KR100430395B1 - Deodorizing agent for removing volatile organic compound and stink, and using method thereof - Google Patents

Abstract

The present invention relates to volatile organic compounds (VOC's) and deodorants for removing odors and methods of using the same, more specifically starches 10,000 to 30,000 mg / l, Na ₂ CO ₃ 30,000 to 80,000 mg / l and CaCO ₃ 1,000 to Deodorant composition for volatile organic compound and odor removal comprising 15,000 mg / l and using the deodorant composition reacting for 3 seconds to 10 minutes by mixing or spraying 100 to 5,000 mg / l to the odor source or volatile organic compound It is about a method. Deodorant of the present invention by controlling the chemical activity of the inorganic oxidizing agent which is an excellent chemical activity of the excellent deodorizing ability, high safety, excellent sustaining effect, there is an effect that can be used for industrial as well as home.

Description

Deodorizing agent for removing volatile organic compound and stink, and using method

The present invention relates to volatile organic compounds (VOC's) and deodorants for removing odors and methods of using the same, and more particularly, to oxidize and decompose odors through a combination of highly oxidizing inorganic chemicals (H ₂ O, N ₂ , CO _2, etc.), and volatile organic compounds and deodorants for removing odors, which can be deodorized by oxidizing and decomposing H ₂ S, CH ₃ SH, NH ₃ and the like, which cause odors, and the use thereof. It is about a method.

Volatile organic compounds scattered in the air environment are prominent substances that have a close influence on the generation of secondary pollutants such as ozone, and in themselves, they can cause very high risks to copper and plants, including humans. It is a major air pollutant that has received much attention recently. As in other countries, the severity of these problems is emphasized in Korea as a result, and from 1999, there has been a strong attempt to regulate the release of these substances. For this reason, VOC's emission control methods have been researched and developed in various ways. The methods generally used up to now are largely to remove pollutants, reduce the amount of pollutants or the amount of carrier gas mixed with them. , Waste gas purification technology, etc. (see Table 1 below).

Methods for Controlling Odor and VOC's Emissions Removal of pollutant sources 1. Seal the system as much as possible to reduce emissions to air 2. Replaced with raw materials and clean fuel with low generation of pollutants 3. altering the production process to prevent or inhibit the accumulation or generation of contaminants; 4. Review whether work steps can be changed 5. Recycle used gas or recycle pollutant to suppress pollutant emission How to reduce the amount of emissions or carrier gases mixed with them 1. To minimize the remaining of contaminants in the gas. 2. Reduce the area where pollutant air emissions can occur in the system. 3. Recycle some of the gas after the process 4. Devise a hood system to release the minimum amount of contaminants into the atmosphere Waste gas purification technology 1. Physical Method: Adsorption, Absorption, Condensation 2.Chemical Method: Incineration, Vapor-phase advanced oxidation 3. Biological methods: Biofilters, Bioscrubber, Biotricking filters

First of all, reducing the use of VOC's emissions should be the first step, but apart from that, it is also urgent to develop the purification technology by using VOC's. Adsorption, absorption, advanced oxidation, concentration, combustion, and biological treatment methods have been developed for use in VOC's control (see FIG. 1).

The various methods of deodorization we have classified so far have their own characteristics and disadvantages and cannot be said to be perfect. In fact, the gas containing the odor component to be treated is often a low concentration complex component, and the properties of the contained component are also different.

Technical data emitted from odor sources include composition and concentration of odor components, temperature, air volume, humidity, working time, process change, operation route, installation area, secondary pollution treatment measures, and fuel used. The most economical deodorization method will be selected.

On the other hand, if you look at the level and trend of the relevant foreign technology,

ADWEST Technologies, Inc. /United States of America

A) RTO (Regenerative Thermal Oxidizer) is produced and supplied under the trade name RETOX. Poppet valves are used to minimize peak time leakage, which has a VOC's destruction efficiency of more than 98% and is a disadvantage of two-can type. The heat recovery of about 95% is possible, and the compact structure of the equipment minimizes the installation site and the device is easy to operate.

