JPH0630978A - Deodorant and activation of deodorant - Google Patents

Abstract

PURPOSE:To provide a deodorant made of cheap material and a method for activating the deodorant wherein an initial deodorizing rate can be accelerated, whereby deodorizing effect can be obtained in a short time. CONSTITUTION:One deodorant contains a hardened matter of calcium chloride system containing lime, alumina, silica and calcium chloride. The other deodorant contains a hardened matter of gypsum system containing line, alumina, silica and gypsum. The mothod of activating the deodorant comprises treating this deodorant with a gas containing sulfurous acid gas and subsequently treating with ammonia.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorant and a method for activating the deodorant, particularly for ammoniacal odor.

[0002]

2. Description of the Related Art An expensive adsorbent is used for removing odors in a relatively narrow space that can be easily sealed, for example, for deodorizing refrigerators and toilets. However, for example, there is still no good method for removing ammoniacal odors generated from manure of domestic animals and pets, sludge, and garbage, and there is a demand for an inexpensive deodorant that is easy to handle and has a high odor absorption rate.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to meet the above-mentioned demands, and provides an economical deodorant for ammoniacal odor, a method for producing the same, and a method for activating the deodorant. That is the purpose.

[0004]

SUMMARY OF THE INVENTION The inventors of the present invention have
First, we found that lime, gypsum, alumina, and silica-based cured products had a deodorizing effect, and filed a patent application (Japanese Patent Application No. 2-302).
706). Further, as a result of research, they found that a cured product containing calcium chloride also had a deodorizing effect, and that these deodorizing agents were activated by treatment with sulfurous acid gas and ammonia, and completed the invention of the present application.

That is, the present invention is: 1. A deodorant characterized by containing a calcium chloride-based cured product containing lime, alumina, silica and calcium chloride. Of the above deodorant characterized by mixing coal ash and / or a used lime-based exhaust gas treatment agent with at least one selected from the group consisting of calcium chloride and slaked lime, quick lime, and volcanic ash to effect hydration hardening. Manufacturing method, 3. _{3. The} method for producing a deodorant as described above, which comprises further treating with a gas containing SO ₂ after hydration curing, and 4. After treating a deodorant containing a calcium sulfate-based cured product containing lime, alumina, silica and calcium sulfate and / or a calcium chloride-based cured product containing lime, alumina, silica and calcium chloride with a gas containing sulfurous acid gas The method for activating a deodorant is characterized by treating with ammonia.

First, a calcium chloride-based cured product and a method for producing the same will be described. As the raw material for the calcium chloride-based cured product, not only industrial single products such as industrial alumina and silica but also natural products and industrial wastes can be used.

That is, as the lime source, for example, quick lime,
Examples include by-products such as slaked lime, lime carbonate, cement, slag, dolomite plaster (containing lime), and acetylene slag.

Examples of the alumina source include aluminum hydroxide, aluminum silicate, agar sulfate, alum, aluminum sulfide, aluminum sulfate, aluminum chloride, calcium aluminate, bentonite, kaolin,
Diatomaceous earth, zeolite, perlite, bauxite,
Examples thereof include compounds containing reactive aluminum such as sodium aluminate, cryolite, and aluminum cleaning residue (alcite).

Examples of the silica source include silicic acid, hydrous silicic acid, metasilicic acid, aluminum silicate, water glass, calcium silicate and cristobalite, tridymite, kaolin, bentonite, talc, perlite, shirasu, diatomaceous earth, glass and fir tree. Examples thereof include compounds containing reactive silicon dioxide such as incinerated ash such as shell ash and wood ash.

Further, as examples of substances capable of simultaneously supplying at least two or more of the above-mentioned three components, coal ash and volcanic ash, coal fluidized bed combustion ash (calcium oxide, silicon dioxide, aluminum oxide source), cement and cement Reactions of clinker (calcium oxide, silicon dioxide, aluminum oxide source), slag and silas, andesite, chert, quartz trachyte, opal, zeolite, feldspar, clay mineral, ettringite (silicon dioxide, aluminum oxide, calcium oxide source), etc. Silicon dioxide and minerals containing oxides, chlorides, sulfates, etc. of aluminum, calcium, etc., in-furnace desulfurization / de-HCl ash such as fluidized bed combustion ash and used lime-based exhaust gas treatment agent, sludge incineration ash, Examples include municipal waste incineration ash, cement waste, acetylene slag, and used wastewater treatment agents. .

