JPH0459038B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is intended to prevent water pollution caused by the elution of heavy metals from the sludge layer accumulated on the bottom of rivers, lakes, and the sea, and to eliminate gases and odors from the accumulated sludge layer. It prevents the occurrence of oxygen deficiency and improves transparency by flocculating and precipitating fine colloid suspensions dissolved in water, blue powder, red tide, etc. that grow in large quantities in water. This article relates to a water purification method that eliminates oxygen deficiency.

Conventional technology When industrial wastewater, domestic wastewater, etc. flows into rivers, lakes, and the sea, the solid organic matter contained therein settles while undergoing decomposition in the water, and some of it is estimated to be It is formed as a sludge layer, the so-called sludge layer. Resuspension and decomposition of organic matter in this sludge layer, etc.
During mineralization, nitrogen compounds and hydrocarbons are generated, and heavy metals are eluted, causing deterioration of water quality and pollution due to odor.

Conventionally, the sludge layer is removed using a dredger. In addition, since there is a limit to the removal of sludge by dredging in large areas such as the ocean, the sludge layer is covered with a sand layer.

Problems to be Solved by the Invention However, the method of removing the sludge layer using a dredger takes a lot of time, and although it is possible to remove the sludge layer in the center of rivers and lakes, it is difficult to remove the sludge layer along the shore. It is not possible to remove the sludge layer in some areas. Additionally, sludge layers cannot be removed in areas where dredgers cannot be used. In addition, in the method of covering the sludge layer with a sand layer, it is possible to remove some organic matter etc. with the sand layer, but a considerable amount remains suspended in the water through the sand layer, and odor and gas cannot be removed at all. . In addition, the sand layer is eroded by waves, and must be replenished each time, requiring enormous construction costs.

To solve these problems, it is possible to treat the sludge layer with an adsorbent, but the conventionally used adsorbents such as activated carbon and synthetic zeolite are expensive and are not used for large-scale treatment of sludge layers. This requires a huge amount of cost, and activated carbon has poor adsorption efficiency in liquid, so it cannot be used to treat sludge layers. Furthermore, until now, there has been no effective way to treat fine colloidal suspensions, blue powder, red tide, etc. dissolved in water, and not only does the water have poor transparency, but especially when blue powder and red tide occur in large quantities. This results in a lack of oxygen and the fish and shellfish die, but the reality is that they are left untreated.

Therefore, the present invention makes it possible to eliminate the cause of pollution caused by the accumulated sludge layer using an adsorbent that can be manufactured easily and at low cost, and also to improve the transparency of water. To provide a water purification method that can eliminate the oxygen deficiency state and, therefore, can purify water even over a large area in a short period of time and at a relatively low construction cost. It is something.

Means for Solving the Problems The technical means of the present invention for solving the above problems is to use coal fly ash and cement as main raw materials, ammonium chloride, potassium chloride, magnesium chloride, sodium chloride, calcium chloride, and sulfuric acid. Sodium, citric acid, and cobalt chloride are added and mixed to form an adsorbent that has an electric charge and is a granulated continuous pore body, and this adsorbent is spread and spread on the bottom of the water to remove the estimated sludge on the bottom of the water. Heavy metals eluted from the layer and gases and odors generated from the accumulated sludge layer are adsorbed onto the above-mentioned adsorbent, or suspensions of particulate colloids dissolved in water, blue powder, red tide, etc. that grow in large quantities in water. It is designed to coagulate and precipitate.

As the above-mentioned adsorbent, ammonium chloride 0.04-0.05%, potassium chloride 0.07-0.095%, magnesium chloride 0.015-0.02 per 1000 kg of coal flyash and 50-200 kg of cement, which are the main raw materials, are used.
%, 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
Used at a blending ratio of 0.0001 to 0.0002%.

When an electromagnetic field is applied, a blending ratio of 5 to 20% kaolinite and 0.001 to 0.01% barium chloride is used, and when potassium permanganate is used, a blending ratio of 0.002 to 0.01% is used.

Mixing coal fly ash and cement with an aqueous solution activates the calcium ion reaction when the cement is in the liquid phase, and also removes humic acid, a polymer compound that inhibits the solidification reaction of cement, with ammonium chloride, sodium sulfate, and citric acid. The particles of SiO ₂ , Al ₂ O ₃ , MgO, K, and Na, which are the main components of coal fly ash, are reacted with the calcium of the cement to normalize the hydration and setting reaction of the cement. The hardened material, which is solidified by providing permeability to calcium ions in the cement through the action of sodium chloride and potassium chloride, becomes a granulated continuous pore material, which is the opposite of a cement solidified material. At this time, by reacting calcium chloride with cement, the hydration and setting time of cement can be shortened, and by reacting calcium ions and magnesium chloride, shrinkage of cement can be prevented, and cobalt chloride can be used. Each of the above reactions can be activated by this.

