JPH0412181B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention purifies harmful metal ions and odors from various waste liquids discharged from factories, etc. by adsorbing them.
The present invention also relates to a method for producing an adsorbent that adsorbs odors from household wastewater such as human waste.

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.

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 a large amount 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.

Therefore, the present invention provides a method for producing an adsorbent for metal ions and odors, which makes it possible to easily produce an adsorbent that can efficiently adsorb metal ions and odors, and to reduce costs. This is what we are trying to provide.

Means for Solving the Problems The technical means of the present invention for solving the above problems is to add ammonium chloride to coal fly ash,
An aqueous solution of potassium chloride is mixed and dried, and cement is mixed with this, and an aqueous solution of potassium chloride, magnesium chloride, sodium chloride, calcium chloride, sodium sulfate, citric acid, and cobalt chloride is mixed and dried to form a continuous porous structure. An aqueous solution of potassium permanganate is impregnated onto the surface of this continuous porous body, and is then dried to be supported.

In the primary treatment of mixing coal fly ash with an aqueous solution of ammonium chloride and potassium chloride and drying it, the mixing ratio of ammonium chloride 0.04 to 0.05%, potassium chloride 0.05 to 0.07%, and water 30 to 40% is applied to 1000 kg of coal fly ash. used, cement, potassium chloride, magnesium chloride, sodium chloride, calcium chloride, sodium sulfate,
In the secondary treatment of mixing an aqueous solution of citric acid and cobalt chloride, 2 to 20% of cement, 0.02 to 0.025% of potassium chloride, 0.02 to 0.025% of potassium chloride,
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 0.0001~0.0002%, water 30
In the tertiary treatment in which an aqueous solution of potassium permanganate is impregnated and supported on the surface of a continuous porous material using a blending ratio of ~40%, 0.002 to 0.01% of potassium permanganate and 20% of water are added to 1000 kg of coal flyash.
Used at a blending ratio of ~30%.

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. At this time, by reacting calcium chloride with cement, the setting time of cement can be shortened, by reacting calcium ions with magnesium chloride, shrinkage of cement can be prevented, and by using cobalt chloride, the above-mentioned Each reaction can be activated. The chemical composition of this continuous porous body is 50-70% _SiO2 ,
Al ₂ O ₃ 10-30%, MgO2-3%, CaO10-20%,
It is 5 to 10% Na, and is connected three-dimensionally while sharing the oxygen atoms at the vertices of the SiO ₄ tetrahedron, and the pore diameter is 10〓.
~300〓, the specific surface area becomes 10m ² /g ~ 15m ² /g,
By replacing some of the Si with Al, a -1 valent charge is generated, and the diameter is to neutralize this.
It becomes an aluminum silicate compound containing cations such as Na ⁺ , K ⁺ , Ca ^{+ ,} etc. inside. Potassium permanganate is supported on the surface of this continuous porous material, which prevents odor from leaving and increases the specific surface area of the continuous porous 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 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 it will be 0.095%.
If the amount is too large, 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 continuous porous material, and if it is more than 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. sodium sulfate
If it is less than 0.001%, it will not be possible to harden the cement quickly, and if it is more than 0.002%, the long-term stability of the cement strength will be poor. If the citric acid content 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 continuous porous body will decrease. If cobalt chloride 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. If potassium permanganate is less than 0.002%, the oxidizing ability will be poor, and if it is more than 0.01%, the effect will not improve.

Also, SiO ₂ contained in coal fly ash,
If the Al ₂ O ₃ component is insufficient, it can be replenished with clay, and if it is necessary to increase the strength of the continuous porous body, sand can be used as aggregate.
In this case, it is desirable to use 20 to 40% of sand per 1000 kg of coal fly ash.

Function The method for manufacturing the adsorbent of the present invention described above can be easily manufactured by simply mixing and drying the main raw material such as coal fly ash and various additives, and
It can be provided at low cost. Since the adsorbent produced by the production method of the present invention is composed of continuous pore pairs of micropores and macropores,
Water and air can be circulated well, and the overall voids, i.e., specific surface area, are large, and Na ⁺ ,
It electrically supplements cations such as K ⁺ and Ca ⁺ .
Various metal ions contained in the waste liquid etc. that are in contact with the adsorbent produced by the production method of the present invention enter a large number of micropores and macropores, and are electrically captured. It is exchanged with ions and adsorbed. For example, when a solution containing Ca ⁺⁺ ions comes into contact with the above-mentioned adsorbent that electrically captures Na ⁺ ions, the following exchange reaction occurs.

2A→Na ⁺ +Ca ⁺⁺ →A ₂ Ca+2Na In addition, the above adsorbent has a large specific surface area of 10 to 15 m ² /g due to micropores and macropores, so
Odors such as waste liquids also enter the large number of micropores and macropores and are adsorbed, and potassium permanganate can prevent the adsorbed odor from leaving.

