KR980008306A - Adsorption / decomposition type powder composition for removing organic phosphorus compounds - Google Patents

Abstract

An adsorption / decomposition type powder composition for removing organophosphorus compounds, which contains, as an active ingredient, a cation exchange resin as a disintegrating agent, and a high performance activated carbon having a BET specific surface area of 2000 m 2 / g as an anion and an adsorbent. The composition according to the present invention is superior in safety to organic phosphorus compounds such as skin irritation and eye mucous membrane irritation while having superior performance to conventional organophosphorus compound.

Description

Adsorption / decomposition type powder composition for removing organic phosphorus compounds

FIG. 1 illustrates an apparatus for desorbing and desorbing organic phosphorus compounds.

FIG. 2 is a graph comparing the detoxification performance of various organophosphorus compound removal compositions with respect to the degree of increase in skin pollution of organic phosphorus compounds.

FIG. 3 is a photographic view showing an admiral effect of the composition of the present invention on a rust-inducing substance against rabbits; FIG.

[TECHNICAL FIELD OF THE INVENTION AND RELATED ART OF THE SAME]

The present invention relates to a powder composition for removing organic phosphorus compounds. More specifically, the present invention relates to a powder composition for removing organic phosphorus compounds which can remove contamination by organophosphorus compounds by effectively adsorbing and then decomposing organophosphorus compounds such as highly toxic pesticides or pesticides in a gaseous or liquid state will be.

Activated carbon has been widely used as an adsorbent for various toxic compounds including organophosphorus compounds. Among them, Ambersorb ^R , a polymer resin type adsorbent developed by Rohm and Haas, USA, is the most powerful adsorbent. Organophosphorus compounds are irreversible inhibitors of neurotransmitter enzymes, acetylcholinesterase, and are fatal compounds that can lead to deaths from trace amounts of poisoning and poisoning. Therefore, it is necessary to develop a method or a composition for his reliable admiral.

Due to this necessity, Rohm and Haas developed a demulsifying agent using a polymer resin as a raw material to prevent secondary contamination due to desorption after adsorption, and then mixed with Ambersorb to prepare an adsorbing / decomposing agent, Ambergard XE-555 Respectively.

[Technical Problem]

The above-mentioned Ambergard XE-555 from Rohm and Haas had some unsatisfactory aspects in terms of human irritation. Accordingly, it is an object of the present invention to provide a new adsorption / decomposition composition which is superior to Adamson XE-555 but which is less toxic to human body and more economical.

[Structure and operation of the invention]

The present inventors have intensively studied to open a new adsorption / decomposition composition which is superior to the above-mentioned Ambergard XE-555, which is the most excellent adsorption / decomposition additive composition for organic phosphorus compounds, A high performance activated carbon having a BET specific surface area of at least 2000 m 2 / g is used as an adsorbent, and an anion exchange resin and a cation exchange resin are used as disintegration agents in an appropriate ratio to obtain an organic phosphorus compound Lt; / RTI > adsorption / decomposition composition for removal can be obtained. On the other hand, it is preferable to add fumed silica to improve fluidity and homogenization of the obtained composition.

Hereinafter, the present invention will be described by way of examples, but the scope of the present invention is not limited to these examples.

[Example 1]

Manufacture of minute release

Cation exchange resin Amberlyst 15 ^R and anion exchange resin Amberlite IRA-900 ^R were used as raw materials.

100 g of Amberlyst 15 ^R was filled in the column and then washed with distilled water until a neutral pH was reached. Dried at 80 ° C to min. 100 ° C, finely pulverized using a pulverizer, and particles having a diameter of 10 μm or less were selected for dissolution 1.

100 g of Amberlite IRA-900 ^R was filled in the column and then washed with IM NaOH aqueous solution until no white precipitation occurred by the AgCl precipitation method. Washed with distilled water from which carbonate ion had been removed until it reached neutral pH, dried at 60 ° C to 80 ° C, and then finely ground to particles of 10 μm or less to obtain dissolution 2.