Here, the used lime-based exhaust gas treating agent is
CaO, Ca (OH)₂ , CaCO ₃ Manufactured from
Used calcium-based desulfurizing agent and Japanese Patent Laid-Open No. 61-1999
-209038, JP-A-63-28374, etc.
CaO, Al₂ O₃ , SiO₂ , CaSO_Four System composition
Used desulfurization agent or dehydrochlorination
Say.

Table 1 shows an example of chemical analysis of these typical raw materials.

[0013]

[Table 1] A preferable combination for obtaining a calcium chloride-based cured product is at least one combination selected from the group consisting of coal ash and / or a used lime-based exhaust gas treatment agent, calcium chloride, and slaked lime, quick lime, and volcanic ash.

In the present invention, the hydration hardening means that water is added to the raw material mixture to hydrate and harden it, and specifically it is the following treatment.

The hydration treatment is carried out, for example, in Japanese Patent Laid-Open No. 64-3813
As disclosed in No. 0, it refers to the treatment necessary to promote the hydration reaction between the above-mentioned various substances (raw materials), and includes, for example, wet air curing, hot water curing, steam curing, etc. It is classified into treatment and non-caking hydration treatment.

The curable hydration treatment means that the mixing ratio (solid-liquid ratio) of the raw materials and water at the time of treatment is made small, for example, 1: 0.2 to.
By setting the ratio to 1: 0.99, the hydration treatment for promoting the bonding between the material particles to obtain a cured product can be carried out in two steps if necessary.

The wet air curing in the curable hydration treatment is preferably carried out at a temperature of 10 ° C. to 40 ° C. and a relative humidity of 50% to 100% for a few minutes or tens of days.
It is preferable that the temperature is 0 ° C. to 180 ° C. and the relative humidity is 100% for several minutes to several days.

The non-consolidating hydration treatment is a treatment for preventing the material particles from binding to each other during the hydration treatment and growing into coarse particles, and the solid-liquid ratio at the start of the treatment is increased to, for example, 1: 1. : 1 to
At 1:20, in hot water curing with hot water treatment,
This is a treatment in which the raw material is dispersed in water at 40 ° C. to 180 ° C., and stirring, bubbling, circulation, shaking, etc. are performed for several minutes to several days so that the raw material does not precipitate and harden in the lower part.

The component ratio of the calcium chloride-based cured product obtained by hydration curing is CaO 2-8% Al ₂ O ₃ 5-70% SiO ₂ 5-80% CaCl ₂ 0.1-50%.

The calcium chloride-based cured product obtained by the above treatment has a deodorizing ability as it is, but the deodorizing ability can be further improved by treating with a gas containing a sulfurous acid gas (abbreviated as SO ₂ treatment). .

The SO ₂ treatment is carried out at 100 ppm to 9 SO ₂
At a gas temperature of 20 ° C to 500 ° C containing 0%, the space velocity is (S
V) 5 to 50,000 h ⁻¹ , SO per 1 kg of cured product
_The treatment may be performed for a sufficient time so that ₂ is in contact with at least 1 mol. Gases for SO ₂ treatment include NO _x , H ₂ O, O
₂ , N _2, etc. may be included.

The cured product of the present invention not treated with SO ₂ is
Since it has a desulfurizing ability, this cured product can be used as a desulfurizing agent first and then as a deodorizing agent. Therefore, in this case, a very economical deodorant can be provided.

The cured product of the present invention is
It is made into a powdery material, a granular material, or a molded product by a known method and used as a deodorant.

When the deodorant of the present invention is used, for example, for treating pet excrement, it can be handled in the same manner as sand. This deodorant has a water-absorption (liquid) force and a water absorption effect to promote a hydration hardening reaction, and the ability of particles to bind to each other is far greater than that of sand. This is extremely advantageous. For a large amount of malodorous sources such as sludge (ammonia, hydrogen sulfide, etc.),
By coating the deodorant for several cm, the coated surface can be cured, and at the same time, the bad odor of ammonia, hydrogen sulfide, etc. can be removed.

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

Next, a method for activating the deodorant will be described.

The deodorant to be activated in the present invention is
The above-mentioned calcium chloride-based cured product and the previously applied lime, gypsum, alumina, silica-based cured product (hereinafter referred to as calcium sulfate-based cured product for calcium chloride-based cured product)
Is.

