JPS59374A - Filtering agent for water disposal - Google Patents

Abstract

PURPOSE:To obtain the filtering agent for the catalytically oxidizing treatment of water to remove Mn content, humic acid, etc. from underground or surface water, by concomposing it from the specified amounts of manganese oxide, an inorganic binder and light-weight aggregate. CONSTITUTION:The filtering agent for water disposal is composed of, by wt%, 40-80 manganese oxide, 15-50 an inorganic binder and 5-50 lightweight aggregate. MnO2 or Mn2O3 as said manganese oxide, one or more of hydraulic cement, air-setting cement, alkali silicate and glass frit as said inorganic binder, and lapilli, puzzolana, acid clay or the like having apparent specific gravity below 2 as said lightweight aggregate are respectively used. These constitutional materials are granulated and used as a granulated body having apparent specific gravity below 1.2g/cc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a P material for catalytic oxidation water treatment that removes soluble metals and soluble organic acids, such as iron, manganese, humic acid, etc. contained in groundwater, surface water, etc.

Conventionally, a catalytic oxidation method has been widely used as a treatment technology for water containing iron and manganese. Offshore materials used in this catalytic oxidation method generally include manganese sand, manganese zeolite, or soft manganese ore, and manganese sand is actually widely used.

Manganese sand is made by coating the surface of sand with manganese oxide. Generally, silica sand is used as a carrier particle, and sand particles of 1 m are used.
After adding 150% of a 3% by weight aqueous solution of manganese chloride and mixing thoroughly, 7501% of a 3% by weight aqueous solution of potassium permanganate was added and stirred again to remove catalytically oxidizing MnO2/H2O from the surface of the sand particles. Manganese zeolite is also produced in a similar manner. The reaction is shown below.

13 Mn” +2 MnO4−+7 H2O−)
5 Mn 02 ・H20+ 4 H”The manganese sand obtained as described above has the following drawbacks.

1) A film of MnO2/H2O is not uniformly formed on the surface of the carrier. 2) The utilization efficiency of manganese chloride and potassium permanganate is poor. 3) The catalytic oxidation performance is low, and although it is effective for iron removal, It has almost no effect on manganese ability, and large amounts of C12 and 03 are required to increase iron removal ability. 4) When backwashing and regeneration operations are repeated, manganese dioxide adhering to the surface of the carrier falls off and flows out, resulting in large losses, resulting in large deterioration. 5) Strict filtration conditions (linear velocity, space velocity). As a result, the iron removal effect will be extremely reduced. However, the advantage is that the apparent specific gravity is 1.2 and 0.1.
Since the target is relatively small, the amount of backwash water during backwashing and regeneration is small, and manganese sand can be regenerated in a short time.

Disadvantages of such mango-'d and manganese zeolites E
In order to solve this problem, the present inventors previously proposed the use of electrolytic manganese dioxide particles (Japanese Patent Publications No. 52-14543 and No. 52-14544).

That is, electrolytic manganese dioxide, which has been electrolytically extracted using a manganese salt solution, is washed with water, deoxidized, and coarsely pulverized using a pulverizer to be used as a furnace material for catalytic oxidation water treatment. These manganese dioxide grains have a higher ability to remove iron and manganese than conventional manganese sand and manganese zeolite, and in particular have a significantly high ability to remove manganese, which is difficult to remove with the catalytic oxidation method using manganese sand. However, the apparent specific gravity of manganese dioxide grains is 2.5±0.6! ? Large 100, backwash.

The drawback is that the amount of backwash water used during regeneration is large, and it takes a long time to regenerate manganese dioxide particles.

However, due to its large catalytic oxidation ability, the number of backwashing and regeneration times is much lower than that of conventional manganese sand, so the total water volume of backwashing water is much smaller.

In addition, the present inventors had previously proposed a furnace material for granular water treatment consisting of manganese dioxide and an inorganic binder (Japanese Patent Publication No. 5
1-36944). That is, appropriate amounts of manganese dioxide powder and alumina cement powder are mixed, water necessary for molding is added and kneaded, and used as a granular molded product. By using this molded product as a furnace material for catalytic oxidation water treatment, it can withstand repeated use better than manganese dioxide grains, although its manganese removal ability is slightly inferior to that of manganese dioxide grains. Also, the apparent specific gravity is 1 compared to manganese dioxide grains.
．． It has many advantages, such as being small at 6±o, 2&1°, and requiring less backwash water. However, compared to manganese sand, the amount of backwash water is large.

As described above, the furnace material proposed by the present inventors has advantages and disadvantages.

The present invention takes advantage of these advantages.

In other words, it is a granular material whose main components are manganese oxide, an inorganic binder, and lightweight aggregate, and the manganese oxide content is 40 to 8.
This water treatment furnace material has a composition range of 0 weight ratio, an inorganic binder of 16 to 60 weight ratio, and a lightweight aggregate of 6 to 45 weight ratio.

