JPH0520140B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Field The present invention is used to adsorb and purify harmful metal ions, gases, and odors in various waste liquids discharged from factories, etc., and to prevent oxygen deficiency conditions.
It is also used to adsorb the odor of domestic wastewater such as human waste, or it is used to coagulate and precipitate microcolloids in water to adsorb and purify various metal ions in water, or it is used to purify blue powder and red tide in water. The present invention relates to a continuous porous body provided with an electromagnetic field for use in coagulating and precipitating to improve transparency and preventing an oxygen deficiency state, and a method for manufacturing the same. Prior Art Conventionally, activated carbon has been used as an adsorbent for metal ions and odors, and synthetic zeolite has been used as an adsorbent for metal ions. Furthermore, in order to treat microcolloids, they are precipitated using a polymer flocculant, and metal ions eluted into water from the coagulated precipitate are adsorbed by activated carbon or synthetic zeolite. Regarding blue powder and red tide in the water, there was no material that could be well coagulated and precipitated. Problems to be Solved by the Invention However, activated carbon and synthetic zeolite require time and effort to produce and are expensive. Additionally, activated carbon has poor adsorption efficiency in liquid. Therefore, it costs a huge amount of money to treat large amounts of various waste liquids and domestic wastewater, so the current situation is that they are discharged untreated and cause pollution by contaminating lakes, rivers, and the sea. On the other hand, since the treatment of microcolloids requires two types of coagulants: a polymer flocculant and activated carbon or synthetic zeolite, the workability is not only poor, but activated carbon and synthetic zeolite also have the above-mentioned problems. In addition, since there is no material to properly coagulate and precipitate blue powder and red tide in the water, there is no choice but to let them reproduce, and the current situation is that the water eventually becomes oxygen-deficient, leading to the death of fish and shellfish. be. Therefore, the present invention can efficiently adsorb metal ions, odors, etc. from various waste liquids, or can efficiently adsorb metal ions eluted into water by coagulating and precipitating microcolloids without using a flocculant. It can efficiently coagulate and precipitate blue powder and red tide in water to prevent oxygen deficiency in the water, and it can be easily manufactured and can be used to reduce costs. The present invention aims to provide an electromagnetic field continuous porous body suitable for large-scale treatment of waste liquid, etc., and a method for producing the same. Means for Solving the Problems The electromagnetic field continuous porous body of the present invention to solve the above problems uses coal fly ash and cement as main raw materials, and contains ammonium chloride, potassium chloride,
Magnesium chloride, sodium chloride, calcium chloride, sodium sulfate, citric acid, cobalt chloride, kaolin clay and barium oxide are added, and an electromagnetic field is applied to form a continuous porous body.
Adsorbs metal ions and odors in water, coagulates and precipitates microcolloids in water, and adsorbs metal ions.
It is designed to coagulate and precipitate blue powder and red tide in the water. Further, in order to solve the above-mentioned problems, the method for producing an electromagnetic field continuous porous body of the present invention is to mix and dry coal fly ash and an aqueous solution of ammonium chloride and potassium chloride, and to mix the dried material with cement, potassium chloride, Aqueous solutions of magnesium chloride, sodium chloride, calcium chloride, sodium sulfate, citric acid, cobalt chloride, kaolin clay, and barium oxide are mixed and dried, and an electromagnetic field is applied during the reaction to form a continuous porous body. It adsorbs metal ions and odors, coagulates and precipitates microcolloids in water, adsorbs metal ions, and coagulates and precipitates blue powder and red tide in water. The electromagnetic field continuous porous body of the present invention has 2 to 20 kg of cement per 1000 kg of coal flyash, which is the main raw material.
%, ammonium chloride 0.04-0.05%, potassium chloride 0.07-0.095%, magnesium chloride 0.015-0.02
%, sodium chloride 0.015-0.02%, calcium chloride 0.015-0.02%, sodium sulfate 0.001-0.002
%, citric acid 0.0005-0.001%, cobalt chloride
It is used at a blending ratio of 0.0001 to 0.0002%, kaolinite 5 to 20%, and barium oxide 0.001% to 0.01%. During production, coal fly ash is mixed with an aqueous solution of ammonium chloride and potassium chloride and then dried.
