CN114436393A - Magnesium-rich micro-electrolysis biological filler and manufacturing method thereof - Google Patents
Magnesium-rich micro-electrolysis biological filler and manufacturing method thereof Download PDFInfo
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- CN114436393A CN114436393A CN202210068697.0A CN202210068697A CN114436393A CN 114436393 A CN114436393 A CN 114436393A CN 202210068697 A CN202210068697 A CN 202210068697A CN 114436393 A CN114436393 A CN 114436393A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
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Abstract
The invention relates to a magnesium-rich micro-electrolysis biological filler and a manufacturing method thereof, wherein the biological filler comprises the following raw materials in parts by weight: 1-10 parts of curing material, 1-10 parts of micro-electrolysis material, 0.1-1 part of pore-forming material, 0.1-1 part of microporous pore-forming material and 1-10 parts of magnesium material; the solidifying material is at least one of resin, clay and bentonite, the pore-forming material is at least one of polyvinyl alcohol and polystyrene spheres, the micro-pore-forming material is at least one of ammonium chloride and ammonium bicarbonate, the micro-electrolysis material comprises an anode material and a cathode material, the anode material is at least one of scrap iron, iron shavings and reductive iron powder, the cathode material is at least one of charcoal, activated carbon and coke as an inert electrode material, and the magnesium material is at least one of light magnesium oxide, magnesium chloride and chemical industrial wastewater with magnesium concentration of more than 100 mg/L. The synergistic effect of the load microorganism and the micro-electrolysis is achieved, and the biodegradability of the sewage is improved; the larger specific surface area can improve the efficiency of packing film formation and demoulding, and the phosphorus can be efficiently adsorbed by multiple adsorption sites.
Description
Technical Field
The invention relates to the field of water treatment in environmental engineering, in particular to a magnesium-rich micro-electrolysis biological filler and a manufacturing method thereof.
Background
With the continuous development of cities, emerging industries continuously appear, the water pollution condition is accelerated to worsen, and the biofilm method becomes an essential method in sewage treatment by virtue of the application advantages of the biofilm method. While the application of the biofilm method can not be separated from various fillers, the removal effect of the commonly used ceramsite and gravel filler on pollutants in sewage is poor, meanwhile, in a patent previously applied by the applicant, application number is CN201810043639.6, a magnesium-rich biological filler is mentioned, the magnesium-rich biological filler comprises a solidifying material, an adsorption material and a magnesium material, the solidifying material is at least one of cement, sodium alginate, resin and bentonite, the adsorption material is at least one of silica gel, activated alumina, activated carbon and a molecular sieve, the magnesium material is at least one of magnesium oxide, magnesium chloride and chemical industrial wastewater with extremely high magnesium concentration, and the component proportion of the solidifying material, the adsorption material and the magnesium material is 1-10: 1-10: 1-10. The magnesium-rich biological filler needs to be made into a hollow or honeycomb shape to increase the gas-liquid contact area, the manufacturing steps are complex, and the phosphorus and nitrogen removal effects need to be improved.
Disclosure of Invention
One object of the present invention: in order to overcome the defects of the prior art, the invention provides the magnesium-rich micro-electrolysis biological filler which is applied to sewage treatment to play a role of loading microorganisms and can generate a synergistic effect with micro-electrolysis to improve the biodegradability of sewage; the large specific surface area can improve the efficiency of packing film formation, and has the advantages of efficient phosphorus adsorption, erosion resistance, scouring resistance and more adsorption sites, thereby reducing the treatment cost of unit water volume and improving the treatment efficiency.
The technical scheme of the invention is as follows: the magnesium-rich micro-electrolysis biological filler comprises the following raw materials in parts by weight:
1-10 parts of curing material, 1-10 parts of micro-electrolysis material, 0.1-1 part of pore-forming material, 0.1-1 part of microporous pore-forming material and 1-10 parts of magnesium material;
the solidifying material is at least one of resin, clay and bentonite, the pore-forming material is at least one of polyvinyl alcohol and polystyrene balls, the micro pore-forming material is at least one of ammonium chloride and ammonium bicarbonate, the micro electrolysis material comprises an anode material and a cathode material, wherein the anode material is at least one of scrap iron, iron shavings and reductive iron powder, the cathode material is at least one of inert electrode material of charcoal, activated carbon and coke, and the magnesium material is at least one of light magnesium oxide, magnesium chloride and chemical industrial wastewater with magnesium concentration of more than 100 mg/L.