Each component will be explained in detail below.

(A) Manganese oxide As manganese oxide, manganese dioxide (Mn02),
Manganese sesquioxide (Mn206), trimanganese tetraoxide (
Mn30a) is a typical example, and usually undergoes crystal transformation as described below by heat treatment.

Mn o2soo-<ao'c Mn2o, cars
o-*ooo'c,,,o4 Especially for MnO2, 7-
There are MnO2, β-MnO2, α-Mn02, and MnO2.
α-Mn205 is well known as n2O3. Among these manganese oxides, the activity for removing iron, removing manganese, and removing humic acid is as follows: 7-Mn0z)β-Mn02≧a-Mn02)a-M
n20s )) Mn3O4 order.

Such activity can be compared by a test method using a column as shown in FIG. In this test method, a column 1 with an inner diameter of 50 mm is filled with various manganese oxides 2 prepared under the following conditions, and the Mn2+ concentration is 5.
ppm, mixed raw water 3 with a sodium hypochlorite concentration of 1.0 to 0.8 ppm converted to residual chlorine at a flow rate e o cc
The Mn in the treated water was
This measures the 2+ concentration and residual chlorine, allowing comparison of the catalytic oxidation ability of various manganese oxides.

Note that a porous glass filter is installed as a hearth 5 below the various manganese oxides.

The γ-MnO2 grains of iK 1 were prepared in a sulfuric acid acidic manganese sulfate bath (Mn"0.6""/1, H2S 040-6
N) at a bath temperature of 95°C and a current density (D4) of 0.
γ-Mn collected by electrolysis at 8 A/dm' for 2 weeks
O2 was peeled off from the anode plate and deoxidized using Na2CO3 so that the Mn02O2O pH value in a 20% by weight aqueous solution of NH4Cl was 4.6 according to JIS-1467.

The a-MnO2 grains of A2 are made by treating the β-Mn02 with dilute H2SO4 (with K+) and 0
．． It was obtained by adding 0.1 mono71 of KCI to 5N H2SOA and treating at 50 to 60°C for 4 hours.

Next, the A3 β-Mn02 grains are the γ-MnO2t)
"f heat treated at 250℃ for 2 hours, A4 a-M
n205 is 1.7-MnO2 grains heat-treated at 5Q/6°C for 2 hours. The Mn3O4 grains of +F1i5 were heat treated at 960° C. for 2 hours, and A6 was manganese sand as a comparative sample. The results of measuring the catalytic oxidation ability of the manganese oxide thus prepared are shown in FIG. Further, the specific surface area (measured by the Bli:T method) of each manganese oxide is as follows.

A1 γ-MnO248m2/ y I6.2 β-MnO223m”/ fA3 a
-MnO218rn”/ fA4 a-Mn2031
0m"/p A 5 Mn304 0-5 m'/fA6
As is clear from the results of manganese sand 0.9 rn” / 9 or more, γ-MnOz has particularly excellent demanganizing ability, followed by β-MnO2, α-MnO2, and α-Mn20.
s has at least 6 times more manganese removal ability than conventional manganese sand. However, although Mn5O< has a slightly better manganese removal ability than manganese sand, it cannot be said to be preferable due to manufacturing methods such as high-temperature firing. That is, as the manganese oxide, manganese dioxide with a concentration of 32 P/cc or less is more preferable. If aggregate with an apparent specific gravity of 2.0'/ca or more is used, the above-mentioned backwashing will occur.

The amount of backwash water during regeneration increases, and the time required for regeneration becomes longer. This leads to an increase in the apparent specific gravity of the water treatment furnace material. That is, it is difficult to reduce the apparent specific gravity of the water treatment furnace material to 1.2'/cc or less.

For the following reasons, preferred lightweight bone materials are artificial zeolite, activated carbon, calcium silicate, coal ash, volcanic rubble, eidoplanu, and resin powder. In particular, it is advantageous to use coal ash because the ash contains trace amounts of minerals (oxides of alkali metals and alkaline earth metals).
Furthermore, it will lead to the effective use of coal ash, which is disposed of in large quantities as industrial waste.

Next, the composition ratio of manganese oxide, inorganic binder, and lightweight aggregate will be explained.

As a typical example, γ-MnOz powder (3
Alumina cement (commercially available, Hi-Alumina Cement manufactured by Denki Kagaku Kogyo Co., Ltd.) was used as the inorganic binder, and synthetic zeolite (F1 manufactured by Toyo Soda Co., Ltd.) was used as the lightweight aggregate. After thoroughly mixing these at the compounding ratio shown in Table 1, water necessary for molding was added and kneaded. This kneaded material was molded using an extrusion molding machine with a diameter of ○ and Bm.
After creating a pellet and drying the surface, immediately use a spherical machine to
The particles were shaped into spheres (beads), and after curing, they were sized to a size of 16 to 48 meshes and used as water treatment furnace material.