Ammonium chloride 0.04-0.05% for 1000Kg,
A mixture of cement, potassium chloride, magnesium chloride, sodium chloride, calcium chloride, sodium sulfate, citric acid, cobalt chloride, kaolinite, and barium oxide is used at a mixing ratio of 0.05 to 0.07% potassium chloride and 30 to 40% water. In the secondary treatment, 2 to 20% cement, 0.02 to 0.025% potassium chloride, 0.015 to 0.02% magnesium chloride, and sodium chloride are added to 1000 kg of coal flyash.
0.015-0.02%, calcium chloride 0.015-0.02%,
Sodium sulfate 0.001~0.002%, citric acid 0.005~
0.001%, cobalt chloride 0.0001-0.0002%, kaolinite 5-20%, barium oxide 0.001-0.01%,
Use at a blending ratio of 30 to 40% water. Primary treatment and secondary treatment are performed at the above-mentioned mixing ratio, and an electromagnetic field is applied during the reaction (during curing) in the secondary treatment. The primary treatment of mixing coal fly ash with ammonium chloride and potassium chloride desorbs the charge held by the fine coal fly ash containing water, and by mixing the coal fly ash with an aqueous solution of cement, when the cement is in the liquid phase, In addition to activating the calcium ion reaction, humic acid, which is a polymer compound that inhibits the cement solidification reaction, is removed by reacting with ammonium chloride, sodium sulfate, and citric acid, and SiO, the main component of coal fly ash, is removed. ₂ , _{Al2O3 ,}
The particles of MgO, K, and Na react with the calcium in the cement to perform its original function. By imparting permeability to calcium ions in the cement through the action of sodium chloride and potassium chloride, the hardened material becomes a continuous porous material, which is the opposite of a solidified cement product. Kaolinite and barium oxide prevent the decrease in the persistence of magnetic force when an electromagnetic field is applied, and calcium chloride can shorten the setting time of cement by reacting with cement, and reacts with calcium ions and magnesium chloride. By using cobalt chloride, shrinkage of cement can be prevented, and by using cobalt chloride, each of the above reactions can be activated. During this reaction (during curing), an electromagnetic field is applied to change the molecular bonds. The chemical composition of a continuous porous material given this electromagnetic field is
_SiO2 50-70%, _{Al2O3 10-30} %, MgO2-3%,
CaO 10-20%, Na 5-10%, connected in three dimensions while sharing the oxygen atoms at the vertices of the SiO ₄ tetrahedron, with a pore diameter of 50 Å to 300 Å and a specific surface area of 10 m ² /g.
15m ² /g, and some of the Si in this is replaced with Al, creating a −1 valent charge, and cations such as Na ⁺ , K ⁺ , Ca ⁺⁺ are added to neutralize this charge. It becomes an aluminum silicate compound contained inside. Here, if ammonium chloride is less than 0.04%, each component will be difficult to dissolve, and if it is more than 0.05%, the strength of the continuous porous body will decrease. If potassium chloride is less than 0.07%, the cement's ability to penetrate calcium ions will be poor, and if it is more than 0.095%, it will not only be difficult to dissolve, but the effect of imparting permeability to calcium ions will not improve. If the magnesium chloride content is less than 0.015%, shrinkage cracks will occur in the continuous porous material.
If it exceeds 0.02%, the continuous porous material will expand. If sodium chloride is less than 0.015%, the cement's ability to penetrate calcium ions will be poor; if it is more than 0.02%, not only will it be difficult to dissolve, but the effect of imparting penetrating power to calcium ions will not improve. If calcium chloride is less than 0.015%, the strength of the continuous porous body cannot be enhanced, and if it is more than 0.02%, there is a risk that the continuous porous body may be destroyed due to water rupture phenomenon.
If sodium sulfate is less than 0.001%, the cement cannot be hardened rapidly, and if it is more than 0.002%, the long-term stability of the cement strength is poor. If the citric acid content is less than 0.0005%, each component will be difficult to dissolve.
If it is more than 0.001%, the strength of the continuous porous body will decrease.