Preferably, the diameter of the pore-forming material is 0.1-2mm, and the diameter of the micro-pore-forming material is 0.05-0.08 mm.
Preferably, the bentonite is a sodium bentonite.
By adopting the scheme, the component proportion of the curing material, the micro-electrolysis material, the pore-forming material, the micropore pore-forming material and the magnesium material is 5: 8: 0.1: 0.1: 5, the proportion is the optimal component proportion, and the curing material is obtained by repeated experiments and is selected from commercially available nano bentonite; selecting iron powder and activated carbon as micro-electrolysis materials; selecting polystyrene balls with the diameter of 1mm as the pore-forming material; selecting ammonium bicarbonate with the diameter of 0.05-0.08mm as the micro pore-forming material; the magnesium material is light magnesium oxide sold in the market, the manufacturing cost of the filler is low, and the treatment effect is good.
The magnesium-rich micro-electrolysis biological filler is applied to sewage treatment, can play a role of loading microorganisms, can generate a synergistic effect with micro-electrolysis, and improves the biodegradability of sewage;
through the addition of pore-forming material and micropore pore-forming material, polystyrene ball loss of burning can increase liquid phase mobility, increases specific surface area, and ammonium bicarbonate can provide the very little site in hole for micropore pore-forming provides the adsorption site, so make the filler have better liquid circulation, increased when preventing to harden the specific surface area of filler for fashioned filler has great specific surface area, can improve filler biofilm formation and demoulding efficiency, still has high-efficient absorption phosphorus simultaneously, and anti erosion is able to bear or endure to erode, more adsorption site, thereby can reduce the treatment cost of unit water yield, improves the treatment effeciency, and simple structure need not make hollow or cellular with the filler.
Another object of the present invention is to provide a method for preparing a magnesium-rich microelectrolytic biological filler, comprising the steps of:
firstly, mixing the solidified material, the micro-electrolysis material, the magnesium material, the pore-forming material and the micropore pore-forming material obtained by sieving in the step one according to the weight ratio of 1-10: 1-10: 1-10: 0.1-1: 0.1-1 to obtain mixed raw materials,
wherein, the solid solidifying material, the micro-electrolysis material and the magnesium material are crushed to 10-100 meshes before mixing, and pass through a sieve with the aperture of 0.15-2 mm;
secondly, mixing the mixed raw materials obtained in the first step with water according to a weight ratio of 5-10: 1-5, obtaining raw material slurry with the viscosity of 10-20 s;
thirdly, drying the raw material slurry obtained in the second step at the temperature of 10-120 ℃ to obtain a solid;
fourthly, coating the solid obtained in the third step with activated carbon powder or calcining for 1 to 3 hours under the condition of nitrogen filling, wherein the calcining temperature is 600 ℃ and 1000 ℃, and naturally cooling to 10 to 25 ℃ to obtain the magnesium-rich micro-electrolysis biological filler;
and fifthly, storing the magnesium-rich micro-electrolysis biological filler in the step four at the shady place, spraying water for maintenance every 1-12 hours, and keeping the surface of the filler wet for 3-7 days.
Preferably, the mixed raw material of the step two and water are shaken in a disc type granulator at the rotating speed of 5-20r/min to prepare 1-10cm spherical raw material slurry.
Preferably, the mixed raw material of the second step is pressed and formed in a mould with water.
The technical scheme of the invention has the following beneficial effects:
firstly, pretreating raw materials to remove impurities, preventing the interference of other impurities and influencing the preparation of the filler, then screening large-particle raw materials through a sieve to enable the raw materials to be as fine as possible and to be convenient for mixing and melting, and in the second step and the third step, the raw materials obtained in the first step are mixed and stirred with water, 400g of water is generally added into every 1kg of mixed raw materials to ensure that the consistency of the raw material mixed solution can be adjusted to 10-20s, a mould can be selected according to actual use and industrial scale for manufacturing or shaking, the raw materials can be manufactured into fillers with different sizes and shapes to ensure the requirements in actual use, or the fillers can be poured into blocks and crushed into particles after the firing is finished;
the calcination of the solid in the step five adopts a loss-on-ignition method, namely, after the temperature is increased, the ammonium bicarbonate and the polystyrene spheres become gas to escape, so that the filler has better liquid circulation, the hardening is prevented, and the specific surface area of the filler is increased; the temperature is controlled to be 600-1000 ℃ in the firing process so as to prevent the light magnesium oxide from being converted into heavy magnesium oxide, so that the porosity is reduced and the sewage treatment effect is reduced, in the example experiment, 750 ℃ is selected for firing, and the mechanical strength of the filler can be increased at the temperature; the nitrogen filling operation is carried out while firing, or the activated carbon powder is wrapped on the surface layer of the filler, so that the oxidation speed of the activated carbon on the surface layer can be reduced to the maximum extent.