The chemical composition of the above granulated continuous pore material is SiO ₂ 50-70%,
Al ₂ O ₃ 10-30%, MgO2-3%, CaO10-20%,
Na is 5-10%, SiO ₄ Al ₂ O ₄ tetrahedrons share oxygen atoms to form oxygen rings, forming a three-dimensional framework structure with a continuous pore size of 50 Å to 300 Å.
The specific surface area becomes 10m ² /g to 15m ² /g, and some of the Si is replaced with Al, resulting in -1
Na ⁺ , K ⁺ ,
It becomes an aluminum silicate compound containing cations such as Ca ⁺⁺ inside.

When producing the granulated continuous pore body, an electromagnetic field is applied as necessary, and at this time, kaolinite and barium oxide can prevent a decrease in the sustaining force of the magnetic force when the electromagnetic field is applied. Further, by supporting potassium permanganate on the surface of the granulated continuous pore material, it is possible to prevent odor from being removed and increase the specific surface area of the granulated continuous pore material.

Here, if ammonium chloride is less than 0.04%, each component except potassium permanganate will be difficult to dissolve, and if it is more than 0.05%, the strength of the granulated continuous pore material will decrease. If the potassium chloride content is less than 0.07%, the cement's ability to penetrate calcium ions will be poor;
If it exceeds %, not only will it be difficult to dissolve, but the effect of imparting permeability to calcium ions will not improve. If magnesium chloride is less than 0.015%, shrinkage cracks will occur in the granulated continuous pore material, and if it is more than 0.02%, the granulated continuous pore material will expand. sodium chloride
If it is less than 0.015%, the cement's ability to penetrate calcium ions will be poor, and if it is more than 0.02%, it will not only be difficult to dissolve, but the effect of imparting penetration power to calcium ions will not improve. Calcium chloride is 0.015
If it is less than 0.02%, the strength of the granulated continuous pore material cannot be enhanced, and if it is more than 0.02%, there is a risk that the granulated continuous pore material may be destroyed due to water breaking 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. citric acid
If it is less than 0.0005%, each component except potassium permanganate will be difficult to dissolve, and if it is more than 0.001%, the strength of the granulated continuous pore material will decrease. cobalt chloride
If it is less than 0.0001%, it will not be possible to activate the ionic activity of each component except potassium permanganate, and if it is more than 0.0002%, not only will the effect not be improved, but it will also be expensive. In addition, among the kaolinite, barium oxide, and potassium permanganate that are added as needed, if kaolinite is less than 5%, the aluminum component and trace elements will be insufficient, resulting in a decrease in replacement ability, and if it is more than 20%, the mixing ratio will decrease. The effectiveness decreases due to lack of Al ₂ O ₃ . 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 expensive. Potassium permanganate
If it is less than 0.002%, the oxidizing ability will be poor, and if it is more than 0.01%, the effect will not improve.

In addition, if the SiO ₂ and Al ₂ O ₃ components contained in the coal fly ash, which is the main raw material, are insufficient, they can be replenished with bentonite or clay. It is sufficient to increase the amount of cement and use sand as aggregate.
In this case, it is desirable to use 20 to 40% of sand per 1000 kg of coal fly ash.

Since the above adsorbent is formed into a granulated continuous pore body with micropores and macropores of 50 Å to 300 Å,
Water and gas can be circulated well, and the voids, that is, the specific surface area as a whole are large, and the liquid phase,
It has adsorption ability for both gas phase and electrically captures cations such as Na ⁺ , K ⁺ , Ca ⁺⁺ by generating −1 valent charge and neutralizing this charge. By dispersing this adsorbent and spreading it on the bottom of the water, various metal ions contained in waste liquid that come into contact with the adsorbent are allowed to enter the many micropores and macropores and are captured electrically. It can be adsorbed by ion exchange with cations. For example, when a solution containing Ca ⁺⁺ ions comes into contact with the adsorbent used in the present invention that electrically captures Na ⁺ ions, the following exchange reaction occurs.

2A→Na ⁺ +Ca ⁺⁺ →A ₂ Ca+2Na Nitrogen compounds, hydrocarbons, gases, and odors in waste liquid can also be adsorbed by entering the large number of micropores and macropores.

The reaction formula of the adsorbent used in the present invention for alkaline malodorous components and acidic malodorous components 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 Furthermore, when the adsorbent used in the present invention is sprayed into water as described above, it settles while softening the properties of the water, and at the same time, it settles as suspended matter in the water, or blue powder,
Red tide can be coagulated and precipitated by the force of electric charge.