If cobalt chloride is less than 0.0001%, the ionic activity of each component cannot be activated, and if it is more than 0.0002%, not only will the effect not be improved, but it will also be expensive. If the content of kaolinite is less than 5%, the aluminum component and trace elements will be insufficient, resulting in a decrease in substitution ability, and if it is more than 20%, Al ₂ O ₃ will be insufficient in the blending ratio, resulting in a decrease in efficacy. If barium oxide is less than 0.001%, the magnetic force will not persist when an electromagnetic field is applied, and if it is more than 0.01%, it will not only be less effective but also more expensive. In addition, if the SiO ₂ and Al ₂ O ₃ components contained in coal fly ash, which is the main raw material, are insufficient, they can be replenished with clay, and if it is necessary to increase the strength of a continuous porous body, it can be used as aggregate. Sand may be used; in this case, the sand is
It is desirable to use 20-40% for 1000Kg. Function The continuous porous body to which an electromagnetic field is applied according to the present invention is configured with continuous pores consisting of micropores and macropores, so water and air can be circulated well, and moreover, there are no voids as a whole, i.e. Large surface area. In addition, it has hydrophobic adsorption and hydrophilic adsorption performance, so-called adsorption performance in both liquid phase and gas phase.
Cations such as Na ⁺ , K ⁺ , Ca ⁺⁺ are captured electrically. As a result, various metal ions contained in the waste liquid etc. that are in contact with the electromagnetic field continuous porous material of the present invention enter many micropores and macropores, and undergo ion exchange with the electrically captured cations. and is absorbed. For example, a solution containing Ca ⁺⁺ ions
When contacted with the electromagnetic field continuous porous material of the present invention that electrically traps Na ⁺ ions, the following exchange reaction occurs. 2A→Na ⁺ +Ca ⁺⁺ →A ₂ Ca+2Na Also, the odor in waste liquid etc. enters the many micropores and macropores and is physically adsorbed. The reaction formula of the electromagnetic field continuous porous material of the present invention with respect to an alkaline malodorous component and an acidic malodorous component is shown below. [Reaction formula for alkaline malodorous components] NH ₃ +A-H→NH ₄ -A (CH ₃ ) ₃ +A-H→(CH ₃ ) ₃ NH-A H ₂ S+B-OH→B-HS+H ₂ O CH ₃ SH+B- OH→CH ₃ S−B+H ₂ O [Reaction formula for acidic malodorous components] NO+KMnO ₄ →KNO ₃ +MnO ₂ 3H ₂ S+8KMnO ₄ →3K ₂ SO ₄ +8MnO ₂ +2KOH
＋2H ₂ O CH ₃ SH＋2KMnO ₄ →CH ₃ SO ₃ K＋2MnO ₂ ＋
KOH 3(CH ₃ ) ₂ S+4KMnO ₄ +2H ₂ O→3(CH ₃ ) ₂
SO ₂ +4MnO ₂ +4KOH By applying an electromagnetic field to a continuous porous body having the above-mentioned exchange-adsorption capacity, in addition to improving the above-mentioned original adsorption-exchange capacity, microcolloids in water, blue powder, Due to the nature of the electromagnetic field, red tide can be rapidly precipitated, resulting in long-term water purification. In other words, the structure of a single water molecule is that among the 10 electrons (5 pairs) present in the molecule, one pair of electrons (inside) is located near the oxygen nucleus, and of the remaining 4 pairs of electrons (outside), One pair is shared between the oxygen nucleus and each proton, while the other two pairs remain undivided by chemical bonds with the proton and occupy the tetrahedral vertices opposite the proton. Water is thus a cooperative system with chains of hydrogen bonds in it, which facilitates hydrogen bonding with neighboring molecules. Water always contains dissolved micro-impurities, and water molecules and their compounds, hydrated ions, or impurity micro-particles undergo vibrational movement corresponding to a certain amount of energy. acts to distort the above-mentioned bonds and change the structural properties, allowing resonance accompanied by the generation of energy.
Changes in the properties of water itself caused by electromagnetic fields change the valence angle of water molecules. That is, it increases the dipole moment of molecules and changes intermolecular interactions, making these polymers coarser. The magnetic susceptibility of water increases as the bond between molecules, which is the sum of the positive polarization magnetic spectrum and the negative diamagnetic component, strengthens, and the magnetic susceptibility of a molecule increases as its chemical potential increases.
When ΔF>0, the magnetization of water within the pseudo defect is greater than that within the pseudo skeleton. When ΔF<0, the opposite correlation holds true. Differences in magnetization under the action of an electromagnetic field lead to changes in the distribution of molecules, which influence the conditions for the progression of chemical reactions in water. Therefore, the action of an electromagnetic field can increase the structure and hydration ability of water, and it has the performance of hydrophilic and hydrophobic adsorption, and the continuous porous body subjected to an electromagnetic field can absorb heavy metal ions, odors, and other substances contained in water. It has an adsorption effect on gases, and has a flocculation and precipitation effect on microcolloids, blue powder, and red tide. Further, according to the manufacturing method of the present invention, it can be manufactured by a simple process of mixing the main raw material such as coal fly ash and various additives, drying, and applying an electromagnetic field during the process. Example: Ammonium chloride for 1000Kg of coal flyash, 130Kg of Portland cement, and 300Kg of sand.