The composition of the calcium sulfate-based cured product is, as disclosed in the above application, CaO 2 to 15% CaSO ₄ 0.1 to 70% Al ₂ O ₃ 5 to 70% SiO ₂ 5 to 80%. . And a preferable combination of raw materials for the production of this cured product is at least one combination selected from the group consisting of coal ash and / or a used lime-based desulfurizing agent, gypsum and slaked lime, quick lime, and volcanic ash, and if necessary, sulfuric acid. Ferrous iron, ferric sulfate, EDTA, etc. can be added.

In the activation treatment, the cured product is first treated with SO ₂ and then with ammonia. SO ₂ process is the same process as SO ₂ treatment of the calcium chloride-based cured product, it is needless to say it is possible to perform the SO ₂ treatment by using a cured product as a desulfurization agent. Ammonia treatment is S
Ammonia water or gaseous ammonia is used in an operation of fixing 3 g or less of ammonia per 1 kg of a cured product having a water content of 30% or less after O ₂ treatment. In the case of gaseous ammonia, ammonia is used by diluting it, but the diluting gas may be any gas that does not contain a substance that reacts with the cured product, and air is usually used. Process gas temperature is -10 ° C
~ 300 ° C, space velocity (SV) 0 ~ 50,000h
⁻¹ , 1 mg to 3,000 mg of ammonia per 1 kg of the cured product may be treated for a sufficient time.

The activation treatment accelerates the expression of the deodorizing effect. An example will be described below.

[0031]

EXAMPLES Parts and percentages in the text are by weight. Example 1 To 30 parts of coal ash B shown in Table 1, 30 parts of slaked lime and 40 parts of used lime-based exhaust gas treating agent A are mixed, and 40 parts of water is added and mixed again. Next, as the first stage curing, keep it in normal temperature and humidity for 30 minutes, and then as the second stage curing at atmospheric pressure 95
It was aged in steam at ℃ for 12 hours, coarsely crushed and dried at 200 ℃ for 2 hours and sized to a particle size of 1.7 to 2.5 mm to obtain a crushed particulate deodorant. The bulk specific gravity was about 0.91 g / cc. Next, SO ₂ 1000ppm, NO _x 500pp
m, CO ₂ 13%, O ₂ 6%, H ₂ O 9% (the balance is N ₂ ) SO ₂ containing gas SV 2,000 h ⁻¹ , 13
It was treated at 0 ° C. for 150 hours. About 80% of Ca in the raw slaked lime was converted to CaSO ₄ by this SO ₂ containing gas treatment.

This deodorant was treated with ammonia by the following procedure.

1 kg of this deodorant was placed in 5 liters of Tetra Pak, and 4 liters of 1% ammonia gas diluted with air at room temperature (25 ° C.) was added to absorb ammonia while gently mixing for 10 minutes. Almost no increase in temperature was observed during this operation. After the treatment, the residual gas in Tetra Pak had no ammonia odor. The fixed amount of ammonia is about 30 mg.

The deodorizing effect was judged by the amount of leakage of ammonia. That is, in the case of molded or crushed granules, 1.
If the particle size is 7 to 2.5 mm, and if it is a powder, 2.0 ml of the deodorant as it is is filled into a 11 mmφ Pyrex glass tube and heated at room temperature without degassing. 1 L / min of N ₂ gas containing 100 ppm of ammonia gas (SV 30,000 h ⁻¹ )
The amount of ammonia (mg) leaked to the outlet side of the deodorant after 0.5, 1, 2, 4, 8, 16 and 32 minutes was measured. The ammonia leakage amounts shown in the following Examples and Comparative Examples were all measured by the same method, and the results are shown in Table 2. Example 2 In Example 1, after curing at room temperature and humid air, extrusion molding was performed with a die having a hole diameter of 5 mm to obtain a molded particulate deodorant. This agent was subjected to the same SO ₂ treatment and ammonia treatment as in Example 1 to determine the ammonia leakage amount. Example 3 A molded particulate deodorant was obtained in the same manner as in Example 2 except that the coal ash B was reduced by 2 parts and Fe ₂ (SO ₄ ) ₃ was added by 2 parts. This agent was subjected to the same SO ₂ treatment and ammonia treatment as in Example 1 to determine the amount of ammonia leakage. Example 4 30 parts of slaked lime shown in Table 1 was added to 500 parts of hot water at 75 ° C., and 20 minutes after stirring, 27 parts of coal ash B and 40 parts of spent lime-based exhaust gas treatment agent A were added, and finally FeSO.
₄ 2 parts, 40 parts of an aqueous solution containing 1 part of EDTA was added,
Keep the temperature at 95 ° C for 12 hours in hot water, and dehydrate for 20 hours.
After drying at 0 ° C. to have a residual water content of 25%, extrusion molding was performed with a disc pelleter. 200 more moldings
After drying at 0 ° C. for 2 hours, the same SO ₂ treatment as in Example 1 was performed, and then ammonia treatment (ammonia fixed amount 10 mg) was performed to obtain an activated molded particulate deodorant. The amount of ammonia leakage was determined in the same manner as in Example 1. Example 5 38 parts of quicklime shown in Table 1 was put into 500 parts of hot water at 75 ° C., and 20 minutes after stirring, 10 parts of coal ash B and 40 parts of spent lime-based exhaust gas treatment agent A were added, and the temperature was raised to 95 ° C. Keep it in hot water for 12 hours, dehydrate and dry at 200 ° C to make 28% moisture content and absolutely dry powder, and extrude the 28% moisture content with a disk pelleter, then 200 ° C again.
And dried to obtain a molded product.