Drawings
FIG. 1 is a flow chart of a manufacturing method in an embodiment of the invention;
FIG. 2 is a diagram of a magnesium-rich micro-electrolysis biological filler in the embodiment of the invention.
Detailed Description
Preparation of different biological fillers
Group 1, control (cured + magnesium material);
group 2, control group + microelectrolytic material;
3-1 group, control group + micro-electrolysis material + pore-forming material (taking polyvinyl alcohol);
3-2 groups, control group + micro-electrolysis material + pore-forming material (taking polystyrene ball);
4-1 group, control group, micro-electrolysis material, pore-forming material (taking polystyrene ball), microporous pore-forming material (taking ammonium bicarbonate);
4-2 groups, control group, micro-electrolysis material, pore-forming material (taking polystyrene ball), microporous pore-forming material (taking ammonium chloride);
and 5 groups, namely a control group, a micro-electrolysis material, a pore-forming material (taking polyvinyl alcohol and polystyrene spheres), and a microporous pore-forming material (taking ammonium chloride and ammonium bicarbonate).
TABLE 1 comparison table of pH values, COD, TN and TP removal rates of different biological fillers
The pH value of above 8.5 can cause ammonia nitrogen volatilization and phosphate precipitation, and is also an important index for judging the reaction activity of the filler and the biological film.
As can be seen from the above table, the removal rates of COD, TN and TP in the experimental groups 2-5 are all higher than those in the control group 1, and the removal rates of PCOD, TN and TP in the experimental group 5 are all higher than those in the other experimental groups 2-4, and the biological filler in the experimental group 5 has lasting material reaction activity and high removal efficiency.
Preparation of magnesium-rich micro-electrolysis biological filler
The weight parts of the curing material, the micro-electrolysis material, the pore-forming material, the micropore pore-forming material and the magnesium material are 5: 8: 0.1: 0.1: 5.
the curing material is selected from commercially available nano bentonite; selecting iron powder and activated carbon as micro-electrolysis materials; selecting polystyrene balls with the diameter of 1mm as the pore-forming material; selecting ammonium bicarbonate as the micro-pore forming material; the magnesium material is light magnesium oxide which is sold in the market. And the material proportion is improved through an orthogonal experiment to obtain the optimized proportion, and the phosphorus removal effect is optimal.
TABLE 2 Cross-contamination level comparison table for biological filler
In the embodiment of the invention, the method for manufacturing the magnesium-rich micro-electrolysis organisms with the optimal mixture ratio comprises the following steps:
crushing the nano bentonite and the active carbon to 100 meshes, then screening by using a sieve with the aperture of 0.15mm, mixing iron powder, light magnesium oxide, ammonium bicarbonate and polystyrene spheres with the diameter of 1mm according to the mass ratio of 100: 60: mixing at a ratio of 100:100:1:1 to obtain a mixed raw material,
step two, mixing the mixed raw materials with water according to a mass ratio of 10: 4, mixing to obtain raw material slurry, wherein the viscosity of the raw material slurry is 10-20 s;
step three, drying the raw material slurry obtained in the step two at 105 ℃ to obtain a solid;
step four, coating the solid obtained in the step three with activated carbon powder or calcining the solid for 2 hours under the condition of nitrogen filling, wherein the calcining temperature is 750 ℃, and naturally cooling the solid to 10-25 ℃ to obtain the magnesium-rich micro-electrolysis biological filler;
and step five, spraying water to the cooled magnesium-rich micro-electrolysis biological filler every 8 hours for maintenance, keeping the surface of the filler wet, and maintaining for 7 days.
l experimental detection is carried out on the prepared magnesium-rich micro-electrolysis biological filler
And detecting the adsorption capacity of the prepared magnesium-rich micro-electrolysis biological filler through an adsorption kinetics curve experiment. Fitting Using Langmuir Curve (R)2Not less than 0.98), and the result shows that the filler has the maximum adsorption capacity of 4.566 mg/g for phosphorus in phosphorus solution in 24 hours and 7.698 mg/g for phosphorus in nitrogen and phosphorus coexisting solution, and has good phosphorus removal effect.