The apparent specific gravity of the γ-MnO2 powder, alumina cement, and synthetic zeolite used here are 2 and 2, respectively.
ts mo. , 1.61i100.1.31'/,. It is.

However, the apparent specific gravity was measured by weighing 20y of the raw material powder into a colorimetric tube with an inner diameter of 12mm and a length of 300g, and tapping it for 30 minutes. Further, in the table, the apparent specific gravity of the water treatment furnace material was measured in the same manner as described above. Mechanical strength was determined by filling the column shown in Figure 1 with 60 cc of water treatment furnace material, and increasing the backwash expansion rate (volume % of the volume before flowing water to the apparent volume increased by backwash water) to 60% (apparent volume). Volume 76
cc) and was evaluated based on the weight loss rate after 1 hour of backwashing, and the weight loss rate was 0 to 5% by weight, ◎, and 5 to 10% by weight.

As is clear from Table 1, when the amount of inorganic binder added is 16% by weight or less, the mechanical strength is significantly reduced. If the amount of synthetic zeolite is less than 6% by weight, the apparent specific gravity will be less than 1.2 mm/cc, which is not preferable. On the other hand, if it exceeds 50% by weight, the apparent specific gravity is favorable, but the mechanical strength decreases.

From the above, if the inorganic binder is 16% by weight or less and the lightweight aggregate is 60% by weight or less, a water treatment furnace material with high mechanical strength can be obtained. On the other hand, when apparent is a specific gravity, if the amount of inorganic binder is 60% by weight or less and the lightweight aggregate is 5% by weight or more, an excellent F material for water treatment with a small apparent specific gravity can be obtained.

Next, regarding the original properties, that is, the purifying ability, the manganese removal ability was compared under the test conditions described in the comparison of the characteristics of manganese oxides. However, if the manganese removal ability of commercially available manganese sand is 1
◎ is 10 times or more, ○ is 6 to 10 times, △ is 2 to
6 times, × represents 2 times or less.

As is clear from Table 1, when the amount of manganese oxide is 30% by weight or less, it is comparable to or slightly better than commercially available manganese sand.

From the above, manganese oxide is 40 to 80% by weight,
Inorganic binder: 16-60% by weight, lightweight aggregate: 5-5%
A range of 50% by weight is preferred.

Below Below Other White Table 1 Hereinafter, the present invention will be explained in more detail based on Examples.

Example 1 γ-Mn0260% by weight, alumina cement 25% by weight, and various aggregates with different apparent specific gravity as shown in Table 2 15
After mixing the weight%, water necessary for molding was added and wet-mixed to create a granulated molded product with a diameter of 0.81 tM, and after curing in warm water, it was washed with water, dried, and sized to 16 to 48 mesh size. did. The apparent specific gravity of the granulated lightweight aggregate 1 was measured using the colorimetric tube described above.

The ability to remove manganese was determined by filling the column shown in Figure 1 with furnace material SOCA, and raw water containing s, opm of Mn2+ and 1.0 to 0, sppm of residual chlorine at a linear density of 1.87 m.
/h and space velocity of 7.2 h-' through the column.

However, the mechanical strength was evaluated by the weight loss rate when backwashing was performed for 1 hour with a backwash development rate of 60%. The regeneration ability was determined by using the above-mentioned raw water, and when the Mn2+ concentration in the treated water became 0.3 ppm or more, that is, 0.35 ppm, the supply of raw water was stopped, and backwash regeneration was performed for 30 minutes at a backwash water rate of 31/min. Decrease rate of manganese removal ability after 20 cycles, that is, amount of treated water with initial manganese removal ability of 0-0.3 ppm Q1
The ratio Q+/Q2 of the manganese removal capacity 0 to o after 20 cycles and the amount of treated water Q2 of appm is 1.0 to 0.9.
, 0.9 to 0.7 was evaluated as 0.0.7 to 0.5 as Δ, and 0.5 or less as ×.

These evaluation results are shown in Table 2.