2. Durr Industries, Inc. / United States of America

A) In the thermal oxidizer (Recuperative (RO) Regenerative (RTO)), RO is a direct oxidation method, which is suitable for low exhaust gas treatment, and the heat recovery efficiency is about 70%. RTO is a hepatic oxidation method suitable for the treatment of high exhaust and high concentrations of VOC's, and the heat recovery is about 95%. Low NOx emissions are expected, and halogen compounds can be processed.

B) Catalytic Oxidizer (Recuperative (CO) Regenerative (RTO))

CO (Recuperative) is a direct (catalyst) oxidation method requires a catalyst exchange for long-term use, RTO (Regenerative) is an indirect (catalytic) oxidation method has the advantage of low operating costs, but catalyst poison may be a problem.

C) Concentrator

It uses the principle of adsorption and desorption, and is suitable for high exhaust gas and low concentration VOC's gas treatment, and requires an oxidizer.

D) Concentrator + Oxidizer

Recuperative, indirect oxidation, catalytic type, and adsorption, desorption, and oxidation.

The devices are suitable for high exhaust and low concentrations of VOC's gas treatment and have a wide range of applications.

3.REECO (Regenerative Environmental Equipment Co., Inc.) / United States

A) It is possible to apply RCO as a technology that divides the ceramic heat storage layer into several spaces and performs inlet, outlet, and purge functions with a single rotary valve. Compared to the existing two-can, three-can and five-can RTOs, as a single can, it can purge up to 100,000 Nm ³ / hr and complete processing, resulting in very low equipment and maintenance costs.

B) Fluidized bed VOC's concentrator

By using fluidized bed adsorption and desorption towers, low concentrations of VOC's can be concentrated to a high concentration ratio of up to 10,000: 1 to minimize the amount of final treatment gas. The smallest footprint and low pressure provide the most economical concentration.

4. Edward Engineering Corp. / United States of America

A) VOC's cooling condenser

It is a VOC's recovery system that can condense and safely recover high concentrations of VOC's using a two-stage mechanical refrigeration system and operate a system that induces high efficiency by adding liquid nitrogen.

5.ENVI VERFAHRENSTECHNIK / GERMANY

A) Biofilter to remove odors and VOC's

It is easy to remove organic substances (V0C's) and to process VOC's-containing gas at low concentration using microorganisms. Odor was removed by economic system with low maintenance cost.

The disadvantage of the conventional odor removal method is that the odor removal rate is significantly lower, or the initial construction cost is high, the operating cost is also uneconomically practically little use value when applied to the site.

In addition, looking at the domestic prior patents related to deodorant, Korean Patent No. 3251 1 is blended with rice bran for yeast, kneaded by adding zeolite, fermented, and then mixed and dried iron sulfate to disclose a malodor treatment agent, Korea Patent No. 30303 discloses a deodorizing and heavy metal removal composition consisting of NaOCl, sodium carbonate, sodium phosphate, alumina alumina, ferrous sulfate, zeolite, acidic clay, sodium sulfite, Aaron Flock, and chlorine dioxide. In addition, Korean Patent No. 182845 discloses a deodorant using tartaric acid, sodium acetate, ascorbic acid and essential oils.

In addition, Korean Patent Publication No. 81-1714 removes odors such as raw waste and manure, and removes heavy metals from wastewater 15-65% iron sulfate, 1-20% garnetite, and 0.5-10% activated clay. And deodorant compositions comprising 0.1 to 5% manganese dioxide and 0 to the remaining amount of water are disclosed. Korean Patent Laid-Open No. 92-2170 discloses a deodorant using a microbial enzyme that removes various odors generated from organic wastes using the microbial enzyme as an active ingredient. In addition, Korean Patent No. 139559 discloses activated carbon fibers and nonwoven fabrics, and Korean Patent Application Publication No. 2000-6882 discloses KMnO ₄ , NaOCl, Ca (OH) ₂ , and NaCO ₃ , FeSO _3. And CuSO ₄ , an industrial deodorant comprising one or more components selected from the group consisting of.

As such, the conventional deodorant used in the chemical oxidation method is mainly composed of chlorine (including chlorine dioxide) and bio-based.

