JPH04176466A - Deodorant - Google Patents

Abstract

PURPOSE:To enable the removal of obnoxious smell in environment and ammonia leakage generated at a factory or the like by incorporating lime, gypsum, alumina or silica based hardening material to accomplish an easy manufacture utilizing relatively inexpensive material or material considered as waste traditionally. CONSTITUTION:This deodorant contains lime, gypsum, alumina and silica based hardening materials. In a preferable combination of materials, coal ashes and/or a lime based exhaust gas treating agent used is combined with at least one selected from among a group of slaked lime, quick lime, gypsum and volcanic ash and water is added to the mixed material to harden by hydration treatment. The hardened product has a deodorizing capacity as it is and the deodorizing capacity can by improved by treating it by a gas containing SO2. For example, in the use of the deodorant thus obtained for treating waste of pets, it can be handled just as sand. The deodorant provides not only a deodorizing effect but also a dehumidifying effect because of liquid capacity by far larger than that of the sane. As for a massive malodorous source such as sludge, several cm of the coverage with the deodorant can remove bad smell.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a deodorizing agent, particularly a deodorizing agent intended for ammonia odor, and a method for producing the same.

[Conventional technology]

Expensive adsorbents are used to remove odors from relatively small spaces that are easy to seal, such as refrigerators and toilets. However, for example, excrement and urine from livestock and beds, etc.
There is no good method for removing ammonia odor generated from kitchen waste, and there is a need for a deodorizing agent that is easy to handle and inexpensive.

[Invention or problem to be solved]

This invention was made in response to the above-mentioned demands.
The object of the present invention is to provide an economical deodorizer for ammonia odor and a method for producing the same.

[Means to solve the problem]

This invention provides: 1. A deodorizer characterized by containing lime, gypsum, alumina, and a silica-based cured product.

2. The above deodorization characterized by mixing coal ash and/or spent lime-based waste treatment agent with at least one selected from the group consisting of slaked lime, quicklime 9 gypsum, and volcanic ash and curing by hydration. 3. After hydration and curing, further treatment with SO2-containing gas 1
- A method for producing the above deodorizing agent. Here, as raw materials for the lime-1 gypsum, alumina, and silica-based cured product, not only industrial single products such as quicklime, slaked lime-1 gypsum, alumina, and silica, but also natural products, industrial waste, etc. can be used.

In other words, sources of lime and gypsum include by-products such as quicklime, slaked lime, carbonated lime, anhydrite, hemihydrate, trihydrate, cement, slag, dolomite plaster (containing lime), and acetylene slag. .

Examples of alumina sources include alumina, aluminum hydroxide, aluminum silicate, sulfuric acid base, alum, aluminum sulfide, aluminum sulfate, aluminum chloride,
Examples include compounds containing reactive aluminum such as calcium aluminate, hentonite, kaolin, diatomaceous, theolite, perlite, bauxite, sodium aluminate, cryolite, and aluminum cleaning residue (alcite).

Examples of silica sources include silicic acid, hydrous silicic acid, metasilicic acid, aluminum silicate, water glass, calcium silicate and cristobalite, tridymite, kaolin,
Examples include compounds containing reactive silicon dioxide, such as bentonite, talc, perlite, shirasu, diatomaceous ash, glass, rice husk ash, and incineration ash of wood ash.

Examples of substances that can simultaneously supply at least two of the four components mentioned above include coal ash, volcanic ash, coal fluidized bed combustion ash (calcium oxide, silicon dioxide, aluminum oxide, calcium sulfate source), cement. and cement clinker (calcium oxide, silicon dioxide, aluminum oxide sources), slag and shirasu, andesite, chert,
Reactive silicon dioxide such as quartz trachyte, opal, zeolite, feldspar, clay minerals, ettringite (source of calcium sulfate, silicon dioxide, aluminum oxide, calcium oxide), and oxides of aluminum, calcium, chloride, sulfuric acid Examples include minerals containing salt, in-furnace desulfurization methods such as fluidized bed combustion ash, spent lime-based exhaust gas treatment agents, sludge incineration ash, municipal waste incineration ash, cement waste, acetylene slag, and used wastewater treatment agents. . Here, the used lime-based exhaust gas treatment agent refers to CaO, Ca (OH) 2 ,
Used calcium-based desulfurization agents manufactured using CaCO2 as raw materials and JP-A-61-209038;
Cab shown in Japanese Patent Application Laid-Open No. 63-283745.