400g, potassium chloride 900g, magnesium chloride
175g, sodium chloride 175g, calcium salt 175
The blending ratio was selected to be 15 g of sodium sulfate, 7.5 g of citric acid, 1.5 g of cobalt chloride, 200 kg of kaolinite, and 1 kg of barium oxide. An electromagnetic field continuous porous body was manufactured in the following manner using the above blending ratio. Coal fly ash 1000Kg as primary treatment
ammonium chloride mixed with powdered
Dissolve 400g and 600g of potassium chloride in 150g of water,
The mixture was mixed with a mixer and dried at 20°C (which can be appropriately selected between 5 and 80°C) to neutralize the ions adsorbed on the coal flyash. Next, as a secondary treatment, 300 kg of sand was added to and mixed with the coal fly ash after the above primary treatment, and then 130 kg of Portland cement was added and mixed. Next, 300g of potassium chloride, which has been mixed and powdered,
Magnesium chloride 175g, sodium chloride 175g,
175 g of calcium chloride, 15 g of sodium sulfate, 7.5 g of citric acid, 1.5 g of cobalt chloride, 200 kg of kaolinite, and 1 kg of barium oxide were dissolved in 100 g of water to make an aqueous solution, and this aqueous solution was sprayed into the mixer during the above mixing. Add and mix 80
It was dried (cured) at a temperature of 0.degree. During the drying reaction (1 to 2 days), an electromagnetic wave generator (manufactured by TDK)
An electromagnetic field was applied for 1 second at 2000 Gauss. After curing in about 28 days, we were able to form a granular electromagnetic field continuous porous material. The electromagnetic field continuous porous material produced in this way is schematically shown in the figure, and this electromagnetic field continuous porous material consists of SiO ₄ Al ₂ O ₄ tetrahedrons sharing oxygen atoms to form oxygen rings. , it has a three-dimensional framework structure in which these are connected, and holes 1a (small) and 1b (large)
The diameter is 50 Å to 300 Å, and the specific surface area is 10 to 15
m ² /g. Since the specific surface area of coal fly ash is 0.9 to 1 m ² /g, the electromagnetic field continuous porous body according to the present invention was able to significantly increase this area. Adsorption tests for various metal ions were conducted under the following test conditions using the continuous porous material of the present invention to which an electromagnetic field was applied and the comparative continuous porous material to which no electromagnetic field was applied. It is shown in Table 1. Test conditions Test equipment: Column water flow test Test method: Pb, Hg, Mn, Cd, Zn, Ni, Cu
Simulated wastewater containing water flow conditions: SV (Space Velocity) = 10H ^-1 LV (Line Velocity) = 1.6m/H Measurement method: Atomic absorption method

[Table] As is clear from the above test results, even a continuous porous material not applied with an electromagnetic field has excellent adsorption capacity, but if a continuous porous material applied with an electromagnetic field of the example of the present invention is used, the adsorption capacity is even higher than that by 10%. % or more. Next, the results of a coagulation-sedimentation test of blue powder in water using the electromagnetic field continuous porous material of the present invention will be explained. Water containing blue powder was collected from Lake Senba in Mito City, Ibaraki Prefecture, and distributed equally into eight beakers. One beaker was not filled with the electromagnetic field continuous porous material of the present invention, and the remaining seven beakers were filled with 1% and 3%, respectively.
