JPS61265145A - Solid deodorant - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a deodorizing agent, and more particularly to a solid deodorizing agent for deodorizing bad odors generated from homes, factories, agriculture, automobiles, and the like.

(Prior Art) Conventionally, solid deodorizing agents include those that adsorb and remove odors through physical adsorption (e.g., activated carbon, zeolite, alumina, etc.), and odorless compounds that chemically remove odor components. (For example, a carrier such as zeolite or alumina is impregnated with a solution deodorizer such as an iron compound or glyoxal). These solid deodorizers are in the form of powder, granules, or irregular shapes, and they can be placed in some kind of well-ventilated container and placed indoors, in a refrigerator, in a car, or filled into a factory exhaust gas treatment tower. It is used as such.

In addition, the shape of the container is mostly cylindrical, prismatic, etc.

(Problems to be Solved by the Invention) However, these solid deodorizing agents have the following problems, and their solution has been strongly desired. That is, firstly, conventional solid deodorizing agents have a slow deodorizing speed and lack quick effectiveness. Second, the deodorizing effect did not last long, and the entire container or contents had to be replaced after about a month. Thirdly, it is difficult to mold deodorants into arbitrary particles or molded objects, and even if they are molded, their strength is weak, and they may lose their shape or turn into powder with weak force, which can adversely affect the environment. could be contaminated. Fourth, the end point of the deodorizing effect was unclear, making it difficult to determine when to replace it. Fifth, when used in a packed tower or the like, there were problems such as large pressure loss due to the particle shape and an increase in the size of the blower.

(Means for Solving the Problems) The present inventors have conducted extensive studies to improve the conventional solid deodorizers, which have many problems as described above, and have previously proposed the following (Patent Application No. 1983). -10535) Porous particles of cellulose acetate have a long-lasting deodorizing effect and are stable even during storage.
) Aqueous solution of composition containing compound as main component (JP-A-58-1989-
No. 156539) and dried, it was found that a solid deodorizer with deodorizing power, durability, and ease of handling was obtained, and the present invention was completed.

That is, the present invention provides porous particles of cellulose acetate with iron (
The object of the present invention is to provide a solid deodorizing agent characterized by comprising a composition containing the compound II) as a main component.

The cellulose acetate used in the present invention is so-called cellulose diacetate, which has a hydroxyl group and an acetyl group and has an acetylation degree of 50 to 58%. If the degree of acetylation is less than 50%, the particle strength is weak and easily absorbs moisture, whereas if the degree of acetylation exceeds 58%,
When immersed in an aqueous solution of a composition that lacks hydrophilicity and has an iron(II) compound as its main component, the penetration of the liquid is slow and the amount of impregnation becomes small, both of which are unfavorable.

Furthermore, the porous cellulose acetate used in the present invention is
It is obtained by extruding a seventone or acetic acid solution of cellulose acetate into a suitable coagulation bath, such as an aqueous acetone solution or an aqueous acetic acid solution, forming it into an arbitrary shape while coagulating it, and washing and drying it. The shape of this molded product can be various, but granular, particularly spherical, is advantageous in terms of increasing surface area, toughness, and ease of handling during use. Products produced by this method are characterized by high crushing strength despite the large pore volume within the particles.

The cellulose acetate used in the present invention has a pore volume of 0.
．． It is a porous molded body with a crushing strength of 10 kg or more and a pressure of 7 cc/g or more. If the pore volume is less than 0.7 c c / g, the amount of impregnation with an aqueous solution of a composition containing an iron (II) compound as a main component is small, and as a result, only a solid deodorizer with a small deodorizing power can be obtained. Also, it is better to have more pores with small pore diameters even if the pore volume is the same, and preferably 1000'A
Below are the average pore diameters. The crushing strength is iron (I
I) The larger the size, the better, in order to prevent particles from contacting or colliding with each other and turning into powder during manufacturing processes such as impregnation with an aqueous solution of a composition containing the compound as a main component, drying process, etc., and during use. A weight of 10 kg or more is desirable, and the solid deodorizer of the present invention satisfies that requirement.