Al2O,,Sin. , (: Refers to used desulfurization agents made of aSO4-based compositions, etc.

Table 1 shows examples of chemical analyzes of these typical raw materials (analytical values for deodorizers in Examples 1 and 5 below are also listed).
.

In this invention, the cured product obtained by mixing these raw materials and hydration-curing, and the cured product after SO2 treatment described below, have a complex hydrated composition, and the analytical component ratio is anhydrous. As CaO2~15% CaSO. 0.1-70% Al2035-70% Si0□ 5-80%.

A preferred combination of the raw materials is at least one combination selected from the group consisting of coal ash and/or spent lime-based exhaust gas treatment agent, slaked lime, quicklime gypsum, and volcanic ash.

In this invention, hydration hardening refers to adding water to a raw material mixture and hydrating it to harden it, and specifically, the treatment is as follows.

As disclosed in JP-A No. 64-38130, the hydration treatment refers to the treatment necessary to advance the hydration reaction between the various substances (raw materials) mentioned above, such as humid air curing, hot water curing,
This includes steam curing, etc., and is classified into hardening hydration treatment and non-caking hydration treatment.

Curing hydration treatment refers to reducing the mixing ratio (solid-liquid ratio) of various raw materials and water during treatment, for example, 1:0.2 to 1:0.99.
This refers to a hydration treatment that promotes bonding between material particles and obtains a cured product, and can be carried out in two stages if necessary.

Humid air curing in hardening hydration treatment is performed at a temperature of 10°C to 40°C.
℃ and a relative humidity of SO% to 100% for several minutes or several tens of days, and steam curing is performed at a temperature of 40℃ to 180℃.
℃ and 100% relative humidity for several minutes to several days.

Non-caking hydration treatment refers to treatment that prevents material particles from bonding together and growing into coarse particles during hydration treatment, and the solid-liquid ratio at the start of treatment is increased, for example from 1:1 to 1:20 and
In hot water curing, which involves hot water treatment, the temperature is 40°C to 180°C.
This is a process in which raw materials are dispersed in water at ℃, and stirring, bubbling, circulation, and shaking are performed for several minutes to several days to prevent the raw materials from settling and hardening at the bottom.

The cured product obtained by the above treatment may have deodorizing ability even as it is, or it may be treated with a scum containing SO2 (S
(abbreviated as O□ treatment), CaO and CaS
The proportion of O4 can of course be varied or the deQ ability can be improved.

SO2 treatment is performed using gas containing 100ppm to 90% SO2 at a temperature of 20℃ to SO0℃, SV5 to SO, 000h.
-1 for a time sufficient to contact at least 1 mol of SO2 per 1 kg of cured product.

The cured product of the present invention, which is not subjected to SO
It can then be used as a deodorizer. Therefore, in this case, a very economical deodorizer can be provided.

The cured product of this invention is used as a deodorizing agent in the form of powder or molded products according to known methods, depending on the application. E
DTA etc. can also be added.

When the deodorizer of the present invention is used, for example, to treat bed excrement, it can be handled in the same way as sand.

Since this deodorizing agent has a much greater water absorption (i) power than sand, it has not only a deodorizing effect but also a dehumidifying effect, and is extremely advantageous in handling excrement. For sources that generate a large amount of bad odor, such as sludge, the bad odor can be removed by covering several centimeters with this deodorizing agent.