In order to detect the treatment effect of the carbon-magnesium biological filler on actual sewage after biological attachment, the magnesium-rich micro-electrolysis biological filler is prepared into a small ball with the diameter of 1-2cm, and the small ball and ceramsite, gravel and iron-carbon filler with the same volume are suspended in four SBR reactors with the same process by using non-woven grid bags. The SBR reactor adopts sand head aeration, the hydraulic retention time is 32h, and a mode of water inlet → 18h aeration → 6h sedimentation is adopted. The DO concentration of the SBR reactor was controlled to be 3 mg/L or more during aeration.
Selecting urine diluted by 10 times as inlet water, wherein the concentrations of COD, TN and TP of the inlet water are 1067 +/-488.73, 596.13 +/-72.46 and 28.16 +/-3.95 mg/L respectively, and inoculating 1L of sludge from the black water in-situ treatment aeration biological filter for inoculation in the starting stage of the device. After one week of microbial culture, the removal effect of the reactor on the pollutants is gradually stabilized, and the end of biofilm culture is judged. The experimental period is two months, the water inlet and the water outlet are sampled and detected every 3 days after the experiment is started, the experimental detection indexes comprise TP, TN, COD and pH, and the detection process and the detection method are carried out according to the national standard.
TABLE 3 comparison table of pH values, COD, TN and TP removal rates of different biological fillers
From the treatment effect: the black water is treated by four commercial fillers of gravel, iron-carbon filler and ceramsite and the magnesium-rich micro-electrolysis biological filler combined with the SBR sewage treatment device, and the ammonia nitrogen and phosphorus removal effects of each filler experimental group are compared. In the aspect of removal efficiency, the magnesium-rich biological micro-electrolysis filler has the highest TN, TP and removal effect. Especially has obvious TP removing effect, and can slowly release Mg under alkaline condition due to the magnesium-rich characteristic2+And the sludge and phosphate generate precipitate, and the phosphorus is removed in a sludge discharge mode. In the aspect of operation stability, compared with the iron-carbon micro-electrolysis filler, the removal effect caused by hardening in the later stage of use is reduced, so that the standard deviation is larger, and the average value of the removal effect on TP in the last nine times is only 5.92%. The magnesium-rich biological micro-electrolysis filler has no hardening and reduced removal effect in an experimental period of two months. In the application range, the magnesium-rich micro-electrolysis biological filler can be used for coping with more water inlet conditions due to the existence of micro-electrolysis, can convert the organic matters which are difficult to decompose by the inlet water with low biodegradability through the micro-electrolysis, and is particularly suitable for the treatment of the wastewater with high TP concentration.
The results in table 3 are the average results over a two month period, measured every 3 days, wherein the average removal rate of the magnesium-rich biological filler to each index, especially the removal rate of TN (13.96%) and TP (78.25%), is much higher than that of other materials, the material reaction activity is durable, and the removal efficiency is high.
In conclusion, compared with the traditional fillers such as ceramsite, gravel and iron-carbon micro-electrolysis material, the magnesium-rich micro-electrolysis biological filler has the advantages of larger specific surface area, more adsorption sites, longer effectiveness and bioactivity, difficulty in hardening, certain mechanical strength, capability of changing the physical form of the filler according to process change, easiness in obtaining materials, high cost performance and the like.
Compared with the prior art, the filler biofilm formation and demoulding efficiency is improved, and the filler biofilm formation and demoulding agent has the advantages of erosion resistance, scouring resistance, large porosity, large specific surface area and the like, so that the treatment cost of unit water volume can be reduced, the treatment efficiency is improved, and the magnesium-rich micro-electrolysis biological filler has higher dephosphorization efficiency and more adsorption points. Furthermore, the biodegradability of the sewage can be increased through micro-electrolysis, and the removal efficiency of pollutants in the sewage is enhanced.
