medicament in the air is reduced, and the potassium ferrate medicament has good slow release capacity, so that the potassium ferrate continuously plays a role in tail water advanced treatment, and simultaneously, the moisture absorption of bentonite is inhibited by combining the potassium ferrate with the bentonite;
(7) according to the invention, the bentonite is modified by high-temperature roasting, so that the bentonite loses surface adsorption water, crystal water in a structural framework and impurities in gaps successively, the adsorption resistance of a water film to pollutants is reduced, the hydrophilicity of the bentonite is reduced, the porosity and the specific surface area of the bentonite are increased, the overall adsorption performance of the bentonite is improved, and the bentonite has good adsorption performance on Pb in a water body2+The removal rate of the catalyst can reach more than 96 percent.
Drawings
FIG. 1 is a schematic diagram showing the decay rate of potassium ferrate in air in the composite potassium ferrate slow-release disinfectant of the present invention;
FIG. 2 is a schematic diagram showing the release rate of potassium ferrate in water of the composite potassium ferrate slow-release disinfectant of the present invention;
FIG. 3 shows the continuous degradation rate of methyl orange by different carbon columns in the present invention.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
The raw materials comprise 20 parts of industrial-grade calcium bentonite, 20 parts of sodium hydroxide sold in the market, 10 parts of potassium hydroxide, 10 parts of calcium hypochlorite, ferric nitrate, 2 parts of n-hexane, 1 part of isopropanol, 1 part of diethyl ether, β -cyclodextrin, 10 parts of epichlorohydrin and 20 parts of carboxymethyl cellulose, the raw materials are divided into 6 groups of medicaments, wherein the mass ratio of the ferric nitrate, the bentonite and the β -cyclodextrin is shown in a table 1-1, and the step of preparing the slow-release water treatment agent is as follows:
TABLE 1-1 raw material ratio of sustained-release preparation
Respectively putting 6 groups of calcium bentonite into a muffle furnace according to the raw material proportion of the table 1-1, roasting for 2h modification at 450 ℃, adding β -cyclodextrin into a 20% sodium hydroxide aqueous solution, slightly heating to dissolve β -cyclodextrin, heating to 50 ℃, dripping epoxy chloropropane under full stirring for about 20min, continuously preserving heat, stirring and reacting, stopping the reaction until gelatinous solid appears, alternately washing the product with water and acetone, drying in vacuum at 50 ℃ to obtain a white solid β -cyclodextrin polymer, grinding and sieving for later use, preparing a saturated potassium hydroxide solution, adding calcium hypochlorite powder, stirring uniformly, standing for 10min, slowly adding ferric nitrate solid, stirring, precipitating a large amount of purple black, filtering to obtain a crude product, dissolving the crude product with a potassium hydroxide solution, stirring for 1h, adding bentonite roasted at high temperature and a β -cyclodextrin polymer, adding potassium hydroxide solid into the solution, stirring, precipitating for 10min, obtaining isopropanol through a mode, washing a filter cake, removing water content of the n-hexane, and the filter cake, removing the water content of the KNO in sequence, and the KN-ether filter cake3And KCl, KOH and other impurities, and drying the product at room temperature in vacuum to obtain 6 groups of potassium ferrate-based slow-release water treatment agents which are respectively marked as agents 1 to 6 in sequence.
Determining the coating rates of the potassium ferrate of the agents 1 to 6 and the uncoated potassium ferrate, which are shown in tables 1-2; placing the medicament in the air, and measuring the decay rate of the potassium ferrate after 5d, 10d, 20d, 30d, 45d and 60d, wherein the specific result is shown in figure 1; the agents were placed in water and the decay rate of potassium ferrate was measured every 5 days until after 30 days, and the results are shown in FIG. 2.
TABLE 1-2 Potassium ferrate coating rates of sustained release formulations
As can be seen from figure 1, the common potassium ferrate is rapidly decomposed by absorbing moisture in the air and is basically completely decomposed after 10 days, while the medicament has good stability when being stored in the air, and the stability of the medicament is continuously improved along with the increase of the content of β -cyclodextrin polymer, the potassium ferrate in the medicament 6 is only decomposed by 10.1% after being stored for 60 days, and by comparing the decay curves of the medicament 1 and the medicament 5, the stability of the potassium ferrate is also improved to a certain extent when the bentonite is added, and the decay rate after 60 days is reduced by about 10%.
According to the figure 2, the ordinary potassium ferrate reagent is fast in decomposition rate in water and is degraded by 99% after one day, and the potassium ferrate reagent subjected to slow release treatment has a certain slow release capacity and can continuously and stably release potassium ferrate in water, so that the functions of oxidizing, decoloring and sterilizing the potassium ferrate are fully exerted. In addition, the bentonite is added, so that the structure of the medicament is more stable, and the release rate is reduced. From the above figure, it can be known that the medicament 5 and the medicament 6 both have good slow release effect, and the residue of the potassium ferrate effective component in the medicament is still more than 50% after 20 days.