The dried powder and molded product were treated with SO ₂ and ammonia as in Example 1 to obtain an activated molded particulate deodorant and an activated dry powder deodorant. The amount of ammonia leakage is shown in Table 2 as 5-1 and 5-2.

Water was sprayed on the shaped particles after the SO ₂ treatment to adjust the water content to 5% and 10%, the same ammonia treatment as in Example 1 was performed, and the ammonia leakage amount was measured to obtain Examples 5-3 and 5-3. It is shown in Table 2 as 5-4. Example 6 An activated molded particulate deodorant was obtained by SO ₂ treatment and ammonia treatment in the same manner as in Example 1 except that 10 parts of volcanic ash was used instead of coal ash B, and the amount of ammonia leakage was measured. Example 7 4 parts by weight of CaCl ₂ was used in place of the spent lime-based exhaust gas treatment agent A in Example 5-1, and 46 parts of coal ash B,
An activated molded particulate deodorant was obtained in the same manner as in Example 5-1 except that the amount of hot water was 300 parts, and the amount of ammonia leakage was measured. Comparative Examples 1 and 2 The deodorants of Examples 1 and 7 before the ammonia treatment were respectively set as Comparative Examples 1 and 2 of the activation test, and the analytical values are shown in Table 3.
In addition, Table 2 shows the measured values of the amount of ammonia leakage, which were measured in the same manner as in the example.

[0037]

[Table 2]

[0038]

[Table 3] Example 8 A deodorizing test for excrement using a cat was conducted as follows. Deodorant 2 before treatment with ammonia obtained in Example 1
1 is made of wire mesh with 1 mm openings and the bottom is 40 cm x 4
It was laid in a 0 cm cage for excretion of domestic cats and used by a cat weighing 6 kg. Feces were removed each time.
After 14 days, a strong ammoniacal urine odor was felt at a position 30 cm from the surface of the deodorant. The deodorizing agent in this state was treated with ammonia to form a roughly two-particle layer (thickness: about 8 m).
When it was spread so as to be m), urine odor was reduced to an unnoticeable level after 1 minute. On the other hand, the same operation,
If additional agents without ammonia treatment are used as well,
There was a urine odor even after 5 minutes, and after 20 minutes, it was barely noticeable.

[0039]

As described above in detail, the deodorant of the present invention is easily produced by using a relatively inexpensive raw material or what was conventionally considered as a waste, and further activation of the present invention. The industrial value of the present invention is very large because the method promotes the removal of offensive odors in the environment and the removal of leaked ammonia generated in factories.

Claims (5)

[Claims] 1. A deodorant comprising a calcium chloride-based cured product containing lime, alumina, silica and calcium chloride. 2. A coal ash and / or a used lime-based exhaust gas treating agent, calcium chloride and slaked lime, quick lime,
The method for producing a deodorant according to claim 1, wherein at least one selected from the group consisting of and volcanic ash is mixed and hydrated and hardened. 3. The manufacturing method according to claim 2, further comprising a treatment with a gas containing a sulfurous acid gas after the hydration curing. 4. A deodorant containing a calcium sulfate-based cured product containing lime, alumina, silica and calcium sulfate and / or a calcium chloride-based cured product containing lime, alumina, silica and calcium chloride, and a sulfurous acid gas. A method for activating a deodorant, which comprises treating with gas and then with ammonia. 5. The activation method according to claim 4, wherein the fixed amount of ammonia of the deodorant after the ammonia treatment is 1 to 3000 mg per 1 kg of the cured product.