Claims (7)
1. The magnesium-rich micro-electrolysis biological filler is characterized by comprising the following raw materials in parts by weight:
1-10 parts of curing material, 1-10 parts of micro-electrolysis material, 0.1-1 part of pore-forming material, 0.1-1 part of microporous pore-forming material and 1-10 parts of magnesium material;
the solidifying material is at least one of resin, clay and bentonite, the pore-forming material is at least one of polyvinyl alcohol and polystyrene balls, the micro pore-forming material is at least one of ammonium chloride and ammonium bicarbonate, the micro electrolysis material comprises an anode material and a cathode material, wherein the anode material is at least one of scrap iron, iron shavings and reductive iron powder, the cathode material is at least one of inert electrode material of charcoal, activated carbon and coke, and the magnesium material is at least one of light magnesium oxide, magnesium chloride and chemical industrial wastewater with magnesium concentration of more than 100 mg/L.
2. The magnesium-rich microelectrolytic biologic filler according to claim 1, wherein the pore-forming material has a diameter of 0.1 to 2mm and the micro pore-forming material has a diameter of 0.05 to 0.08 mm.
3. The magnesium-rich microelectrolytic biofilm carrier of claim 1, wherein the bentonite is a sodium bentonite.
4. A method of manufacturing a magnesium-rich microelectrolytic biofilm carrier according to any one of claims 1 to 3, characterized in that it comprises the following steps:
firstly, solidifying material, micro-electrolysis material, magnesium material, pore-forming material and micropore pore-forming material are mixed according to the weight ratio of 1-10: 1-10: 1-10: 0.1-1: 0.1-1 to obtain mixed raw materials,
wherein, the solid solidifying material, the micro-electrolysis material and the magnesium material need to be crushed before mixing and pass through a sieve with the aperture of 0.15-2 mm;
secondly, mixing the mixed raw materials obtained in the first step with water according to a weight ratio of 5-10: 1-5, obtaining raw material slurry with the viscosity of 10-20 s;
thirdly, drying the raw material slurry obtained in the second step at the temperature of 10-120 ℃ to obtain a solid;
fourthly, coating the solid obtained in the third step with activated carbon powder or calcining the solid for 1 to 3 hours under the condition of filling nitrogen, wherein the calcining temperature is 600-1000 ℃, and naturally cooling the solid to 10 to 25 ℃ to obtain the magnesium-rich micro-electrolysis biological filler;
and fifthly, storing the magnesium-rich micro-electrolysis biological filler in the step four at the shady place, spraying water for maintenance every 1-12 hours, and keeping the surface of the filler wet for 3-7 days.
5. The method of manufacturing magnesium-rich microelectrolytic biologic filler according to claim 4, characterized in that: in the step one, the solidified material, the micro-electrolysis material and the magnesium material which are in a solid state are crushed to 10-100 meshes.
6. The method of manufacturing magnesium-rich microelectrolytic biofiller according to claim 4, wherein: and shaking the mixed raw materials in the step two and water in a disc type granulator at the rotating speed of 5-20r/min to prepare 1-10cm spherical raw material slurry.
7. The method of manufacturing magnesium-rich microelectrolytic biologic filler according to claim 4, characterized in that: and pressing and molding the mixed raw materials and water in a mold.
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| CN108191041A (en) * | 2018-01-17 | 2018-06-22 | 温州大学 | A kind of richness magnesium biologic packing material and its manufacturing method |
| CN111137969A (en) * | 2020-01-17 | 2020-05-12 | 湖南三友环保科技有限公司 | Preparation method of biological filter filler and biological aerated filter |
| CN112409013A (en) * | 2020-11-30 | 2021-02-26 | 温州市工业科学研究院 | Modified ceramsite filler for adsorption and preparation method thereof |
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- 2022-01-20 CN CN202210068697.0A patent/CN114436393A/en active Pending
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| CN105036256A (en) * | 2015-08-20 | 2015-11-11 | 江苏大学 | Novel microelectrolysis filler, and preparation method and application thereof |
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| CN108191041A (en) * | 2018-01-17 | 2018-06-22 | 温州大学 | A kind of richness magnesium biologic packing material and its manufacturing method |
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