JPS63147543A - Desulfurizing agent - Google Patents

Abstract

PURPOSE:To enhance the capacity of the title agent to adsorb and remove the sulfur compds. such as hydrogen sulfide, methyl mercaptan, etc., by mixing ascorbic acid or erythorbic acid and a water-soluble cupric compd. to prepare the desulfurizing agent. CONSTITUTION:Ascorbic acid or erythorbic acid and a water-soluble cupric compd. such as cupric sulfate, cupric nitrate, and cupric chloride are mixed to prepare a liq. mixture. From 0.01-100pts.wt. water-soluble cupric compd. as metallic copper, based on 1pt.wt. ascorbic acid or erythorbic acid, is appropriately incorporated into the liq. mixture. The liq. mixture can be used as such as a desulfurizing agent, and the concns. of the two components are appropriately controlled to 1-10wt%. The desulfurizing agent has a strong affinity for the sulfur compds. such as hydrogen sulfide and methyl mercaptan which are the malodorous or offensive-odor components, and has a strong action to adsorb and remove the components.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a desulfurizing agent that is excellent in removing sulfur-based compounds such as hydrogen sulfide and mercaptans that cause malodors and off-flavors.

Conventional technology In recent years, with the development of industry and improvements in consumer life, opportunities for a wide variety of bad odors and strange odors to occur have increased.

There is growing interest in the removal or reduction of

Traditionally, incineration has been used as a method to remove or reduce bad odors and odors generated from industrial waste.

Scraping methods are used. Also, hospital 1
When it comes to filth and waste generated from grocery stores, agricultural and livestock processing plants, and fisheries processing plants, it is possible to remove odors by using a youth absorbent such as activated carbon, or by using acid or alkali to absorb odors. A processing method such as a method of summing is generally adopted. In addition, in home life, the kitchen, refrigerator,
Various deodorizing products using activated carbon, for example, have been developed for places where bad odors occur, such as toilets.

The present inventors have found that a composition containing ascorbine and an iron (II) compound exhibits a high odor control effect against a wide range of malodorous substances (for example, Japanese Patent Application Laid-open No. 132937/1982). Focusing on this, we investigated compositions containing various metal compounds and ascorbic acid and their effects, and found that a composition consisting of ascorbic acid and a water-soluble cupric salt was one of the substances that cause bad odors and off-odor. It has been found that it is particularly effective in removing bad odors associated with sulfur-based compounds such as hydrogen sulfide and mercaptans.

The present invention was completed as a result of further studies based on this knowledge.

Examples of the water-soluble cupric compound used in the present invention include cupric salts of inorganic acids. Specific examples of such substances include cupric sulfate, cupric nitrate, cupric chloride, and hydrates thereof.

The blending ratio of these water-soluble cupric compounds to ascorbic acid (or erythorbic acid) is 1
0.0 as copper metal for heavy M part. The content ranges from 1 to 100 parts by weight, preferably from 0.05 to 15 parts by weight. If the proportion of copper is lower than this range, the desulfurization effect will be weak, and if it exceeds this range, the copper salt component will only act alone and no synergistic effect with ascorbic acid will be observed.

The desulfurizing agent of the present invention can be used in the form of an aqueous solution by dissolving each of the above two components in water. In this case, the concentration of the aqueous solution is not particularly limited, but a solution in which the concentrations of the two components are generally in the range of approximately 1 to 30% by weight is also used. It is preferable to use distilled water, ion exchange water, pure water, etc. as the water. The aqueous solution of I) I+ can be adjusted as appropriate depending on the purpose of use. If pII becomes high, turbidity may occur, but it may be used as is.

The desulfurizing agent of the present invention can be used in solid form, such as powder or granules. More preferable usage forms include (i) supporting on a porous carrier;
ii) Used by attaching it to fibrous materials such as paper, textiles, and non-woven fabrics; (iii) Used by blending with various plastic resins; or (iv) Used by applying it to base materials such as plastic films. can be mentioned. When used in solid form, it is prepared by dissolving ascorbic acid or erythorbic acid and a water-soluble cupric compound in water or an alcohol such as methanol to form a solution, and then removing the solvent from this solution. For example, a powdered desulfurization agent can be obtained by spray drying a water/8 solution or a metal solution. When supported on a porous carrier such as activated alumina, zeolite, activated carbon, sepiolite, silica, diatomaceous earth, activated clay with a viscosity of 1, etc., the carrier is sufficiently immersed in a solution and dried to form a carrier. be able to.