Further, in order to remove ammonia from ammonia-containing gas generated in a factory, it may be used by filling a known packed tower or the like.

This will be explained below using examples.

(Example) Parts and percentages in the text are by weight.

Example 1 870 parts of coal ash shown in Table 1 are mixed with 10 parts of slaked lime and 20 parts of gypsum hemihydrate (calculated as CaS04), and 40 parts of water is added and mixed again. Next, after curing for 30 minutes in humid air at room temperature as the first stage of curing, extrusion molding was performed using a die with a hole diameter of 5 mm, and after curing in the second stage for 12 hours in steam at normal pressure of 95°C, Dry for 2 hours and use deodorizer 95.
I got the department.

The analytical values are shown in Table 1.

The deodorizing effect was determined based on the ammonia absorption capacity. i.e. 3.36 to 4.7 for molded or crushed granules
6. Size the particles to a +no+ particle size, and if it is powdery, use S as it is.
The amount of ammonia absorbed (+nl) when the deodorizing agent 401 is brought into contact with 99% concentration ammonia gas at room temperature and normal pressure without heating or degassing under reduced pressure, and the absorption of ammonia reaches almost equilibrium. was measured. The ammonia absorption amounts shown in the following Examples and Comparative Examples are values measured by this method.

The amount of ammonia absorbed in Example 1 was 2700 ml.

Example 2 A deodorizer was produced in the same manner as in Example 1, except that the raw materials and water were changed to the coal ash BIO part, 10 parts of slaked lime, 80 parts of a spent lime-based exhaust gas treatment agent, and 45 parts of water as shown in Table 1. 9
Got 5 copies. The amount of ammonia absorbed was 2800ml.

Example 3 95 parts of a deodorizer was obtained in the same manner as in Example 1 except that volcanic ash shown in Table 1 was used instead of coal ash among the raw materials.

Ammonia absorption amount was 2700+nl.

Example 4 7.57 parts of quicklime shown in Table 1 was added to 75°C hot water SO0.
After 20 minutes without stirring, 870 parts of coal ash and 20 parts of gypsum trihydrate (calculated as CaS04) were added, and the temperature was kept at 95°C and cured in hot water for 12 hours, dehydrated and heated to 200°C.
The mixture was dried for 2 hours to obtain 98 parts of powdered deodorizer. The amount of ammonia absorbed was 2700ml.

Example 5 98 parts of a powdered deodorizer was obtained in the same manner as in Example 4, except that 80 parts of a spent lime-based exhaust gas treatment agent was used instead of gypsum and the amount of coal ash B was reduced to 10 parts. The analytical values are shown in Table 1. The amount of ammonia absorbed was 3000 ml.

Example 6 Example 4 except that 70 parts of volcanic ash was used instead of coal ash.
In the same manner as above, 98 parts of powdered deodorizing agent was obtained. The amount of ammonia absorbed was 2700ml.

Example 7 In Example 5, the slurry was dehydrated and dried at 200°C to make the moisture content 25%, extruded using a disk pelleter, and then dried again at 200°C for 2 hours to prepare 93 parts of deodorizer. . The amount of ammonia absorbed was 2700ml.

Example 8 830 parts of coal ash shown in Table 1 are mixed with 30 parts of slaked lime and 40 parts of a spent lime-based exhaust gas treatment agent, and 40 parts of water is added and mixed again. Next, as the first stage of curing, it is kept at room temperature and humidity for 30 minutes, and then as the second stage of curing, it is kept at normal pressure of 95%.
It was cured for 12 hours in steam at 0.degree. C., crushed and dried at 200.degree. C. for 2 hours, and sized to a particle size of 3.36 to 4.76 mm. Next, the granulated material was treated with So21000ppm, NOXSO(
l'ppm, (:0212%, 026%, 8208%(
The rest is SO2-containing scum of N2).SV 2000h-
', and treated at 130° C. for 140 hours to obtain 98 parts of crushed particulate deodorizer. Approximately 80% of C and a in the raw slaked lime were converted to CaSO4 by this SO□-containing gas treatment. The amount of ammonia absorbed was 3300 ml.

