JPS6357056A - Deodorizing method - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a deodorizing method. More specifically, the present invention relates to a deodorizing method using phthalocyanine metal complexes as a deodorizing component.

[Prior art] and [Problems to be solved by the invention] Methods for eliminating various odors including malodors include sensory deodorization,
Methods such as chemical deodorization, physical/chemical deodorization, physical adsorption deodorization, and biological deodorization are used.

Most of the main malodorous substances are contained in mobile hydrogen, and deodorization is thought to be possible by dehydrogenating, oxidizing, dimerizing, water-soluble, and non-volatile, and in vivo enzymes act on the malodorous substances. You can see some examples. The enzymes that carry out these reactions contain hematoporphyrin, which binds to apoproteins to place iron in a trivalent spin state, and the histidine imidazole nitrogen of the protein is coordinated to the fifth coordination site.

Phthalocyanine-based metal complexes with similar catalytic activity, such as octacarboxylic acid phthalocyanine iron complexes, are decomposed by a reaction mechanism similar to that of catalase, and exhibit a relatively high specific activity of about 6 times that of hemin. There is.

The present inventors have made a hollow fiber hold a phthalocyanine-based metal complex having such an effect, and contacted either the inside of the hollow fiber or the outside of the hollow fiber with a fluid containing water, and the other side contains a malodorous substance. It has been found that the deodorizing effect can be more effectively exerted by bringing the fluids into contact with each other and allowing them to flow together.

[Means for Solving the Problems] and [Operation] Therefore, the present invention relates to a deodorizing method, which uses a hollow fiber module holding phthalocyanine metal complexes, and A fluid containing moisture is brought into contact with one of the outsides, and a fluid containing a malodorous substance is brought into contact with the other, allowing them to flow together.

As the phthalocyanine-based metal complexes, phthalocyanine tetrafunctional or octafunctional group substances are used alone or in the form of being supported on a polymer.

Specifically, 4, 4', 4'- expressed by the following formula.

4″″-Tetracarboxyphthalocyanine-metal complex (this page, below margins) α Katana H or 4. 5. 4', 5', 4-,
5=, 4″″.

A substance based on 5-octacarboxyphthalocyanine-metal mirror or the like is used.

These tetra- or octacarboxyphthalocyanine-metal complexes can be prepared, for example, in the case of iron complexes, by trimellitic anhydride (in the case of tetracarboxylic acid) or pyromellitic anhydride (in the case of octacarboxylic acid), urea in a solvent such as nitrobenzene. The carboxylic acid type iron phthalocyanine is first obtained by reacting ammonium molybdate and ferric chloride to form a carboxylic acid amide type iron phthalocyanine, which is then hydrolyzed in the presence of an alkali such as an aqueous sodium hydroxide solution. Ru. Similarly, by replacing ferric chloride with chlorides of nickel, cobalt or copper, the corresponding metal phthalocyanines of the carboxylic acid type are obtained.

As the hollow fibers, those spun by a dry-wet method or the like from polyvinyl butyral, polysulfone, cellulose acetate, polyvinylidene fluoride, polycarbonate, polypropylene, etc. can be used.

As a method for retaining phthalocyanine-based metal complexes in hollow fibers, if the hollow fibers are spun by a dry-wet method, the metal complexes are mixed into the spinning dope (dope solution). It can be contained within the hollow fibers. In addition, methods such as immersion or spraying using a metal complex solution may also be used. The amount of the phthalocyanine-based gold mud complex retained is generally about 1 to 10% by weight, preferably about 2 to 8% by weight, based on the weight of the polymer hollow fiber.

The hollow fiber module is used, for example, in the form of a module 10 as shown in FIG. 1 as a centerline sectional view. The hollow fibers 1 are bundled using strings 2, 2', etc., with the openings 3, 3' at both ends aligned (this does not need to be strictly aligned, but as long as they are bundled so that they are substantially aligned). A closed part 4.4' is provided in which the outer circumferential surfaces of each hollow fiber are adhered to each other using an adhesive or the like, leaving a hollow part of each hollow fiber at the openings at both ends. Such a group of hollow fibers is housed in the housing 5 so that the closing portion 4.4' is inscribed therein. At both ends of the housing 5, fixed or removable lids 6.6' are attached.
Holes 7 and 7' are provided in each of the holes 7 and 7' in the body 5a of the housing 5.
are each provided with at least one, in the illustrated embodiment two holes 9.9' located opposite each other.

In such a module 10 of the hollow fiber 1, as shown in FIG. ing. Further, the two holes 9 and 9' in the body 5a of the housing 5 communicate with each other via a gap 1c between the hollow outer parts 1b of the hollow fibers 1.