Furthermore, by applying an electromagnetic field to the adsorbent used in the present invention as described above, the above-mentioned original adsorption effect,
It can promote the coagulation and sedimentation effect, thereby purifying water in the long term. 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, the other two pairs remain undivided and occupy the tetrahedral vertices opposite the proton. In this way, water is a cooperative system with chains of hydrogen bonds in it, which facilitates hydrogen bonding with neighboring molecules. And water always contains dissolved micro impurities, including water molecules and their compounds, hydrated ions,
Alternatively, microparticles of impurities are performing vibrational movement corresponding to a certain amount of energy, but when an electromagnetic field of an optimal frequency acts on this system, the above bonds are distorted and the structural characteristics change, accompanied by the generation of energy. Resonance becomes possible. 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 vector 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. ΔF＞0
When , 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 has the performance of hydrophilic and hydrophobic adsorption. It has an adsorption effect on odors and gases, and has a flocculation and sedimentation effect on microcolloids, blue powder, red tide, etc.

The above adsorbent absorbs 0.05 of the amount of water in rivers, lakes, and oceans.
It is desirable to spread it on average in the range of ~5%. 0.05
If it is less than 5%, the adsorption effect of heavy metals, gases, and odors, or the coagulation and precipitation effect of suspended matter in water, blue powder, red tide, etc., will not be sufficient, and up to 5%, sufficient adsorption and coagulation and precipitation effects will be achieved. Therefore, it is economically wasteful to use more than 5%.

Function The adsorbent used in the present invention can be manufactured easily and at low cost by mixing the material in an aqueous solution and then drying it, and has adsorption performance in both liquid phase and gas phase, and has electric charge. By dispersing this adsorbent and spreading it on the water bottom, heavy metals eluted from the sludge layer at the bottom of the water, nitrogen compounds and hydrocarbons generated from the sludge layer,
It can adsorb gases and odors, or it can coagulate and precipitate suspended particles of colloids dissolved in water, blue powder, red tide, etc. that grow in large quantities in water, due to the charge of the adsorbent, which improves water quality. It is possible to eliminate the causes of pollution such as pollution, or improve the transparency of water and eliminate oxygen deficiency conditions.

Embodiments Hereinafter, embodiments of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic explanatory diagram of an example in which the present invention is applied to a lake.

In FIG. 1, 1 is water, 2 is a sludge layer that is a sludge layer accumulated at the bottom of water 1, and 3 is land.

While moving the hull 4 at low speed on the water 1, the adsorbent 6 is applied to the water 1 using the sprayer 5 loaded on the hull 4.
Spread inside. On the other hand, while moving the vehicle body 7 sequentially on the land 3, the adsorbent 6 is spread into the water 1 by a sprayer 8 loaded on the vehicle body 7. Then, the adsorbent 6 is evenly spread on the sludge layer 2.

The details of the adsorbent 6 will be explained.

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 chloride
The blending ratio was selected to be 175g, sodium sulfate 15g, citric acid 7.5g, and cobalt chloride 1.5g.

Adsorbent 6 was manufactured in the following manner using the above blending ratio.

Dissolve 1000 kg of coal frying ash, 400 g of ammonium chloride and 600 g of potassium chloride that have been mixed and powdered into 150 liters of water, and mix with a mixer to make 20
°C (can be selected appropriately 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 the coal fly ash after the primary treatment and mixed, followed by 130 kg of Portland cement.
Kg was added and mixed. Next, mix and powder potassium chloride 300g, magnesium chloride 175g,
175 g of sodium chloride, 175 g of calcium chloride, 15 g of sodium sulfate, 7.5 g of citric acid, and 1.5 g of cobalt chloride are dissolved in 100 liters of water to make an aqueous solution, and this aqueous solution is added by spray into the mixer during the above mixing, and mixed. It was dried at 80°C (the temperature can be appropriately selected between 5 and 80°C, and curing can be accelerated by increasing the temperature).
This made it possible to form a granulated continuous pore body (potassium permanganate attached to the surface of the granulated continuous pore body did not affect the adsorption of metal ions, so it was not attached). .

The granulated continuous pore body, _which is the adsorbent ₆ produced in this way, is shown schematically in _FIG . It has a three-dimensional framework structure in which the oxygen rings are formed in common and are made continuous, and the holes 6a
(small) and 6b (large) had a diameter of 50 Å to 300 Å, and a specific surface area of 10 to 15 m ² /g. Since the specific surface area of coal fly ash is 0.9 to 1 m ² /g, the above adsorbent 6 was able to significantly increase this area.

Next, an example in which a metal ion adsorption test was conducted using the granulated continuous pore material that is the adsorbent 6 will be described.

[First test example] Experimental solution (unit: PPM) PH4.45 Cu Zn Al ₂ O ₃ MgO 24.30 21.90 45.25 18.90 Granulated continuous pore body (adsorbent) with outlet at the bottom
The above experimental solution was supplied to a container containing the solution and discharged from the outlet, and the amount of adsorption and exchange in the granulated continuous pore body was measured.The results are as follows.