This deodorizer 22 was placed in a cage for excretion for a pet cat with a bottom surface of 40 cm x 40 cm made of wire mesh with 1 mm openings, and a cat weighing 6 kg was allowed to use it for 7 days. Feces were removed each time. During this time, the deodorizer was not replaced or replenished, and the urine odor was hardly noticeable.

Example 9 In Example 8, after curing in room temperature and humid air, the pore size was 5 [ll0I
95 parts of a molded particulate deodorizer was obtained in the same manner as in Example 8, except that it was extruded using a die. The amount of ammonia absorbed was 3100 ml.

Example 10 Molded particulate deodorizer 10 was prepared in the same manner as in Example 9 except that coal ash B was reduced by 2 parts and Fe2 (SO4)3 was added by 2%.
I got 0 copies. Ammonia absorption amount was 3000+nl.

Example 11 30 parts of slaked lime shown in Table 1 was added to 0 parts of 75°C hot water, and after 20 minutes with stirring, 827 parts of coal ash and 40 parts of a spent lime-based exhaust gas treatment agent were added, and finally FeSO
Add 0 parts of an aqueous solution SO containing 42 parts and 1 part of EDTA, maintain the temperature at 95°C and cure in hot water for 12 hours, dehydrate,
After drying at 00° C. to a residual moisture content of 25%, it was extruded using a disc beretter. 20 more moldings
After drying at 0° C. for 2 hours, the same SO2 treatment as in Example 8 was performed to obtain 95 parts of a molded particulate deodorizer. The amount of ammonia absorbed was 3100 ml.

Example 12 38 parts of quicklime shown in Table 1 was put into 0 parts of hot water at 75°C, and after 20 minutes with stirring, 10 parts of coal ash B and 40 parts of a spent lime-based exhaust gas treatment agent were added, and the temperature was raised to 95°C. The mixture was cured in hot water for 12 hours, dehydrated, and dried at 200°C to reduce the moisture content to 28%, extruded using a disc pelleter, and then dried again at 200°C for 2 hours to obtain a molded product.

This molded product was subjected to the same SO2 treatment as in Example 8 to obtain 91 parts of a molded particulate deodorizer. Ammonia absorption amount is 320
It was 0i+l.

Water is sprayed onto the molded particles after the above S02 treatment to reduce the moisture content to 5%.
, 10% and the ammonia absorption amount was measured, and it was 3300.3400 ml, respectively.

Example 13 Molded particulate deodorizer 92 treated with S02 in the same manner as in Example 12 except that 10 parts of volcanic ash was used instead of coal ash B.
I got the department. The amount of ammonia absorbed was 3200ml.

Comparative Example The same ammonia absorption test as in Example 1 was conducted on four types of commercially available theolites and one type of activated carbon. The test results are shown in Table 2 along with the chemical analysis values of the stiff grain samples.

〔Effect of the invention〕

As described in detail above, the deodorizing agent of the present invention can be easily manufactured using relatively inexpensive raw materials or materials that were conventionally considered to be waste, and can be used to remove bad odors in the environment and to remove odors generated in factories. Since ammonia leakage can be removed, the industrial value of this invention is very large.

Patent applicant: Hokkaido Electric Power Co., Inc.

Claims (1)

[Claims] 1. A deodorizing agent containing lime, gypsum, alumina, and a silica-based cured product. 2. At least one selected from the group consisting of slaked lime, quicklime, gypsum and volcanic ash is mixed with the coal ash and/or spent lime-based exhaust gas treatment agent and cured by hydration. A method for producing a deodorizer. 3. The manufacturing method according to claim 2, further comprising treating with a gas containing SO_2 after hydration curing.