Further, the particle size varies depending on the place where the deodorizing agent is used, but from the viewpoint of yield in the manufacturing process and ease of handling, a diameter of 3 to 5 mm is preferable. However, it is also possible to use particles formed by forming these particles into an arbitrary shape.

The composition containing an iron (II) compound as a main component used in the present invention is an iron (II) compound, ascorbic acid and/or
Alternatively, it can be combined with citric acid, which can be made into an aqueous solution and impregnated into cellulose acetate.

Examples of the iron(II) compound used in the composition of the present invention which has an iron(II) compound as a main component include ferrous sulfate,
Ferrous chloride, ferrous nitrate, ferrous bromide.

In addition to iron(II) inorganic salts such as ferrous iodide, iron(II) salts such as ferrous gallate, ferrous malate, and ferrous fumarate
I) Examples include organic salts. The iron(II) compound is not limited to those exemplified above, and any compound can be used as long as it dissolves in water and forms divalent iron ions.

Ascorbic acid, L-7scorbic acid, D-
Isoascorbic acid (erythorbic acid) is used, but L-ascorbic acid is preferred.

In the present invention, ascorbic acid and citric acid may be used alone or in combination. When used together, citric acid is thought to also act as a stabilizing agent for ascorbic acid.

In addition, iron (II) in compositions containing iron (II) compounds as the main component
n) The ratio of the compound to ascorbic acid and/or citric acid is preferably in the range of 0.02 to 0.3 (weight ratio), more preferably in the range of 0.03 to 0.1.

If ascorbic acid and/or citric acid are used in excess of this range, the composition will become colored and become uneconomical.
Freshness preservation and deodorizing functions deteriorate, and below the lower limit, iron (
II) becomes insufficient in stability.

In the present invention, it is preferable that the iron (II) compound and ascorbic acid and/or citric acid are combined, and this can be easily done by forming a composition containing the iron (II) compound as a main component into an aqueous solution. be able to. Further, for impregnating the carrier with this aqueous solution, a known method such as a method of impregnating the carrier into the above-mentioned aqueous solution or a method of sprinkling the aqueous solution onto the carrier can be used.

There is no problem with the subsequent drying by a known drying method, and by this drying only the deodorant is trapped in the pores of the particles, making it possible to obtain an excellent solid deodorizer extremely easily.

Furthermore, the solid deodorizer of the present invention can achieve its purpose by putting it in a container and placing it indoors, in a car, etc.

Furthermore, when used as a deodorizing agent for malodorous gas in factories, etc., it can be filled into exhaust ducts. In that case, the pressure loss due to the packed bed can be reduced by making the product of the present invention spherical.

Furthermore, by coating the surface of the product of the present invention with a special water-insoluble film, it can also be used as a water deodorizer.

(Effects of the invention) Comparing the product of the present invention with the conventional product, the following table shows that:
It can be seen that the product of the present invention is superior.

(Example) EXAMPLES The present invention will be explained in more detail with reference to Examples below.

In addition, the physical property values of cellulose acetate in Examples were measured by the following method.

(a) Degree of acetylation After drying 5 g of a pulverized sample in a dryer at 100 to 105°C for 2 hours, it is accurately weighed. Add 50% of purified acetone to this sample.
After adding ml and completely dissolving, add 50ml of 0.2N-NaOH aqueous solution.
, then 50 ml of 0.2N-HCI aqueous solution was sequentially added, and 0.2N-NaOH was added using phenolphthalein as an indicator.
Titrate with an aqueous solution and calculate using the following formula.

However, A: 0.2N-NaOH aqueous solution titration number (ma1
) Titration number of 0.2N-NaOH aqueous solution in B blank test (m sentence) F: 0.2N-NaOH aqueous solution (7) 77 liters The degree of acetylation calculated by this method is the acetic acid content (%).