The present invention is essentially different from patent 201610383272.3 (patent name: a ferrate-based composite water treatment agent and a preparation method thereof), and firstly, the application range of patent 201610383272.3 is directed at the pretreatment of industrial wastewater, the pollutant components of the industrial wastewater are complex and have high concentration, and the subsequent biochemical treatment can be performed only by the pretreatment, so that the agent used for the pretreatment must have strong oxidizing property. The invention aims at the advanced treatment of tail water, the pollutants in the water are greatly reduced at the moment, the main problem is that the chromaticity and bacteria do not reach the standard, and therefore, the decoloration and the continuous disinfection are needed, so the greatest characteristic of the invention, namely the slow release property, embodies the advantages of the invention, and the decoloration and the disinfection can be continuously achieved after the medicament is added. Secondly, the patent 201610383272.3 utilizes the technology of combining potassium ferrate with fenton, while the invention mainly relates to the technology of combining potassium ferrate with slow release, which is a completely different field from the patent 201610383272.3, and the technical scheme and the principle based on the technology are also different, so the invention has essential difference to the patent 201610383272.3.
Example 2
Raw materials of 110 parts of industrial grade calcium bentonite, 20 parts of sodium hydroxide sold in the market, 13 parts of potassium hydroxide, 13 parts of calcium hypochlorite, 16 parts of ferric nitrate, 3 parts of n-hexane, 2 parts of isopropanol, 1 part of diethyl ether, 300 parts of β -cyclodextrin, 15 parts of epichlorohydrin and 30 parts of carboxymethyl cellulose, and the step of preparing the slow-release water treatment agent comprises the following steps:
calcining calcium bentonite in proportion in muffle furnace at 450 deg.C for 2h for modification, adding β -cyclodextrin into 20% sodium hydroxide water solution, slightly heating to dissolve β -cyclodextrin, heating to 60 deg.C, dropping epichlorohydrin while stirring thoroughly for about 30min, keeping the temperature and stirring for reaction, gradually increasing the viscosity of the mixture, stopping reaction until gel solid appears, alternately washing the product with water and acetone, vacuum drying at 70 deg.C to obtain β -cyclodextrin polymer, grinding and sieving for use, preparing saturated potassium hydroxide solution, adding calcium hypochlorite powder, stirring uniformly, standing for 15min, slowly adding ferric nitrate solid, stirring to obtain a large amount of purple black precipitate, vacuum filtering to obtain crude product, dissolving the crude product with potassium hydroxide solution, stirring for 1h, adding bentonite and β -cyclodextrin polymer modified by high temperature calcination into the solution, adding potassium hydroxide solid into the solution, stirring, precipitating for 15min, obtaining filter cake by normal hexane, isopropanol, ether, and KNO filter cake washing sequentially3KCl, KOH and other impurities will be producedThe product is dried in vacuum at room temperature to obtain the slow-release water treatment medicament based on potassium ferrate, which is marked as medicament 7. The medicament 7 is mixed with 400 parts of powdered activated carbon and 40 parts of carboxymethyl cellulose to prepare an activated carbon column with the granularity of 5mm, which is marked as a carbon column 7.
Preparing simulated wastewater containing 30mg/L of acid scarlet by using an acid scarlet solution as a model pollutant, continuously enabling the wastewater to flow upwards through a carbon column 7, taking an effluent water sample once every 5 days, measuring the content of the acid scarlet in the water by using a fluorescence spectrophotometer, and calculating the degradation rate of the carbon column 7 on the acid scarlet, wherein the degradation result is shown in a table 2-1:
TABLE 2-1 degradation Effect of carbon column 7 on acid scarlet solution
As can be seen from the table above, the prepared carbon column has good degradation rate for acid bright red solution, and most importantly, the persistent degradation rate is kept above 85%, and the persistent decolorizing capability of the compound medicament is fully shown.