Adsorption exchange amount Cu Zn Al ₂ O ₃ MgO 3 days 2528 1001 452 14 days 99100 31900 63900 12200 [Second test example] Experimental solution (unit: PPM) Cu Zn Pb 19.73 9.77 0.03 Continuous granulation with outlet at the bottom The above experimental solution was supplied to a container containing a porous body (adsorbent), discharged from an outlet, and received by another container. The results of detecting the water components are as follows.

Water component Cu Zn Pb 0.98 0.68 0.002 As is clear from this, the amounts of Cu, Zn, and Pb contained in the liquid are lower than the standard values.

Note that the adsorbent 6 used in the present invention can also adsorb metal ions other than those shown in the above experimental examples.

Next, the results of a flocculation sedimentation test of blue powder in water using the adsorbent 6 used in 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 charged with the adsorbent used in the present invention, and the remaining seven beakers were filled with 1%, 3%, 5%, and 1%, respectively.
The adsorbent used in the present invention was added at a ratio of 7%, 10%, 15%, and 20%. 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 adsorbent used in the present invention was not charged was cloudy, whereas in the beaker in which the adsorbent used in the present invention was charged, blue powder gradually agglomerated as the amount added increased. The precipitation increased, and the transparency also increased accordingly. In particular, the effect was remarkable when 5% or more was added, but a coagulation-sedimentation effect that caused no practical problems could be obtained even when the amount was less than 5%. In addition, when adding 5% or more, the coagulation and sedimentation effect does not change much, and a sufficient coagulation and sedimentation effect can be obtained even with a lower amount. Considering economic efficiency, it is recommended to use an average amount of 0.05 to 5%. was found to be desirable.

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.

Further, nitrogen compounds can also be adsorbed on the adsorbent 6 used in the present invention, as is clear from the reaction formula for the malodorous components described above.

Then, as mentioned above, the adsorbent 6 spread evenly on the sludge layer 2 adsorbs nitrogen compounds and hydrocarbons generated from the sludge layer 2, heavy metals eluted from the sludge layer 2, and gases and odors generated from the sludge layer 2. Therefore, causes of pollution such as water pollution can be removed and oxygen deficiency can be prevented. In addition, it has been experimentally confirmed that the adsorbent 6 has the property of softening the water it comes into contact with, thereby preventing water from spoiling and activating it. , blue powder, and red tide can be aggregated and precipitated, improving transparency and preventing oxygen deficiency.

In order to apply an electromagnetic field to the adsorbent 6 used in the present invention, it is sufficient to add 200 kg of kaolinite and 1 kg of barium oxide in the secondary treatment step, and apply an electromagnetic field during the reaction of the secondary treatment step. The above adsorption effect is achieved by applying an electromagnetic field to
The coagulation and sedimentation effect can be further improved. After the above secondary treatment, as a tertiary treatment, 50 g of powdered potassium permanganate is dissolved in 100 liters of water, mixed with a mixer, and heated at 20℃ (5 to 80℃ can be selected as appropriate). By drying, an adsorbent supporting potassium permanganate can be produced, thereby preventing odor from being removed.

Effects of the Invention In summary, according to the present invention, the adsorbent used can be easily produced at low cost by mixing the material in an aqueous solution and then drying the adsorbent. Then, by dispersing the above adsorbent and spreading it evenly in the water, the causes of pollution caused by the accumulated sludge layer can be removed, or suspended matter in the water, blue powder, red tide, etc. can be coagulated and settled to improve transparency. , oxygen deficiency can be prevented, and therefore water can be purified in a short period of time and at relatively low construction costs even in large areas of rivers, lakes, and oceans.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing an embodiment of the water purification method of the present invention, and FIG. 2 is a schematic diagram showing an adsorbent used in the present invention. 1...Water, 2...Sludge layer (sludge layer), 3
... land, 4 ... hull, 5 ... spreader, 6 ... adsorbent, 7 ... vehicle body, 8 ... spreader.

Claims (1)

[Claims] 1 Coal fly ash and cement are used as the main raw materials, ammonium chloride, potassium chloride, magnesium chloride, sodium chloride, calcium chloride, sodium sulfate, citric acid and cobalt chloride are added, mixed and charged to form a granulated continuous pore material. An adsorbent is formed, and this adsorbent is spread and spread on the water bottom, and the heavy metals eluted from the estimated sludge layer at the bottom of the water, as well as gases and odors generated from the estimated sludge layer, are adsorbed to the above adsorbent. , or suspension of particulate colloid dissolved in water, blue powder that grows in large quantities in water,
A water purification method characterized by coagulating and precipitating red tide, etc.