%, 5%, 7%, 10%, 15%, and 20% of the electromagnetic field continuous porous material of the present invention. After 28 hours had passed, the coagulation and sedimentation status of the blue powder was examined. As a result, the entire beaker in which the electromagnetic field continuous porous material of the present invention was not charged was cloudy, whereas
In the beaker into which the electromagnetic field continuous porous material of the present invention was charged, the amount of blue powder coagulated and precipitated gradually increased as the amount added increased, and the transparency also increased accordingly. In particular, the effect was remarkable when it was added in an amount of 5% or more, but it was possible to obtain a flocculation-sedimentation effect to the extent that there were no practical problems even when the amount was less than 5%. In addition, when adding 5% or more, the coagulation-sedimentation effect does not change much, and a sufficient coagulation-sedimentation effect can be obtained even if the amount is less than that. Considering economic efficiency, the average amount in the range of 0.05% to 5% It turned out that it is desirable to lay it down. Since blue powder can be coagulated and precipitated as described above, it is clear that suspended matter in water, red tide, etc. can also be coagulated and precipitated. Furthermore, nitrogen compounds can also be adsorbed to the electromagnetic field continuous porous material of the present invention, as is clear from the reaction formula for the malodorous components described above. The fact that the continuous porous body provided with the electromagnetic field of the present invention can exhibit excellent effects in the above-mentioned ion exchange adsorption capacity and coagulation and precipitation of pollutants in water is as follows:
This is also clear from the fact that the water brought into contact with the electromagnetic field continuous porous body increases the oxygen ion concentration in the water depending on the magnetic force and contact time as described below. As the first to fourth embodiments of the present invention, the magnetic force was set to 10, 30, 100, and 130 H・KAm, respectively, and the oxygen ion concentration in water was measured twice for contact time of 3 hours and 5 hours.The results are as follows. (The oxygen ion concentration in the water was measured 3 hours and 5 hours after the water was left in contact with the electromagnetic field continuous porous material, and it was 26.72 mg/.)

[Table] As mentioned above, by using the electromagnetic field continuous porous material of the present invention, it adsorbs heavy metals, gases, and odors, so it is possible to eliminate causes of pollution such as water pollution. It has been experimentally confirmed that porous materials have the property of softening the water they come into contact with, which can prevent water from spoiling and activate it.
It can aggregate and precipitate blue powder and red tide, improve transparency, and prevent oxygen deficiency. After the above secondary treatment, the electromagnetic field continuous porous body of the present invention is subjected to a tertiary treatment by dissolving 50 g of powdered potassium permanganate in 100 g of water, mixing with a mixer, and heating at 20°C (5 to 80°C). Potassium permanganate can be supported by drying with a drying agent (which can be selected as appropriate), thereby preventing the release of odor. In this case, an electromagnetic field may be applied during the drying reaction by this tertiary treatment. Effects of the Invention In summary, the electromagnetic field continuous porous body of the present invention has the following features:
It is a continuous porous body with fine pores that allow water and air to circulate well, has a large specific surface area, has hydrophobic adsorption and hydrophilic adsorption, and has an electric charge.
Furthermore, since an electromagnetic field is applied, it is possible to efficiently adsorb metal ions and odors from various waste liquids, etc., or to coagulate and precipitate microcolloids without using a flocculant to efficiently remove metal ions eluted into water. It can be well adsorbed, or it can efficiently coagulate and precipitate blue powder and red tide in water to prevent oxygen deficiency in water. Further, according to the manufacturing method of the present invention, main raw materials such as coal fly ash and various additives are mixed, dried,
Moreover, it can be manufactured through a simple process of just applying an electromagnetic field during the process, and costs can be reduced. Therefore, it is suitable for processing large quantities of various waste liquids, etc.

[Brief explanation of the drawing]

The figure is a schematic diagram showing the electromagnetic field continuous porous body of the present invention.

Claims (1)

[Claims] 1 Coal fly ash and cement are the main raw materials, ammonium chloride, potassium chloride, magnesium chloride, sodium chloride, calcium chloride, sodium sulfate, citric acid, cobalt chloride, kaolin clay and barium oxide are added, Formed in a continuous porous body that is applied with an electromagnetic field, it adsorbs metal ions and odors in water, coagulates and precipitates microcolloids in water, adsorbs metal ions, and removes blue powder in water.
An electromagnetic field continuous porous body that coagulates and precipitates red tide. 2. Mix coal fly ash with an aqueous solution of ammonium chloride and potassium chloride, dry it, and mix this dried product with cement, potassium chloride, magnesium chloride, sodium chloride, calcium chloride,
An aqueous solution of sodium sulfate, citric acid, cobalt chloride, kaolin clay, and barium oxide is mixed and dried, and an electromagnetic field is applied during the reaction to form a continuous porous body, which adsorbs metal ions and odors in the water. A method for producing a continuous porous body using an electromagnetic field that coagulates and precipitates microcolloids to adsorb metal ions, and coagulates and precipitates blue powder and red tide in water.