Therefore, in the mosier 10 of the hollow fiber 1, which is a bundle of a large number of hollow fibers 1 as shown in FIG.
The hollow fiber exterior 1b is brought into contact with the water, and the fluid containing the malodorous substance is brought into contact between the holes 7 and 7' of the other lid body 6 and 6', that is, the hollow fiber interior 1a, so that they can flow with each other. let

The hollow fiber 1 holding the phthalocyanine metal complexes contacts moisture at the outside 1b of the hollow fiber and has a large surface area, so the deodorizing efficiency of the phthalocyanine metal complexes increases and the phthalocyanine metal complexes circulate inside the hollow fiber 1a. Malodorous substances are significantly reduced and deodorized at the outlet hole 7'.

In addition to the method described above, contact of the hollow fibers with water can be carried out using the lid 6.6.
Water may be sent between the holes 7 and 7' of the housing 5, that is, into the hollow fiber interior 1a, and a fluid containing a malodorous substance may be caused to flow between the holes 9 and 9' of the body 5a of the housing 5.

Further, instead of the liquid water that is sent in, a fluid such as a humid gas containing moisture can also be used.

Furthermore, instead of continuously feeding the fluid water or the gas containing water into the hollow fiber interior 1a or the hollow fiber exterior 1b, the hollow fibers and water or the fluid containing water are always kept in the module in the previously described state. They may be in contact.

〔Effect of the invention〕

In the deodorizing method according to the present invention, a fluid containing moisture is brought into contact with either the inside or the outside of a large number of modular hollow fibers holding phthalocyanine-based metal complexes, so that the hollow fibers are Always in a moist state due to water. Therefore, the deodorizing ability of phthalocyanine-based metal complexes, which are more effective in the presence of moisture, is greatly improved, and the deodorizing efficiency of hollow fibers can be greatly increased.

The malodorous substances that should be deodorized are malodorous substances that have active hydrogen, such as hydrogen sulfide, alkylmerocabucnes, aldehydes, and ammonia, and the deodorization of these substances is greatly promoted by the presence of moisture. Ru. However, ammonia is thought to be absorbed into water and form ammonium salts.

〔Example〕

Next, the present invention will be explained with reference to examples.

Example 1 A hollow fiber obtained by dry-wet spinning polyvinyl butyral (Wako Pure Chemical Industries) with water as the core liquid was drained and then placed in an aqueous solution of octacarboxyphthalocyanine iron complex at a concentration of 5% by weight at room temperature for 1 hour. After soaking it, pulling it up once and air drying it, it became 0. It was immersed in an IN acetic acid aqueous solution for 30 minutes, washed with water until neutral, and then air-dried.

The polyvinyl butyral hollow fiber with an inner diameter of 0.5 mm and an outer diameter of 1.0 mm, to which the carboxyphthalocyanine metal complex was attached in this way, was cut into a length of 300 mm.
After thoroughly drying at 0°C, 300 of them were cut into 40m inner diameter.
The module was housed in a polycarbonate case having a length of 300 mm and a length of 300 mm, and a module O was prepared as shown in FIG.

Using this module 10, while passing water from the inlet hole 9 to the outlet hole 9', that is, through the hollow fiber exterior 1b, 50p of ammonia, which is a malodorous component, is extracted from a malodor generator (not shown).
pm (inlet concentration) from the inlet hole 7 to the outlet hole 7', that is, into the interior 1a of the hollow fiber.
When pressurized to g/1 and fed at a flow rate of 10 m1 per minute, the outlet hole 7' was connected to a detection tube (not shown) and the outlet concentration of malodorous components was measured, and it was found to be significantly reduced to 1 ppm. Ta.

Comparative Example 1 In Example 1, without passing water through the module 10,
When a gas containing 50 ppm (inlet concentration) of ammonia, a malodorous component, was fed under the same conditions, the outlet concentration of the malodorous component was as high as 20 ppm, and deodorization was not sufficient.

Example 2 In Example 1, 10% of hydrogen sulfide was used instead of ammonia.
When using a gas containing ppm (inlet concentration), the outlet concentration of malodorous components was significantly reduced to t ppm.

Comparative Example 2 In Example 1, without passing water through the module IO,
When a gas containing 10 ppm (inlet concentration) of hydrogen sulfide, a malodorous component, was fed under similar conditions, the outlet concentration of the malodorous component was a ppm, and deodorization was not sufficient.

[Brief explanation of drawings]

FIG. 1 is a sectional view along the center line showing an embodiment of an apparatus for carrying out the deodorizing method according to the present invention. FIG. 2 is an enlarged view of the main part of FIG. 1. [Explanation of symbols] 1--Hollow fiber, 1a--Hollow fiber interior, 1b--Hollow fiber exterior, 10--Module. Agent Patent Attorney Toshio Yoshida 4;'t L Figure 2

Claims (1)

[Claims] 1. Using a hollow fiber module holding phthalocyanine-based metal complexes, one of the inside and outside of the hollow fiber is contacted with a fluid containing moisture, and the other is brought into contact with a fluid containing a malodorous substance. A deodorizing method characterized by mutual circulation.