The reaction formula of the above adsorbent 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 C 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 →3C 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 + 2H ₃ O → 3 (CH ₃ ) ₂ SO ₂ +4MnO ₂ +4KOH Example Dissolve 1000 kg of coal flyash, 400 g of ammonium chloride and 600 g of potassium chloride, which have been mixed and powdered, in 150 g of water. mix with mixer
It was dried at 20°C (which can be appropriately selected between 5 and 80°C) to neutralize 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 125 kg of Portland cement was added and mixed.
Next, mix and powder potassium chloride 300
g, magnesium chloride 175g, sodium chloride 175g
g, calcium chloride 175g, sodium sulfate 15g,
7.5g citric acid and 1.5g cobalt chloride in 100% water
This aqueous solution is added by spraying into the mixer during the mixing process, and mixed at 80℃ (it can be selected appropriately between 5 and 80℃, and the temperature can be increased). (can accelerate curing). This made it possible to produce a continuous porous body. Next, as a tertiary treatment, 50g of powdered potassium permanganate was dissolved in 100% water and added to this continuous porous body, mixed with a mixer, and heated at 20℃ (5 to 80℃ can be selected as appropriate). By drying, an adsorbent supporting potassium permanganate could be produced.

The adsorbent produced in this way, when mixed and dried during the above secondary treatment, is as shown in the electron micrograph (4200x) combined with X-rays shown in Figure 1, and this is shown in Figure 2. After going through the growth process shown in the electron micrograph (19,000x) shown in Figure 3, it becomes a continuous porous body as shown in the electron micrograph (19,000x).
This continuous porous body is schematically shown in Figure 4, and this continuous porous body 1 is three-dimensionally connected while sharing the oxygen atoms at the vertices of the SiO ₄ tetrahedron, and the pores 2 (small ), 3 (large) had a diameter of 10 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 0.9-1 m ² /g, the adsorbent prepared according to the embodiment of the present invention was able to significantly increase this area.

Next, an example in which a metal ion adsorption test was conducted using the continuous porous body produced in the above example will be explained (since potassium permanganate attached to the surface of the continuous porous body does not affect the adsorption of metal ions, This was tested without any attachment.)

First test example Experimental solution (unit: ppm) PH4.45 Cu Zn Al ₂ O ₃ MgO 24.30 21.90 45.25 18.90 It had a discharge port at the bottom and contained a continuous porous body (adsorbent) manufactured according to the example of the present invention. The experimental solution was supplied to the container and discharged from the outlet, and the amount of adsorption and exchange in the continuous porous 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 The adsorption exchange state of Cu and Zn on the 14th day was taken at 300x using an electron microscope combined with As shown in FIG.

Second Test Example Experimental container (unit: ppm) Cu Zn Pb 19.73 9.77 0.03 The above experimental solution was supplied to a container having a discharge port at the bottom and containing a continuous porous body (adsorbent) manufactured according to an example of the present invention. The water was discharged from the outlet and received in another container, and 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 manufactured by the manufacturing method of the present invention can also adsorb metal ions other than those shown in the above test examples, such as Ca,
The adsorption state of Mn was measured using an electron microscope combined with X-rays.
Photographs taken at 300x are shown in Figures 7 and 8, respectively. Further, FIG. 9 shows a photograph taken with an electron microscope at a magnification of 300 times of the surface of the continuous porous body in which each of the metal ions has been adsorbed.

Effects of the Invention In summary, the present invention provides an adsorbent that can efficiently adsorb metal ions and odors in waste liquid, etc., which can be easily manufactured by simply mixing and drying, and can be provided at a low cost. can. Therefore, by using the adsorbent produced by the production method of the present invention, waste liquid can be treated at a cost several tenths of that of conventional methods, and the problem of lakes, rivers, and oceans, which cannot be solved without large-scale treatment, can be treated. Helps prevent pollution.

[Brief explanation of drawings]

Figure 1 shows the manufacturing process according to the manufacturing method of the present invention.
An electron micrograph with X-ray magnification of 4200 times showing the mixed and dried state of each component as a continuous porous body. Figure 2 is an electron micrograph of 19000 times showing the growth process.
Figure 3 is a 19,000x electron micrograph showing the continuous porous material after growth, Figure 4 is its schematic diagram, and Figures 5 to 8 show the continuous porous material shown in Figures 3 and 4, respectively. , 300x electron micrograph showing the adsorbed state of Zn, Ca, and Mn. Figure 9 is a 300x electron micrograph showing the surface of the continuous porous material adsorbing Cu, Zn, Ca, and Mn. It is.

Claims (1)

[Claims] 1 Mix an aqueous solution of ammonium chloride and potassium chloride with coal fly ash and dry it, then mix cement with this and mix an aqueous solution of potassium chloride, magnesium chloride, sodium chloride, calcium chloride, sodium sulfate, citric acid, and cobalt chloride. and drying to form a continuous porous body, impregnating an aqueous solution of potassium permanganate on the surface of the continuous porous body, and drying to support the metal ion adsorbent.