JPS62254838A - Additive for adsorbent for metallic ion and odor - Google Patents

Abstract

PURPOSE:To efficiently adsorb both metallic ions contained in waste liquid or the like and odor by blending potassium permanganate powder to the mixed powder of ammonium chloride and potassium chloride or the like and the mixed powder of citric acid and cobalt chloride or the like. CONSTITUTION:Ammonium chloride and potassium chloride are mixed and pulverized and potassium chloride, magnesium chloride, sodium chloride, sodium sulfate, citric acid and cobalt chloride are mixed and pulverized. Furthermore potassium manganate is mixed thereto and the mixture is pulverized to prepare an additive for an adsorbent for metallic ions and odor. Coal fly ashes and cement, etc., are used as an essential raw material and this additive for the adsorbent is constituted to a continuous porous body due to micro pores and macro pores. This continuous porous body is large in the specific surface area and cations are trapped thereon, and various kinds of metallic ions are ion- exchanged with the above-mentioned cations and adsorbed.

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 in frozen areas etc. The invention relates to additives added to main raw materials such as coal fly ash in order to produce a smoke absorbent 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, and the current situation is that they are discharged untreated, causing pollution by contaminating lakes, rivers, and the sea.

Therefore, the present invention aims to provide an additive that can easily produce an adsorbent that can efficiently adsorb metal ions and odors, and that can reduce costs. .

Means for solving the problems The technical means of the present invention for solving the above problems are as follows:
ammonium chloride, potassium chloride, magnesium chloride,
Consisting of sodium chloride, calcium chloride, sodium sulfate, citric acid, cobalt chloride and potassium permanganate, ammonium chloride and potassium chloride are mixed and powdered, potassium chloride, magnesium chloride, sodium chloride, calcium chloride, sodium sulfate, Citric acid and cobalt chloride are mixed and powdered, and potassium permanganate is powdered.

And for 1000 kg of coal fly ash and 50 to 200 kg of cement, which are the main raw materials, there is no ammonium chloride.
．． 04-0.05%, potassium chloride 0.07-0.09
5%, 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 o, ooos~o, ooi%, cobalt chloride 0.0001~0.0002%, potassium permanganate o,.

Used at a blending ratio of O2 to 0.01%, ammonium chloride 0.04 to 0.05% and potassium chloride 0.05%.
~0.07% and powdered potassium chloride 0.0
2-0.025%, magnesium chloride 0.015-0.
02%, sodium chloride 0.015-0.02%, calcium chloride 0.015-0o02%, sodium sulfate 0
．． ool ~0.002%, citric acid 0°0005~0
．． 001% and 0 cobalt chloride.

0001 to 0.0002% are mixed and powdered, and 0.002 to 0.01% of potassium permanganate is powdered.

By mixing coal fly ash with an aqueous solution of cement, calcium ion reactions are activated when the cement is in the liquid phase, and humic acid, which is a polymer compound that inhibits the solidification reaction of cement, is removed by ammonium chloride, sodium sulfate, and citric acid. 5ift, AhOs, and MgO1, which are the main components of coal fly ash, are removed by reacting with acid.
The particles of K and Na react with the calcium in the cement to perform the original function of the cement. 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 5i02.50-70%, AIzO310-30%
, Mg02-3%, Ca010-20%, Na5-1
0%, they are three-dimensionally connected while sharing the oxygen atoms at the vertices of the SiO+tetrahedron, the pore diameter is IOA ~ 300A, the specific surface area is 10rn'/g ~ L5rn'/g, and some of these Si By replacing with AI, a monovalent charge is generated, which is neutralized by adding + and Ca+ to Na1.
It becomes an aluminum silicate compound containing cations such as 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,
If it exceeds 5%, 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; 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 it is less than .015%, shrinkage cracks will occur in the continuous porous material;
If it exceeds 2%, 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, and if it is more than 0.02%, it will not only be difficult to dissolve, but the effect of imparting Pm force to calcium ions will not improve. If it is less than .015%, the strength of the continuous porous material cannot be improved, and the
．． If it exceeds 0.02%, there is a risk that the continuous porous body will be destroyed due to water breaking phenomenon. If the sodium sulfate content is less than o, oot%, the cement cannot be cured rapidly;
If it exceeds 0.02%, 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 o, oot%, the strength of the continuous porous body will decrease. Cobalt chloride is 0.
If it is less than 0.001%, the ionic activity of each component except potassium permanganate cannot be activated;
If it is more than 0.02%, not only will the effect not be improved, but it will also become 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.

In addition, S contained in coal fly ash, which is the main raw material,
If the ioz and AlzOi components are insufficient, they 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, the sand can be replaced with 1000 kg of coal fly ash. Against, 20
It is desirable to use ~40%.

Function The adsorbent additive of the present invention uses coal fly ash, cement, etc. as the main raw materials, and is constructed into a continuous porous body with micropores and macropores, which allows water and air to circulate well, and has a The voids, that is, the specific surface area are large, and H
It is possible to produce an adsorbent that electrically captures cations such as a'', K'', Ca+, etc. Various metal ions contained in the waste liquid, etc. that are in contact with the adsorbent produced in this way enter many micropores and macropores, and are separated from the electrically captured cations. When a solution containing 0, for example, Ca ions to be ion-exchanged and adsorbed, comes into contact with the above-mentioned adsorbent that electrically captures Na+ ions, the following exchange reaction occurs.

2 A + Na” + Ca +AzCa+ 2
Ha and odors in waste liquid etc. also enter the numerous micropores and macropores and are adsorbed, and potassium permanganate can prevent the adsorbed odors from leaving.