However, the patents include NaOCl, which is classified as a toxic substance, as the main raw material or vegetable essential oil, etc., in the case of NaOCl, which reacts with an organic compound containing nitrogen to generate chloroamine compounds, and sulfur (S). Reaction with the compound to produce a sulfenyl chloride (Sulfenyl Chloride) compound (Gmelin Handbook vol 6. 410-410). These amine chlorides and sulfenyl chlorides not only diffuse easily in the air, but also irritate the mucous membranes of the eyes, skin, and oral cavity, and cause problems of secondary pollution as substances harmful to the human body. Bio-based, which is composed of pine oil caster oil and natural plant essential oil (essential oil), contains fruit or acacia flavor but has no lasting effect as aromatic plant, and can show side effects such as headache when exposed for a long time. On the other hand, deodorizing ability is not even and foam is generated a lot of disadvantages such as economic disadvantages or difficult process conditions.

If the incompletely treated odor spreads to the surroundings, it will pollute the natural environment, destroy the ecosystem, threaten humanity, and it will be a major impediment to the development of the industry due to the pollution of the working environment.

Therefore, the present invention is a deodorant that can remove odors and VOC's, and is a method that combines the techniques of advanced oxidation treatment and absorption currently used, and is easy to apply to existing treatment systems, and is inexpensive in operating costs and processing efficiency. It has been developed an excellent deodorant that can maximize the, and prevent the occurrence of secondary pollution by converting to harmless materials through oxidative decomposition of VOC's, the present invention was completed based on this.

Accordingly, an object of the present invention is to provide a deodorant composition which can be used not only for industrial use but also for home use because it has excellent deodorizing ability, high safety, and long lasting effect by controlling the chemical activity of inorganic oxidizing agent which is a material having excellent chemical activity. It is.

Another object of the present invention is to provide a method of using the deodorant.

Deodorant of the present invention for achieving the above object comprises starch 10,000 to 30,000 mg / l, Na ₂ CO ₃ 30,000 to 80,000 mg / l and CaCO ₃ 1,000 to 15,000 mg / l. In addition, the deodorant composition may further comprise 500 to 2,000 mg / l NaOCl.

The method of using the deodorant to achieve the above another object is made of starch 10,000 ~ 30,000mg / l, Na ₂ CO ₃ 30,000 _~ 80,000mg / l and CaCO ₃ 1,000 _~ 15,000mg / l with respect to odor source or volatile organic compounds The deodorant composition, or a composition further comprising 500 to 2,000 mg / l of NaOCl, is mixed or sprayed with 100 to 5,000 mg / l to react for 3 seconds to 10 minutes.

1 is a diagram schematically illustrating the deodorization methods commonly used.

Looking at the present invention in more detail as follows.

The main components of the deodorant (odor treatment agent) according to the present invention include starch, Na ₂ CO ₃ and CaCO ₃ essentially, and may further include NaOCl depending on the type of malodor source or volatile organic compounds.

According to the present invention, the amount of starch having strong adsorption capacity to malodorous sources or volatile organic compounds is preferably 10,000 to 30,000 mg / l, and the adsorption power is lowered to less than 10,000 mg / l, and it is supersaturated when it exceeds 30,000 mg / l. It tends not to dissolve anymore. The starch is preferably dissolved by heating to 30 to 50 ° C. in an aqueous solution state to prevent increase in solubility and precipitation of starch.

The Na ₂ CO ₃ has a function of removing H ₂ S, the amount of the use is preferably 30,000 to 80,000 mg / l, less than 30,000 mg / l removal capacity is lowered, if it exceeds 80,000 mg / l deodorant The pH (hydrogen ion concentration) becomes a strong alkali, which may adversely affect the active microorganisms in the wastewater treatment plant. In addition, CaCO ₃ has a decolorizing ability, the amount of use is preferably from 1,000 to 15,000mg / l, less than 1,000mg / l decolorization effect is lowered, when exceeding 15,000mg / l is difficult to completely dissolve remains as a solid When spraying deodorant, clogging of the nozzle of the spray device may cause the wear of the machine.