(b) Pore volume The volume of mercury injected with a mercury injection porosimeter (manufactured by Carlo Elpa) at a pressure in the range of θ to 1000 [kg/crrI″G] corresponds to a pore volume of 75 to 75,000 OOA. .It is expressed in volume per 1 g of sample.

(c) Crushing strength Using a Monsanto II tablet hardness tester (manufactured by Daikun Yakuhin Kikai Seisakusho), determine the average value of the measured values of 10 particles.

In addition, parts and percentages indicating the A#1 composition in the examples indicate parts by weight and percentages by weight, respectively, unless otherwise specified.

Example 1 10 g of spherical cellulose acetate having acetylation degree of 54.5%, pore volume of 0, 95 cc/g, average pore radius of 900 A, crushing strength of 15 kg, and average particle diameter of 4.6 mm was mixed with 1 part of ferrous sulfate. The sample was immersed in 50 g of a 25% aqueous solution of a deodorizing composition containing 0.05 part of L-ascorbic acid at room temperature for 8 hours with stirring.

Thereafter, the solid and liquid were separated using a wire mesh, and the solid content was dried in a steam dryer at 105° C. for 2 hours to obtain a spherical solid deodorizer. This product contained about 14% of the deodorizing composition and had the same apparent shape and size as the first one. Moreover, the crushing strength did not change, and the color was pale green. Furthermore, there was no destruction or powdering of the particles during impregnation.

Take 1 g of this solid deodorizer in its original form and place it in a 1× glass container with an ammonia gas concentration of 540 pp.
After shaking the container well, the ammonia gas concentration was measured after 30 minutes and found to be 1.5 ppm, with no ammonia odor at all.

Comparative Example 1 When activated carbon (Kuracol 4GG, manufactured by Kuraray Chemical Co., Ltd.), which is a commercially available solid deodorizer, was used instead of the solid deodorizer of Example 1, the ammonia gas concentration after 30 minutes was 300.
There was a strong ammonia odor at ppm. When the retention period was further extended and the concentration was measured after 2 hours, 200 ppm of ammonia remained.

Example 2 Acetylation degree 54.9%, pore volume 0, 9 c c / g
Spherical cellulose acetate with an average pore radius of 500 A, a crushing strength of 20 kg, and an average particle diameter of 3.5 mm was filled into a rectangular wire mesh mold measuring 50 cm long, 50 cm wide, and 3 cm high, and poured into an ethyl acetate solution for 30 seconds. After soaking, immediately remove from the solution and air dry for 10 minutes.

The solvent was completely evaporated in a dryer at 105°C, and the product was removed from the dryer, and the metal frame was removed to obtain a rectangular parallelepiped molded product. This product was immersed in the same deodorizing composition aqueous solution as in Example 1 for 8 hours so that the entire product was immersed in the liquid.

Thereafter, it was dried to obtain a solid deodorizer. When this was used as a filter for the exhaust duct of a factory with a strong ammonia odor, the ammonia concentration of exhaust gas of 10,000 ppm was reduced to 2 to 3 ppm after passing through the filter.

Comparative example? When the activated carbon of Comparative Example 1 was used as a binder with carboxymethyl cellulose to make a molded body similar to that of Example 2 and used as a filter similar to that of Example 2, the ammonia concentration of the exhaust gas after passing through the filter was 11,000 pp.

Furthermore, the molded product was extremely brittle and broke when tapped lightly.

Patent applicant Todoroki Director of the Agency of Industrial Science and Technology Minato Sangyo Co., Ltd.

Claims (1)

[Scope of Claims] 1) A solid deodorizer comprising porous particles of cellulose acetate supporting a composition containing an iron (II) compound as a main component. 2) Cellulose acetate porous particles have acetylation degree of 50-58%
The solid deodorizer according to claim 1, which has a pore volume of 0.7 cc/g or more and a crushing strength of 10 kg or more. 3) The solid deodorizer according to claim 1, wherein the composition containing an iron (II) compound as a main component is a combination of an iron (II) compound and ascorbic acid and/or citric acid.