[Example 2]

Selection of adsorbent and preparation of mixed composition with disintegration

The specific surface area thereof for a candidate substance such as Xen348F (manufactured by Rohm and Hass), Merck Carbon (manufactured by Merck), Maxsorb (manufactured by Kansai Chemical Co.), and Carbon cloth (manufactured by Carbon Cloth, Ltd.) As a result of testing the saturated adsorption amount for phosphate (DMMP), Maxsorb, which has the largest specific surface area and saturated adsorption amount to DMMP, was selected as a high performance active bath and used in the experiment. As shown in the following table, in order to achieve the desired effect, the BET specific surface area is generally at least 2000 m 2 / g, which is sufficient to satisfy the object of the present invention.

¹⁾ Rohm and Hass products

²⁾ Merck products

³⁾ Products of Kansai Chemical Co.

⁴⁾ Carbon Cloth Ltd. Company Products

A preliminary experiment was conducted on the composition of the adsorbent and the disintegration to adjust the composition so that the amount of the adsorbent 20-50 wt%, the cation resin 22-40 wt%, the anion resin 22-40 wt%, and the fumed silica were 2 wt% To prepare an antidandruff composition according to the invention (wherein the% by weight is the mass% of solids excluding water content). An antidote composition consisting of 43% by weight of Maxsorb, 28% by weight of cation exchange resin Amberlyst 15 ^R, 28% by weight of anion exchange resin Amberlite IRA-900 and 1% by weight of fumed silica was prepared as an adsorbent and named as M-Kit, Was used for the experiment.

[Example 3]

Performance comparison

1. Comparison of structural characteristics

The most important characteristic in the analysis of the characteristics of the adsorbent using the adsorption phenomenon is the structure of the adsorbent itself, particularly the pore characteristics. This characteristic is determined by the raw material of the adsorbent and various changes occurring in the carbonization / activation treatment process. Generally, nitrogen gas is adsorbed at -196 ° C., which is the liquefaction temperature of nitrogen. The BET specific surface area, BET specific surface area, pore size distribution obtained by Kelvin eq., Diameter and shape of the pores, etc., are calculated from the equilibrium adsorption pressure based on the BET (Brumauer, Emett, Teller) It provides basic properties of adsorbent selection with appropriate pore shape and surface area depending on the application by revealing by various methods. The results of comparison of the surface characteristics of the composition M-Kit according to the present invention and Ambergard XE-555 of Rohm and Haas Co., USA are as follows.

Table 1 Comparison of surface properties of Ambergard XE-555 with the present invention (mixed composition, M-Kit)

As can be seen in Table 1, the composition M-Kit according to the present invention is superior to Ambergard XE-555 in B.E.T. It has superior properties in terms of surface characteristics including specific surface area and pore distribution diagram, and thus it is predicted that the adsorption performance is also superior. To demonstrate this fact, DMMP (dimethyl methylphosphate) vapor adsorption and desorption rate comparative tests were performed as follows.

2. DMMP vapor adsorption / desorption

Admiral ability of adsorbent and adsorbent was considered to be more important than decomposition ability because it absorbs / adsorbs the liquid contaminated with the skin rapidly. Although there are various measurement methods for the adsorption capacity, in the case of fine powders like the powder type agent, a liquid adsorption method is generally used. However, the antiseptic agent for the skin is directly contacted with the liquid agent in powder form, and the desorption process is also used in a situation where the solid-gas interface phenomenon is not ultimately liquid adsorption. Therefore, the adsorption performance evaluation by the gas-phase adsorption method is more realistic, and the practical methods of vapor-phase adsorption are common to the methods applied to the particulate adsorbent. The flowability of the weight of the adsorbent due to the scattering phenomenon of the fine particles and the powder contamination in the adsorption device are concerned, and it is difficult to carry out the adsorption test by the precise measurement method.

In this experiment, the amount of adsorbed DMMP and desorption amount were measured using a desiccator method generally used for the measurement of saturated adsorption amount. The amount of sample was about 200 mg of dried powder in a vial, and DMMP was used in Aldrich product. The experimental temperature was maintained at 35 ° C using a Humidity Chamber of Blue M Company. The vial containing DMMP was placed in the desiccator together with the samples, and the desiccator was outgassed to saturate the inner space with DMMP vapor The amount of saturated adsorption was determined by using the weight increase.