In addition to the above components, NaOCl has excellent oxidizing power as a component to be further added depending on the type of malodor source or volatile organic compound, and its amount is preferably 500 to 2,000 mg / L. If the amount is less than 500mg / L, the oxidizing power is lowered. If it is over 2,000mg / L, the microorganisms in the wastewater treatment plant not only have a bad effect, but also combine with organic matter in the wastewater, causing severe odor and forming carcinogens. Tends to cause

The concentration of the deodorant to the target malodorous substance or volatile organic compound is in a preferred range of 100 to 5,000 mg / l to treat a normal malodorous or volatile organic compound and does not adversely affect microorganisms, but the odor or volatile organic substance to be treated. Depending on the concentration of the compound may be out of the concentration. In conclusion, the concentration of the deodorant according to the invention may vary depending on the concentration of the malodor, but can be treated with the preferred examples mentioned above, except in special cases.

In addition, looking at the manufacturing process of the deodorant according to the present invention, ① after the quality and specification inspection of the raw material received, ② precisely weighing the raw material at the mixing ratio according to the odor to be treated, ③ increase the activity of each, ④ chemical activity control Adjust the pH (hydrogen ion concentration) according to the place of use through the work, and then measure and pack it as a finished product.

In addition, the method of using the deodorant according to the present invention is when the odor source is dispersed (garbage landfill, public restroom, food waste transfer place, etc.), the deodorant of the present invention is diluted directly or in water according to the concentration (odor) of the odor. After spraying using spray or power sprayer, or ⓑ the water quality (sewage, sewage, wastewater treatment plant, etc.) by precisely analyzing the odor concentration of the water quality and then mechanically injecting it using a metering injection pump, etc. In air pollution prevention facilities, when used for cleaning wet scrubbers, the odor can be removed by contacting the gas while diluting it in rinsing water (circulating water) 30 to 100 times.

When the deodorant of the present invention is used, the deodorizing effect is rapid and excellent in sustaining effect (reaction time: 3 seconds to 10 minutes, duration of 7 days), and is harmless and odorless to produce secondary pollutants. (CO ₂ + H ₂ O), does not cause soil contamination (no heavy metals detected), is hypoallergenic to skin and is not acutely toxic (PII: 0.15, LD ₅₀ : 2,000 mg / kg or more).

Table 2 below describes the properties of the deodorant according to the present invention.

Properties of Deodorant According to the Present Invention Item standard Remarks Main components Inorganic oxidizer Color Transparent gray pH 5 to 12 smell Odorless Statue Liquid phase Heavy metals Fire detection Acute Toxicity Test (LD ₅₀ ) 2,000 mg / l KFDA Notification No. 98-116 Skin irritation test (P.I.I) 0.15 " Microbial test clear E.Coli ATCC 25922

On the other hand, the performance of the deodorant according to the invention and the performance of the existing product is described in Table 3 below.

Comparison of Deodorant of the Invention with Competitive Products in Korea Performance Category Invention Competitive products pH 5 to 12 7.1 Ignition residue 0.25 0.72 Solid water 0.31 0.94 Deodorization ability Ammonia Removal rate: 86.7% Removal rate: 73.3% Trimethylamine 83.3% 70.0% Hydrogen sulfide 98.3% 85.5% Methyl mercaptan 96.0% 80.0% Dilution factor 150 times 60 times LD ₅₀ (mouse) 2,000 mg / l or more 2,000 mg / l or more P.I.I 0.12 0.35 Microbial test clear clear

As shown in Table 3, the deodorizing ability of the deodorant according to the present invention can be seen that the deodorizing effect is very excellent.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to the following Examples.

Example 1

After diluting the deodorant of the present invention consisting of starch 20,000mg / l, Na ₂ CO ₃ 50,000mg / l, CaCO ₃ 10,000mg / l and NaOCl 1,000mg / l to the standard gas from Korea Research Institute Injected at a concentration of 30mg / l and the measurement results are shown in Table 4, Table 5 and Table 6. The starch aqueous solution was used by dissolving and storing in an aqueous solution (water) maintained at about 40 ℃.

division Measurement item Test Items unit ammonia Yellow hydrogen Methyl mercaptan Trimethylamine Deodorization test Initial concentration ppm 60 60 50 60 30 minutes later ppm 30 12 25 22 1 hour later ppm 23 8 20 19 2 hours later ppm 19 4 12 18 4 hours later ppm 16 2 8 12 6 hours later ppm 8 One 2 10 Removal rate 86.7 98.3 96.0 83.3