In this case, there is no restriction on the supported m, but usually 0.1 to 1.0, preferably 0.2 to 1.0, of the desulfurizing agent per 1 part by weight of the carrier.
The range is 0.6 parts by weight. This is an amount commensurate with the pore surface area of the carrier; if it is more than this, the difference from the case where the powder is used alone will not be clear, and if it is less than this, the absorption capacity per unit volume will decrease. Furthermore, a solution can be applied to the fibers, or the fibers can be immersed in the solution and then dried to obtain a fiber impregnated with the desulfurizing agent of the present invention. Furthermore, when used by blending with resins such as polyethylene, polypropylene, epoxy resins, and urethane resins, the powdered desulfurizing agent may be kneaded with these resins and then molded and used. In addition, U supported on a carrier
- The desulfurizing agent can also be used by impregnating, coating, or kneading paper, cloth, plastic, etc.

In addition, when performing impregnation 1 coating, etc., it can be carried out by dispersing it in a liquid medium such as an aqueous solution or a resin liquid.

The desulfurizing agent of the present invention has a strong affinity with sulfur-based compounds, for example, malodor/off-odor components such as hydrogen sulfide and methyl mercaptan, and has an extremely strong effect of absorbing and removing sulfur-based compounds. Furthermore, it also has the effect of removing odors based on ammonia and amines.

Therefore, the desulfurizing agent of the present invention is specifically suitable for household use.

In addition to being used as a deodorizing agent in hospitals, shops, and various processing plants, it is also used as a corrosion inhibitor for metals, and as a silver.

Useful as a copper sulfidation inhibitor. In particular, various papers impregnated and attached with the desulfurizing agent of the present invention are suitable as wrapping papers for metals.

When using the desulfurizing agent of the present invention as a deodorizing agent, it is necessary to
In addition to being able to be used by directly spraying or scattering on the source of the off-odor, the solid agent can also be used by installing it at the source of the off-odor.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 12.35 g of cupric sulfate pentahydrate was dissolved in distilled water. To this aqueous solution, 2.3 g of ascorbic acid and distilled water were further added to obtain an aqueous solution with a total volume of 50 rrdl.

On the other hand, 13.75 g of ferrous sulfate heptahydrate was dissolved in distilled water, and then 2.5 g of ascorbic acid and distilled water were added thereto to form an aqueous solution having a total amount of 50.

10 d of the two types of aqueous solutions obtained in this way were mixed with distilled water IO
- diluted with -. 20 g of activated alumina (Neobeads MSDL-3, Mizusawa Chemical Products) was immersed in this diluted solution, stirred sufficiently to penetrate the solution, and then dried under reduced pressure in a silica gel desiccator for 24 hours to be supported on the activated alumina. A desulfurizing agent was obtained.

Sample A1 was obtained from an aqueous solution containing cupric sulfate and ascorbic acid, and sample B was obtained from an aqueous solution containing ferrous sulfate and ascorbic acid.

9.5 for each sample! n1. A glass tube (diameter 1.56
Sample A, sample A,
The gas absorption ability of B was measured. For control purposes, activated alumina alone was used to measure the absorption capacity of the mixed gas.

The mixed gas used was made by mixing 80% (volume) of air with 100% humidity and 20% (volume) of nitrogen gas.
This R, H, was adjusted to 780%, and further ammonia (Nl+), hydrogen sulfide (It, S), and methyl mercaptan (C11,311) were added to reduce N113 to 30%.
ppm, II, S is 15ppm, CII, SII is 3
It was confirmed that ppm was included.

The measurement results of the absorption capacity for odor components of C11.3 and Cll33II are shown in FIGS. 1 and 2, respectively.

In addition, the IItS and Cll5SIl absorption ability of each sample was expressed as transmittance. The transmittance is calculated based on the concentration of each odor component in the mixed gas after passing through the sample layer and the concentration of each odor component in the mixed gas before introduction into the sample layer.
The lower the transmittance, the higher the absorption capacity.