Example: 1000 kg of coal fly ash, 125 kg of Portland cement, 300 kg of sand, 400 kg of ammonium chloride, 900 g of potassium chloride, 175 g of magnesium trichloride, 175 g of sodium chloride, 175 g of calcium chloride, 15 g of sodium sulfate, 7.5 g of citric acid.
, cobal chloride) 1.5g, potassium permanganate 50g
Ammonium chloride 4
00g and 600g of potassium chloride were mixed and powdered,
Potassium chloride 300g, ffi magnesium 175g
, sodium chloride 175g, calcium chloride 175g,
15 g of sodium sulfate, 7.5 g of citric acid, and 1.5 g of cobal chloride were mixed and powdered, and 50 g of potassium permanganate was powdered.

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

400 g of ammonium chloride and 60 g of potassium chloride mixed with coal fly ash and powdered.
Dissolve 0g in 150ml of water, mix with a mixer and heat to 20°C.
As a secondary treatment, the coal fly ash is dried at a temperature of 5 to 80°C (which can be selected as appropriate) to neutralize the coal fly ash.
Add 0 kg and mix, followed by 1 kg of Portland cement.
25 kg was added and mixed. Next, mix and powder 300g of potassium chloride and 175g of magnesium chloride.
, aNIZ sodium 175g, calcium chloride 175g
g, 15 g of sodium sulfate, 97.5 g of citric acid, and 1.5 g of cobal chloride) were dissolved in 100 g of water to make an aqueous solution, and this aqueous solution was added by spray into the mixer during the above mixing, and mixed to 80 g. It was dried at a temperature of 5°C to 80°C (which can be appropriately selected between 5 and 80°C, and curing can be accelerated by increasing the temperature). As a result, a continuous porous body was formed.6 Next, as a tertiary treatment, 50 g of powdered potassium permanganate was dissolved in 10041 water, mixed with a mixer, and heated to 20"C. By drying at a temperature of 5 to 80°C (which can be appropriately selected), an adsorbent supporting potassium permanganate could be produced.

The adsorbent produced in this way, when mixed and dried during secondary treatment, is as shown in the electron micrograph (4200x) combined with X-rays shown in Figure 1, which is shown in Figure 2. After the growth process in the electron micrograph (19,000x), the electron micrograph (19,000x) shown in Figure 3 is obtained.
It becomes a continuous porous body as shown in . A schematic representation of this continuous porous body is shown in FIG. 4, and this continuous porous body 1 has 5
They are three-dimensionally connected while sharing the oxygen atoms at the vertices of the ino tetrahedron, and the diameters of pores 2 (small) and 3 (large) are IOA ~ 3.
00λ and the specific surface area was 10 to 15 tf/g.The specific surface area of coal fly ash was 0.9 to 1 m'/g.
Therefore, we were able to significantly increase this.

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) pH 4,45 Cu Zn AlzO3MgO24,30
21,9045,2518,90 Has an outlet at the bottom,
The experimental solution was supplied to a container containing the continuous porous body (adsorbent) and discharged from the outlet, and the amount of adsorption exchange in the continuous porous body was measured. The results are as follows.

Adsorption exchange amount Cu Zn Al2O3Mg03 days 252
8 1001 45214 days 9
9100 31900 63900 12200
The adsorption and exchange state of Cu and Zn on the 14th day was photographed at a magnification of 300 times using an electron microscope combined with X-rays, as shown in FIGS. 5 and 6, respectively.

[Second test example] Experimental solution (unit: PPM) Cu Zn Pb +9.73 9.77 0.03 The experimental solution was supplied to a container containing the continuous porous body, which had a discharge port at the bottom, and the discharge port The results of detecting the components of the discharged water are as follows.

Water component Cu Zn Pb 0.98 0.88 0.002 As is clear from this, the amounts of Cu, Zn, and Pb contained in the liquid are lower than the standard values.

The above adsorbent can also adsorb metal ions other than the metal ions shown in the above test examples.
, Figures 7 and 8 show the state of Mu adsorption taken using an electron microscope combined with X-rays at a magnification of 300 times, respectively, and the surface of the continuous porous body with the above metal ions adsorbed was taken using an electron microscope. Figure 9 shows a photograph taken at 300x magnification.

Effects of the Invention In short, the present invention provides an adsorbent that can efficiently adsorb metal ions and odors in waste liquid, etc., and can be easily manufactured by simply mixing and drying the main raw material such as coal fly ash. Therefore, we can provide it at low cost,
Waste liquid can be treated at a cost several tenths of that of conventional methods, and it helps prevent pollution in lakes, rivers, and the sea, which cannot be solved without large-scale treatment.

[Brief explanation of drawings]

Figure 1 is a 4200x xvi electron micrograph showing the state in which each component is mixed and dried as a continuous porous body during the production of an adsorbent using the additive of the present invention, and Figure 2 shows the growth process. Electron micrograph at 19,000x magnification, No. 3
The figure shows a 19,000x electron micrograph showing the continuous porous material after growth, Fig. 4 is a schematic diagram thereof, and Figs. 5 to 8 show Cu,
Figure 9 is an electron micrograph taken with X-rays at a magnification of 300 times showing the adsorbed state of Zn, Ca, and Mn.
This is a 300x electron micrograph showing the surface of a continuous porous material that has adsorbed n. Patent applicant Taguchi Research Institute Co., Ltd. Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8

Claims (1)

[Claims] ammonium chloride, potassium chloride, magnesium chloride,
Consisting of sodium chloride, calcium chloride, sodium sulfate, citric acid, cobalt chloride and potassium permanganate, ammonium chloride and potassium chloride are mixed and powdered, potassium chloride, magnesium chloride, sodium chloride, calcium chloride, sodium sulfate, An additive for a metal ion and odor adsorbent, characterized in that citric acid and cobalt chloride are mixed and powdered, and potassium permanganate is powdered.