On the other hand, desorption was induced by a 35 ° C vacuum pump for about 6 hours to compare desorption phenomena. The inside vacuum pressure was about 5 u Torr or less, and the retention ratio was obtained by comparing the residual adsorption amount after desorption to the saturated adsorption amount. Since the residual adsorption amount after desorption is comparatively strong and safely adsorbed, it can not easily be desorbed under ordinary conditions. Therefore, it can be considered as the basic performance value of adsorbing agent, and comparison of the adsorbing amount of adsorbing agent can be made by comparing these values. The retention rate is a value that allows estimation of the amount that can be desorbed after adsorption and cause secondary contamination.

Desorption amount measurement

Unlike the measurement of DMMP vapor adsorption / desorption using a desiccator, the vapor desorption amount of DMMP, which is desorbed from an adsorbent that has been contaminated by a constant concentration condition and desorbed by air flow, is collected by DEP (diethyl phthalate) . This condition is similar to the situation that can occur in a field by using an air flow instead of a vacuum method, and therefore, there are many variables such as a contamination concentration and an air flow as a more practical method of measuring the desorption amount.

The experimental conditions were as follows: 60 μL (about 73 mg) or 20 μL (23 mg) of DMMP was added to 200 mg of antidote to a weighing bottle with a lid, and the mixture was stirred for about 10 minutes in a closed space with a magnetic bar to uniformly adsorb it. It is poured into a weighing bottle container in the desorption container of the experimental apparatus. Put it in a chamber maintained at 35 ° C and sweep the desorbed DMMP through the surface of the detergent by flowing air at a flow rate of 0.5 L / min (be careful not to blow off the adduct powder).

Two trappers were placed in 20 ml of DEP, respectively, and were collected in 30 minutes and 30 minutes in the initial stage, and analyzed by HP 5890 II GC equipped with FPD.

DMMP adsorption / desorption results

The amount of saturated adsorption of each adsorbed / decomposed powder or partially activated carbon to DMMP, which is widely used as a similar agent, was tested and the results are shown in Table 2 below.

Table 2 Result of saturated absorption desorption test

Carbon: Powder activated carbon from Merck

C.C .: A product made by Charcoal Cloth Co. of the United Kingdom was crushed and passed through a 325 mesh sieve

The residues shown in Table 2 are adsorbed amounts remaining after vacuum desorption for 6 hours. These adsorbed amounts are strongly adsorbed amounts that are not desorbed even when they are allowed to stand for a considerable period after natural adsorption. It can be used as an important value for judging relevant characteristics. As shown in Table 2, in the case of the adduct powder mixed with the ion exchange resin, the residual amount was considerably decreased as compared with the adsorbent itself, which was simply adsorbed on the surface, and the ion exchange resin adsorbed relatively weakly Of the total population. Since the ion exchange resin has a resolution, it decomposes the desorbed contaminants and converts them into relatively non-toxic substances in the human body. However, when the desorption amount of the ion exchange resin itself is large, it is necessary to compare with the case where only the adsorbent is used. When the decomposition ability possessed by the resin can not sufficiently extinguish the desorption amount and the pollutant is released as it is, it is disadvantageous in terms of admiral effect and secondary pollution avoidance rather than only using the adsorbent. It is estimated to be insignificant when used. In particular, when a high performance adsorbent is used, the adsorption amount is increased several times and the retention time is good. Especially, the resin activated carbon was compared with general activated carbon at the time of the development of Ambergard in USA, but it was estimated that the high adsorption amount of high activated carbon was not compared.

In addition, the adsorption characteristics of the high-performance activated carbon are different from those of the adsorbent using Ambersorb because the pore size distribution is different.

In the case of Ambersorb, mesopores in the range of tens of angstroms are considerably developed, so there may be some advantages in the adsorption rate, but the adsorption force is somewhat weak, so desorption can easily occur. This is because only the micropore is intensively attracted and has a relatively strong adsorption capacity, and the high pore volume having a large amount of pores has a considerable proportion of Mesoporous in the case of Ambersorb compared with the activated carbon.