Example 3
The raw materials comprise 120 parts of industrial grade calcium bentonite, 20 parts of sodium hydroxide sold in the market, 15 parts of potassium hydroxide, 15 parts of calcium hypochlorite, 18 parts of ferric nitrate, 4 parts of n-hexane, 2 parts of isopropanol, 2 parts of diethyl ether, 200 parts of β -cyclodextrin, 20 parts of epoxy chloropropane and 40 parts of carboxymethyl cellulose, and the step of preparing the slow-release water treatment agent comprises the following steps:
adding β -cyclodextrin into 20% sodium hydroxide aqueous solution, slightly heating to dissolve β -cyclodextrin, heating to 70 ℃, dropping epichlorohydrin while fully stirring, continuously keeping the temperature and stirring for reaction, gradually increasing the viscosity of the mixture until the reaction stops when gelatinous solid appears, alternately washing the product with water and acetone, vacuum drying at 60 ℃ to obtain white solid, namely β -cyclodextrin polymer, grinding and sieving for later use, preparing saturated potassium hydroxide solution, adding calcium hypochlorite powder, uniformly stirring, standing for 10min, slowly adding ferric nitrate solid, stirring, adding a large amount of purple bentonite, and stirring for 2hPrecipitating with black precipitate, vacuum filtering to obtain crude product, dissolving the crude product with potassium hydroxide solution, stirring for 1 hr, adding bentonite and β -cyclodextrin polymer modified by high temperature roasting, adding potassium hydroxide solid, stirring, precipitating for 15min, vacuum filtering to obtain filter cake, sequentially washing with n-hexane, isopropanol and diethyl ether to remove water and KNO in the filter cake3And KCl, KOH and the like, and drying the product at room temperature in vacuum to obtain the potassium ferrate-based slow-release water treatment medicament, which is marked as medicament 8.
15g of the medicament 8 is put into a solution containing 25mg/L of active black 5 dye, the solution is stirred and then precipitated for 15min, the content of the active black 5 in water is measured by a fluorescence spectrophotometer, the degradation rate of the composite medicament on the active black 5 is calculated, more than 95% of the active black dye is degraded, and the good decoloring performance of the composite medicament is fully demonstrated.
Example 4
Raw materials: agents 1 to 6, carboxymethyl cellulose, powdered activated carbon in example 1
The agents 1 to 6 in example 1 were mixed with 200 parts of powdered activated carbon and 20 parts of carboxymethyl cellulose, respectively, to prepare activated carbon columns having a particle size of 5mm, which were sequentially designated as carbon columns 1 to 6, respectively.
Adopting methyl orange solution as a model pollutant, preparing simulated wastewater containing 20mg/L of methyl orange, respectively and continuously flowing upwards through a carbon column 1 to a carbon column 6, taking an effluent water sample once every 5 days, measuring the content of the methyl orange in the water by using a fluorescence spectrophotometer, and calculating the degradation rate of the methyl orange by different carbon columns, wherein the figure is 3.
As can be seen from FIG. 3, the activated carbon column prepared in this example has a certain degradation capability to methyl orange, wherein the initial degradation effect of the carbon column 2 and the carbon column 3 is the best, and reaches more than 95%, while the initial degradation rate of the carbon column 5 and the carbon column 6 is relatively low, but is also more than 90%, and the degradation rate of each carbon column to methyl orange after 5 days is reduced to less than 90%, because when the composite potassium ferrate sustained-release agent is just put into water, part of uncoated potassium ferrate molecules are quickly released in water, and together with the coated potassium ferrate, the potassium ferrate molecules are oxidatively decomposed, so that the initial degradation rate of methyl orange is high. And with the complete release of the uncoated potassium ferrate molecules, only the coated potassium ferrate is left to be slowly released to decompose the methyl orange in water, so that the subsequent degradation rate of the methyl orange is reduced, and the normal phenomenon is realized.
Because the cyclodextrin content of the carbon column 5 and the carbon column 6 is higher, the relative content of potassium ferrate is lower, and thus the oxidation capacity for methyl orange is not higher than that of the carbon column 2 and the carbon column 3, the degradation rate for methyl orange in the initial stage is lower. The potassium ferrate content of the carbon column 1 is similar to that of the carbon column 3, the degradation rate of the carbon column 3 to methyl orange is higher than that of the carbon column 1, and the carbon column 3 contains modified bentonite which has certain adsorption and degradation capacity to dye molecules.
In the figure, after 16 days, the degradation rates of the carbon columns 1 to 4 to the methyl orange are reduced to a certain extent, the degradation rates of the carbon columns 5 and 6 to the methyl orange are basically stabilized at about 85%, and the analysis reason is that the cyclodextrin content of the carbon columns 5 and 6 is higher, the coating performance to potassium ferrate is better, so that the potassium ferrate can be stably and slowly released in water, and the slow release effect is achieved, the release rate of the potassium ferrate of the carbon columns 1 to 4 is higher, the content of the effective component potassium ferrate in the medicament is reduced in the later period, the release amount is also reduced, and the degradation rate of the methyl orange is also reduced to a certain extent. This example demonstrates that carbon column 5 and carbon column 6 have good and stable sustained release effects.