As is clear from Figures 1 and 2, the present desulfurization agent (Sample A
) is superior in the initial (about 20 hours) absorption capacity for hydrogen sulfide and methyl mercaptan compared to the composition containing iron (II) and ascorbic acid (sample B), and is capable of rapidly removing bad and off-odor odors. This is expected to have a significant effect.

Example 2 2.47 g of cupric sulfate pentahydrate was dissolved in distilled water,
To this aqueous solution, 6.3 g of ascorbic acid and distilled water were further added to obtain a total ff150 aqueous solution. On the other hand, 12.35 g of cupric sulfate pentahydrate was dissolved in distilled water, and to this aqueous solution, 0.31 g of ascorbic acid and distilled water were further added to obtain an aqueous solution with a total ff of 150-. Each aqueous solution 1
0d with 10m of distilled water to dilute it, and add activated alumina (Neobeads MSDL-3: Mizusawa Chemical Products) 2 to this diluted solution.
After 0 g was immersed, thoroughly stirred, and dried under reduced pressure in a silica gel desiccator for 24 hours, a desulfurizing agent supported on activated alumina was obtained.

2.47 g of cupric sulfate pentahydrate and 6. ascorbic acid.
The desulfurizing agent prepared using 3g of sample C1 cupric sulfate 5
A desulfurizing agent prepared using 12.35 g of hydrate and 0.31 g of ascorbic acid was used as sample pD.
The absorption capacity of 33I+ was measured. The results are shown in FIGS. 3 and 4.

Figures 3 and 4 show that in the absorption of hydrogen sulfide and methyl mercaptan using the desulfurization agent of the present invention, when the blending ratio of ascorbic acid is high and the ratio of copper is low (sample C), the initial activity is slightly lower, but it becomes a long-lasting desulfurization agent. , conversely, a high copper ratio (sample D) indicates that the initial activity increases.

Example 3 12.35 g of cupric sulfate pentahydrate was dissolved in distilled water, and 2.5 g of erythorbic acid and distilled water were added to this aqueous solution to obtain an aqueous solution with a total ff of 150+nl. This aqueous solution 1
20 g of activated alumina (Neobeads MSDL-3, Mizusawa Chemical Products) was immersed in this diluted solution, thoroughly stirred, and then dried under reduced pressure in a silica gel desiccator to form activated alumina. A supported desulfurization agent was obtained. This material was designated as Sample E, and a mixed gas was passed through it under the same conditions as in Example 1.
．． The absorption capacity of 5, CI1, and S11 was measured. The results are shown in FIG.

Example 4 6.5 g of cupric chloride CuC1t dihydrate was dissolved in distilled water, and 2.5 g of ascorbic acid was further added to this aqueous solution.
and distilled water to obtain a total f150d aqueous solution.

10 volumes of this aqueous solution was diluted with 10 volumes of distilled water, 20 g of zeolite (Mizuka Sieves 5A-812B; Mizusawa Chemical Products) was immersed in this diluted solution, stirred thoroughly, and then dried under reduced pressure in a silica gel desiccator to be supported on the zeolite. A desulfurizing agent was obtained. This was used as Sample F, packed in a glass tube, and a mixed gas was passed through it under the same conditions as in Example 1, and the absorption capacity of the odor component molecules its and C113S 11 was measured. The results are shown in FIG.

[Brief explanation of the drawing]

Figure 1 shows the desulfurization agents prepared in Example 1 (Samples A and B).
) shows the hydrogen sulfide absorption capacity curve. Figure 2 shows the methyl mercaptan absorption capacity curve of the desulfurization agent prepared in Example 1. Figure 2 shows a methyl mercaptan absorption capacity curve and a methyl mercaptan absorption capacity curve. FIG. 5 shows a hydrogen sulfide absorption capacity curve and a methyl mercaptan absorption capacity curve of the desulfurization agent (sample E) prepared in Example 3. Moreover, FIG. 6 shows a hydrogen sulfide absorption capacity curve and a methyl mercaptan absorption capacity curve of the desulfurization agent (sample E) prepared in Example 5. Figure 1 11 books (fir) Figure 2 Time (hr) Figure 3 Kano 1', i7 (hr) 1 Kyou 4 Figure 5

Claims (1)

[Claims] A desulfurizing agent containing ascorbic acid or erythorbic acid and a water-soluble cupric compound.