The mesopore is a pore having a diameter of 20-500A. It is known that the adsorption progresses by volume filling method after the adsorption is almost completed in the micropores where adsorption occurs at a low partial pressure. These adsorbed materials are known to be desorbed prior to adsorption to micropores. This indicates that the pore structure of the adsorbent is directly related to the adsorption / desorption of adsorbates, and the theoretical basis for estimating the size and shape of the pores from the adsorbed amount It is also.

On the other hand, in the case of high-performance activated carbon, when it is used as an antidote, it absorbs liquid droplets directly and the adsorption phenomenon proceeds. Therefore, there is a difference from the phenomenon of adsorption of vapor in the air. In this case, the adsorption rate will be relatively insignificant and absorption or wetting phenomenon As well.

Desorption amount measurement test result

The amount of DMMP desorbed from the antiseptic was collected and analyzed under constant pollution conditions. The amount of desorption was determined by comparing the amount of desorption after 30 minutes with the initial period of 30 minutes.

Experimental Results As shown in Table 3, except for the case of using high-performance activated carbon, the desorption amount in the initial 30 minutes is somewhat higher than that in the latter 30 minutes, which is in agreement with the assumption that the excess adsorption amount will be desorbed at an early stage .

Adsorption / decolorization powders using high - performance activated carbon showed very good desorption resistance at higher contamination concentrations than those using ambersorb type adsorbents. This indicates that the saturated adsorption amount is extremely high and therefore there is sufficient adsorption capability even at a high contamination concentration.

Table 3 DMMP desorption amount analysis

^* Quote from suction / desorption performance using desiccator

⁺ Merck activated carbon powder

3. Comparison of efficacy of skin antiseptic through animal experiment

Dunkin Hartley species male guinea pig (250 ± 50 g) for the evaluation of the toxicity of the organic phosphorus formulation, Adoxidation test for the pollutants and New Zealand White male rabbit (3 ± 0.3 kg) for the first irritation test The experiment was applied to the laboratory environment in which the temperature, humidity, and lighting cycle were adjusted for more than one week.

For the evaluation of the skin adherence ability of the organic phosphorus preparation, male guinea pigs were shaved with an electric clipper and an electric shaver to prevent scratches 24 hours before the experiment. After the animals were calibrated, the control group, which was not to be detoxified with a Gilson pipette, was applied evenly with a diameter of about 2 cm. Two minutes after application, the drug was decalcified with an adductor powder. The median lethal dose (LD ₅₀ ) was calculated based on the survival rate after 24 hours, and the admiral ability of each adduct was expressed as a protection ratio (PR).

As an evaluation of skin adherence to water-repellent substances, rabbits were also shaved and shaved 24 hours ago with an electric clipper and a razor. The left and right sides of the vertebra were separated by about 3 cm. 0.6 [mu] L of water-repellent material was applied to each area to a diameter of about 6 mm, and only two of the right three areas were fully decontaminated with admiral powder (Fig. 3). The size (diameter) and area of edema and necrosis after admission were measured and compared with the control site to evaluate adoxicity (% of control).

Evaluation results of skin toxicity of organic phosphorus compounds

LD ₅₀ of unexposed peanut at 250 ± 50 g of guinea pig exposed to skin organic phosphorus compounds was about 7.0 mg / kg. However, after two minutes, the LD ₅₀ of the admiral rose about nine times. The results are shown in Table 4 and shown in FIG. As shown in Table 4 and FIG. 2, the M-Kit showed an excellent defense rate of about 9.5 times (66.5 mg / kg) and Ambergard had a defense rate of about 8.9 times (62.6 mg / kg).

Table 4 Effect of Organophosphoric Acid on Skin Adverse Effect (GuineaPic)

^* Survival / Survival

These adverse effects may be influenced by various factors such as the skin condition of the poultry, the detoxifying time, the adsorbing capacity of the adsorbent, and the amount of the released antidote. Admixture of M-Kit, which has the best adsorption capacity and relatively the highest initial release

The effect was the best.

