JPH0412178B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention adsorbs and purifies harmful metal ions and odors in various waste liquids discharged from factories, etc., and also purifies odors such as domestic wastewater such as human waste. It relates to an adsorbent that adsorbs.

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 metal ions that can efficiently adsorb metal ions and odors, can be easily manufactured, can reduce costs, and are suitable for mass treatment of various waste liquids. and an odor absorbent.

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, sulfuric acid, etc. A continuous porous body was formed by adding sodium, citric acid, and cobalt chloride.

And 1000kg of coal flyash, which is the main raw material.
and ammonium chloride for 50~200Kg of cement.
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% and cobalt chloride at a blending ratio of 0.0001~0.0002%.

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 Å.
At ~300Å, the specific surface area is 10m ² /g ~ 15m ² /g,
By replacing some of the Si with Al, a -1 valent charge is generated, which is neutralized.
It becomes an aluminum silicate compound containing cations such as Na ⁺ , K ⁺ , Ca ^{+ ,} etc. 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.

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.

Effect Since the adsorbent of the present invention has a continuous porous body with micropores and macropores, water and air can be circulated well, and the voids, that is, the specific surface area as a whole are large, and Na ⁺ , K ⁺ , Ca ⁺ and other cations are electrically captured. As a result, various metal ions contained in the waste liquid etc. that are in contact with the adsorbent of the present invention enter many micropores and macropores and are ion-exchanged with the electrically captured cations. It is adsorbed. For example, when a solution containing Ca ⁺⁺ ions comes into contact with the adsorbent of the present invention that electrically captures Na ⁺ ions, the following exchange reaction occurs.

2A→Na ⁺ +Ca ⁺⁺ →A ₂ Ca+2Na Furthermore, since the adsorbent of the present invention has a large specific surface area of 10 to 15 m ² /g due to micropores and macropores, it eliminates many odors in waste liquid, etc. It enters micropores and macropores and is adsorbed.

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 →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 Example Ammonium chloride for 1000Kg of coal fly ash, 125Kg of Portland cement, and 300Kg of sand
400g, potassium chloride 900g (total amount), magnesium chloride 175g, sodium chloride 175g, calcium chloride 175g, sodium sulfate 15g, citric acid 7.5g
g, cobalt chloride 1.5 g.

An adsorbent was manufactured in the following manner using the above blending ratio.

Dissolve 1000 kg of coal fry ash, 400 g of mixed powdered ammonium chloride and 600 g of potassium chloride in 150 kg of water, and mix with a 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.

The adsorbent made of a continuous porous body produced in this way is as shown in the electron micrograph (4200x) taken with X-rays shown in Figure 1 when mixed and dried during the secondary treatment. After the growth process shown in the electron micrograph (19000x) shown in Figure 2,
A continuous porous body is formed as shown in the electron micrograph (19000x) shown in Figure 3. 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)
The diameter is 10 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 adsorbent of the present invention was able to significantly increase this area.

Next, an example will be described in which a metal ion adsorption test was conducted using the adsorbent manufactured according to the above example.

[First test example] Experimental solution (ppm) PH4.45 Cu Zn Al ₂ O ₃ MgO 24.30 21.90 45.25 18.90 The above experimental solution was placed in a container that had a discharge port at the bottom and contained the adsorbent of the present invention example. The results of measuring the amount of adsorption exchange in the adsorbent after supplying and discharging it from the outlet 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 solution (unit: ppm) Cu Zn Pb 19.73 9.77 0.03 The above experimental solution was supplied to a container that had a discharge port at the bottom and contained the adsorbent of the example of the present invention, and was discharged from the discharge port. , was received in a separate container, and the results of detecting this water component 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.

In addition, the adsorbent of the present invention can also adsorb metal ions other than the metal ions shown in the above test examples,
As an example, the adsorption state of Ca and Mn is shown in FIG. 7 and FIG. 8, respectively, taken with an electron microscope using X-rays at a magnification of 300 times. Further, FIG. 9 shows a photograph taken with an electron microscope at a magnification of 300 times of the surface of the adsorbent in a state in which each of the metal ions has been adsorbed.

Effects of the Invention In summary, the present invention is a continuous porous body with fine pores that allow water and air to circulate well, has a large specific surface area, and can electrically conduct cations such as Na ⁺ , K ⁺ , Ca ^{+ ,} etc. It can efficiently adsorb metal ions and odors in waste liquid, etc. In addition, since it can be easily manufactured by simply mixing and drying, it can be provided at low cost, and waste liquid can be processed at a cost several tenths of that of conventional methods, making it possible to process large quantities. Without lakes, rivers,
Helps prevent marine pollution.

[Brief explanation of drawings]

Figure 1 is an electron micrograph taken with X-rays at a magnification of 4,200 times, showing the state in which the various components are mixed and dried during the production of the adsorbent of the present invention, and Figure 2 is an electron microscope photograph taken at a magnification of 19,000 times showing the growth process. The photograph, Figure 3 is a 19000x electron micrograph showing the adsorbent after growth, Figure 4 is its schematic diagram, and Figures 5 to 8 are each
The adsorbent of the present invention shown in Figs.
Figure 9 is an electron micrograph taken with X-rays at a magnification of 300 times showing the state in which Zn, Ca, and Mn are adsorbed.
300 showing the surface of the adsorbent of the present invention adsorbing Mn
This is a magnified electron micrograph.

Claims (1)

[Claims] 1. A metal whose main raw materials are coal flyash and cement, and which is formed into a continuous porous body by adding ammonium chloride, potassium chloride, magnesium chloride, sodium chloride, calcium chloride, sodium sulfate, citric acid, and cobalt chloride. Adsorbent for ions.