Heavy metal detection test by soil deodorant of the present invention (soil pollution) Test Items unit The present invention (deodorant) Remarks CD ppm Not detected Water Pollution Process Test Method Cu ppm Not detected As ppm Not detected Hg ppm Not detected Pb ppm Not detected Cr ⁺⁶ ppm Not detected Organic ppm Not detected PCB ppm Not detected CN ^- ppm Not detected Phenols ppm Not detected n-hexane extract ppm 1 or less

Microbial treatment test by deodorant of the present invention Biological test strain (E.Coli) unit Early After 24 hours Remarks 200 ppm (150 times diluent) CFU / ml 4.7 × 10 ⁵ 5.7 × 10 ⁶ 300 ppm (") CFU / ml 4.1 × 10 ⁵ 5.1 × 10 ⁶ Control CFU / ml 4.5 × 10 ⁵ 6.4 × 10 ⁶ Test strain: Escherichia Coli ATCC 25922 Inoculate bacteria cultured in sterile water, adjust the number of Escherichia coli to 2-8 × 10 ⁵ , and measure the initial bacterial count of the prepared contaminated water.

Example 2

For the performance analysis of the deodorant drug (deodorant) after diluting the deodorant of the present invention consisting of starch 20,000mg / l, Na ₂ CO ₃ 50,000mg / l, CaCO ₃ 10,000mg / l and NaOCl 1,000mg / l 50 times The removal rate was measured at a concentration of 100 ppm. The results are shown in Table 7 below.

Treatment efficiency by odor type and concentration division Measurement item Before inputting medicine After chemical injection Processing efficiency Remarks Experiment 1 CH ₃ SH 50 ppm 0.4 ppm 99.2% Result after 10 minutes of drug administration. H ₂ S 12 ppm 0.00 ppm 100% NH ₃ 25 ppm 4.6 ppm 81.6% Experiment 2 CH ₃ CHO 2.6 ppm 0.06 ppm 97.7% This is the result of analysis after collecting gas of S company. C ₆ H ₅ CHCH ₂ 0.8 ppm 0.00 ppm 100% Experiment 3 NH ₃ 10 ppm 1.06 ppm 89.4% Results of industrial waste incineration gas analysis. H ₂ S 2.3 ppm 0.00 ppm 100% . The above sample was collected in the Tedlar bag, and the analysis was a result of comparing the analysis to the standard gas. The analysis method was: GC-FID analysis.

Example 3

After removing the components of NaOCl in Example 2, it was carried out in the same manner except for changing the concentration of the deodorant to 200ppm for the malodor of poultry farm. The results are shown in Table 8 below.

Odor elimination efficiency according to duration in poultry farm division duration unit Hydrogen sulfide Mercaptan Analysis method Remarks Initial concentration ppm 24.3 4.7 GC-FID Analysis 0.5 hour ppm N.D N.D " 1 hours ppm 0.01 N.D " 4 hours ppm N.D 0.003 " 1 day ppm 0.10 N.D " 2 days ppm 0.03 0.002 " 3 days ppm 0.07 0.004 " 7 days ppm 0.15 0.003 " Average removal rate (%) 99.8 99.9

As described above, the deodorizing agent of the present invention is an inorganic oxidizing agent which is an excellent chemical activity by controlling the chemical activity of its own excellent deodorizing ability, high safety, excellent sustained effect can be used not only for industrial use but also for home use There is.

Claims (3)

A volatile organic compound and a deodorant composition for removing odors, comprising starch 10,000 to 30,000 mg / l, Na ₂ CO ₃ 30,000 to 80,000 mg / l, and CaCO ₃ 1,000 to 15,000 mg / l. The deodorant composition of claim 1, wherein the deodorant composition further comprises 500 to 2,000 mg / l of NaOCl. For removing volatile organic compounds and odors by reacting for 3 seconds to 10 minutes by mixing or spraying 100-5,000 mg / l of the deodorant composition according to claim 1 or 2 with respect to malodorous sources or volatile organic compounds. Method of using the deodorant composition.