Evaluation results of skin toxicity of waterborne materials

After 4 hours in the skin of rabbits coated with 0.6 μL of the water-repellent compound with a diameter of about 6 mm, edema of 21.0 - 22.4 mm in diameter, 32.0 - 34.3 mm in 1 day, and 29.3 - 31.7 mm in 2 days were formed, The necrosis was formed in the size of 5.50 - 6.17 mm on day 1, 8.33 - 9.83 mm on day 2, and about 8.33 - 9.17 mm on day 3 (see Table 5 and Table 6).

Table 5 Effect of skin irritant substance (rabbit) - Size of lesion (mm)

Table 6 Effect of skin irritant causing skin rash (rabbit) - area of lesion (㎣)

The edema and necrotic area size after admiral Zero Adoption greatly decreased (Fig. 3B), and the effect of M-kit was good. In the size of edema, M-Kit decreased 32.8 - 34.8% of the control area and 39.4 - 42.4% of Ambergard. In the case of Ambergard, the size of necrosis was reduced to 11.0% on day 1, 53.8% on day 2, And decreased to 51.5% on the third day. When this result was converted into area (㎟), it showed relieved skin damage after decontamination as shown in Table 6.

4. Assessment of mucosal irritation

In the right eye of 9 male rabbits, 50mg of each antidote powder was injected and 3 mice were left untreated. The remaining 6 mice were washed with 50ml of physiological saline solution for 1 minute after 30 seconds. Unadulterated

The left eye was used as a control. The grade of mucosal irritation in the eye was evaluated according to the criteria of "Toxicological Tests of Drugs etc." (6)

The scores were scored according to the grade table, and the degree of stimulation was evaluated according to the ocular mucosal stimulation table in Table 7.

Table 7 Mucous membrane stimulation in the eye

^a) Acute ocular irritation index (maximum value of mean mucosal irritation index during the experimental period, usually on the first day)

^b) mean ocular irritation index (total stimulus score / number of rabbits)

^c) Individual ocular irritation index (7 days)

The mucosal irritation of the two reconstituted powders was observed on days 1, 2, 3, 4, and 7 after instillation, and the degree of irritation was evaluated by Ambergard (Table 8 - Table 11).

Table 8 Ocular mucosal primary irritation of M-kit (wash group)

Table 9 M-kit first mucosal irritation (non-washing group) 2 days

Table 10 Ambergard's mucous membranes primary irritation (wash group)

Table 11 Ambergard's mucosa primary irritation (non-rinsing group)

This irritancy is also due to the irritation of the adsorbent or the disintegration itself, but the effect of sulfonic acid and hydroxyl groups which can flow out from the decomposer when mixed with tears is great. Therefore, in the case of M-Kit, it is considered that these acid and base groups are effectively adsorbed by activated carbon having excellent adsorbability, whereby the irritation caused by these acids and base groups is extinguished and only the irritation of the powder itself is shown. Therefore, the change of irritation caused by washing seems to be not great in M-Kit. On the other hand, in the case of Ambergard, the adsorbent has a relatively low ability to be scratched so that it can not effectively remove the liberated sulfonic acid and hydroxyl groups, thereby exhibiting high irritation and showing marked reduction in irritation by washing.

These antidotes were assessed as M-Kit as a non-irritant-to-mild irritant and Ambergard as a mild irritant as assessed on the mucosal irritation table (see Table 7). Table 12 summarizes all the above results.

[Table 12] Comparisons of first mild irritation index

Claims (4)

Cation exchange resins and anion exchange resins as demulsifiers and B.E.T. An adsorption / decomposition type powder composition for removing organophosphorus compounds having a specific surface area of 2000 m < 2 > / g or more and high-performance activated carbon as an active ingredient. The composition of claim 1, further comprising silica gel as flowability and homogenization enhancer. The method according to claim 2, wherein 20 to 50 wt% of high performance activated carbon, 22 to 40 wt% of cation exchange resin, 22 to 40 wt% of anion exchange resin and 2 wt% or less of fumed silica Wherein the amount does not include zero. The composition of claim 3, wherein the composition comprises 43% by weight of high performance activated carbon, 28% by weight of cation exchange resin, 28% by weight of anion exchange resin, and 1% by weight of fumed silica. ※ Note: It is disclosed by the contents of the first application.