Below Margin When the specific gravity of bone H is 2.0'/cc or more, the specific gravity of the molded material of water treatment furnace material is 1 or 2! ? /c
c or more, and the deterioration of life especially during reuse becomes significant. In other words, if the apparent specific gravity of the molded product is large during backwash regeneration, the backwash expansion rate will be small and the MnO2/H2O layer attached to the surface of the P4A particles for water treatment will be less likely to be desorbed, which will have a large impact on the lifespan. give. On the other hand, if the backwash expansion rate becomes too large, the furnace material particles collide with the particles, which increases the wear of the particles, which is not preferable. From the table, the apparent specific gravity of preferable P uses for water treatment is 0.8 to 1. ,21'/,0. Although not specified in the table, in the case of chemically treated γ-MnO2 (apparent specific gravity 1.8, p-/cc), the preferred water treatment furnace material has an apparent specific gravity of 0.6 to 1.2 units. It was within the range of From the above, the apparent specific gravity is preferably 2'/'cc or less3. Example 2 γ-MnO 250% by weight, as an inorganic binder, light calcium carbonate 40% by weight, and coal ash 1% as a lightweight aggregate.
Table 3 shows the results of making a furnace material using the same manufacturing mold as in Example 1 and evaluating it under the same conditions as S using 0% by weight.

Table 3 Example 3 Chemical treatment of manganese oxide in the plate 4 of Example 1 γ-Mn
O2 (specific surface area 110''7'y) and tx-M obtained by heat treating the chemically treated γ-Mn02 at 550°C for 2 hours.
In place of nzOs (specific surface area 20 rr?7.), a furnace material was made of 3U made in the same manner as in Example 1, and the results were evaluated under the same conditions as shown in Table 4.

As is clear from Table 4, there is almost no difference depending on the crystal system or manufacturing quality of manganese oxide. In particular, the ability to remove manganese is another 11.
In the order of 〉A4〉Flat 12, A11 obtained excellent results. This is the specific surface area of manganese oxide, in other words, P4-A
Due to the difference in specific surface area. The specific surface area of NOFlli11°4.12 is 70/y+32'/y+211+, respectively, and it can be said that 1 o rn'/or more is preferable.

Example 4 The lightweight bone phase of Example 10A3 was mixed with polyethylene powder (100
(100% below mesh) instead. Furnace materials were made using the same method as in Example 1 and evaluated under the same conditions. Table 6 shows the results.

Table 5 Example 5 Table 6 shows the evaluation results of the furnace materials of Example 2 with various inorganic binders.

The composition is shown in Table 7. The furnace material using this frit as a binder is a mixture of manganese oxide, binder and aggregate.
0.6 parts by weight of carboxymethylcellulose as a molding aid was added to 0.00 parts by weight to form a molded product, which was then baked at 500° C. for 10 minutes to produce a molded product.

As is clear from FIG. 6 and Table 6, good results were obtained when various inorganic binders were used alone or in combination. Further, molding can be carried out by adding molding aids such as secondary binders and moldability improving agents. Although it is preferable to use a forming aid that thermally decomposes at a relatively low temperature (6o O'C or less), it may be included in the furnace material in a small amount, preferably 5 weight or less.

As shown in E-H, the water treatment furnace material of the present invention has excellent catalytic oxidation ability, particularly high manganese removal ability, is easy to regenerate, and can withstand long-term use.

[Brief explanation of the drawing]

FIG. 1 is a schematic vertical cross-sectional view of a column test device for measuring the manganese removal ability of water treatment swamp materials, and FIG. 2 shows a comparison of the manganese removal ability of various manganese oxides. Name of agent: Patent attorney Toshio Nakao and one other name
1. Written amendment to figure procedure (method) October 3, 1988 Mr. Commissioner of the Japan Patent Office ■Case description 1988 Patent Application No. 109415 2. Name of the invention r-material for water treatment 3. Person making the amendment Relationship to the case Special Permission Application Appointment Address 1006 Bold Kadoma, Kadoma City, Osaka Prefecture Name
(582) Matsushita Electric Industrial Co., Ltd. Representative Yama
Toshihiko Shimo 4 Agent 571 Address Matsushita Electric Industrial Co., Ltd. 1006 Kadoma, Kadoma City, Osaka Prefecture The composition of the glass frit powder used in No. 17 was
Shown in the table. R material using this frit as a binder is made by adding 0.6 parts by weight of carboxymethyl cellulose as a molding aid to 100 parts by weight of a mixture of manganese oxide, binder and aggregate, and forming a molded product at 500°C. It was produced by baking for a minute. Table 7

Claims (1)

[Scope of Claims] (1) A water treatment furnace material comprising manganese oxide, an inorganic binder, and lightweight aggregate in an amount of 5 to 50% by weight. (2) The P material for water treatment according to claim 1, wherein the manganese oxide is selected from the group consisting of manganese dioxide and manganese sesquioxide. (3) The inorganic binder is hydraulic cement, Claim 1, which is at least one member selected from the group consisting of air-hard cement, alkali silicate, and glass frit.
Use of P for water treatment as described in section. (4) The F material for water treatment according to claim 1, wherein the apparent specific gravity of the light-sparing bone material is 2.0 or less. (6) The F material for water treatment according to claim 1, which consists of granules having an apparent specific gravity of 1.2'/QC or less.