Example 5
Taking the effluent of a secondary sedimentation tank of a certain sewage treatment plant, wherein the water quality is faint yellow and alkalescent, and the main water quality indexes are shown in a table 3-1:
TABLE 3-1 quality index of effluent from secondary sedimentation tank of certain sewage plant
The water sample continuously flows upwards through the carbon column 5 prepared in the embodiment 4, effluent is collected every 5 days, and the water quality index of the effluent is measured, wherein the specific numerical values are shown in a table 3-2:
TABLE 3-2 Water quality index after treatment with composite potassium ferrate sustained-release agent
As can be seen from the table above, the carbon column 5 has a good disinfection effect on secondary effluent of a sewage treatment plant, the total amount of bacteria is reduced by two orders of magnitude, and simultaneously, the decoloration capacity is good, the initial decoloration efficiency is up to 93.33%, the decoloration rate in the following 25 days is also stabilized to more than 85%, and the decoloration and disinfection effects are not obviously reduced, so that the slow-release effect of potassium ferrate is fully exerted, the COD (chemical oxygen demand) of the effluent is further reduced, the capability of continuous disinfection and continuous decoloration of the composite potassium ferrate slow-release agent can be fully demonstrated, and the first-class A standard of pollutant discharge Standard of municipal wastewater treatment plant (GB18918-2002) is reached.
Claims (6)
1. The preparation method of the composite potassium ferrate slow-release disinfectant comprises the following preparation raw materials, by mass, 20 parts of sodium hydroxide, 10-15 parts of potassium hydroxide, 10-15 parts of calcium hypochlorite, 15-18 parts of ferric nitrate, 2-4 parts of n-hexane, 1-2 parts of isopropanol, 1-2 parts of diethyl ether, 100-120 parts of calcium bentonite, 100-200 parts of β -cyclodextrin and 10-20 parts of epoxy chloropropane, and comprises the following preparation steps:
(1) weighing the components in proportion, and roasting and modifying the calcium bentonite for later use;
(2) synthesizing β -cyclodextrin polymer, namely dissolving β -cyclodextrin in sodium hydroxide aqueous solution, heating to 50-70 ℃, dripping epoxy chloropropane under the condition of stirring, continuing to keep the temperature and stir for reaction until a gel solid appears, stopping the reaction, cleaning a reaction product, drying to obtain a white solid, namely β -cyclodextrin polymer, and grinding and sieving for later use;
(3) preparing a saturated potassium hydroxide solution, adding calcium hypochlorite powder, uniformly stirring, standing, slowly adding ferric nitrate solid, stirring, precipitating in a large amount, and performing suction filtration to obtain a crude product of potassium ferrate;
(4) dissolving the crude potassium ferrate product obtained in the step (3) by using a potassium hydroxide solution, stirring, and adding the modified bentonite obtained in the step (1) and the β -cyclodextrin polymer obtained in the step (2) into the solution;
(5) adding a potassium hydroxide solid into the solution obtained in the step (4), stirring, precipitating for 10-15 min, and performing suction filtration to obtain a filter cake;
(6) and (5) washing the filter cake in the step (5) with normal hexane, isopropanol and diethyl ether in sequence to remove water and impurities, and drying to obtain the composite potassium ferrate slow-release disinfectant.
2. The preparation method of the composite potassium ferrate slow-release disinfectant as claimed in claim 1, wherein the preparation method comprises the following steps: the conditions for roasting and modifying the calcium bentonite in the step (1) are as follows: roasting at 450-550 ℃ for 2h for modification.
3. The preparation method of the composite potassium ferrate slow-release disinfectant as claimed in claim 1, wherein the preparation method comprises the following steps: the mass concentration of the sodium hydroxide aqueous solution in the step (2) is 10-20%; dripping the epoxy chloropropane within 10-30 min; the reaction product was washed alternately with water and acetone.
4. The preparation method of the composite potassium ferrate slow-release disinfectant as claimed in claim 1 or 3, wherein the preparation method comprises the following steps: the concentration of the potassium hydroxide solution in the step (4) is 2-4 mol/L.
5. The preparation method of the composite potassium ferrate slow-release disinfectant as claimed in claim 1, wherein the preparation method comprises the following steps: when the prepared slow-release disinfectant is used, 200-400 parts of powdered activated carbon and 20-40 parts of carboxymethyl cellulose are combined to prepare the activated carbon column.
6. The preparation method of the composite potassium ferrate slow-release disinfectant as claimed in claim 1 or 2, wherein the preparation method comprises the following steps: the preservation conditions of the prepared slow-release disinfectant are as follows: storing in dark under the dry condition below 35 ℃.
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| CN111892155A (en) * | 2020-08-20 | 2020-11-06 | 江苏苏美达成套设备工程有限公司 | Slow-release oxidizing agent for removing underground water polluted organic matter and process thereof |
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