KR101060671B1 - Odor removal deodorant using biomaterials and manufacturing methods thereof - Google Patents

Abstract

PURPOSE: An odor removal deodorant and a manufacturing method thereof are provided to improve removal efficiency of a bad smell material. CONSTITUTION: An odor removal deodorant comprises protein 53-68 weight%, enzyme 9-15 weight%, alkaloid 7-18 weight%, allicin 5-5.7 weight%, tartaric acid 1.8-4.2 weight%, liquiritin 2-5 weight%, sesamol 3-6 weight%, and lipid 5-10 weight%. A manufacturing method of an odor removal deodorant comprises: a step of aging a component of the odor removal deodorant at 22-27 deg.C for 15-17 days; a step of drying the component at 30-40 deg.C; a step of hydrolyzing a dried composition; and a step of separating the composition into solid and liquid and concentrating the composition.

Description

Odor removal deodorant using biomaterials and manufacturing methods

The present invention relates to a method for preparing a deodorant having a deodorizing function for odor removal and livestock facilities generated in livestock wastes wastewater treatment plant sewage sludge treatment plant and other industrial processes, and more specifically, Patent No. 0515923 (biocomposite protein composition) The present invention relates to a method for preparing a deodorant using a protein, an enzyme, an alkaloid, allicin, liqueurine, tartaric acid, sesamol, and lipid components in a bio-combined protein composition by the method.

Patent No. 0515923 discloses a biocombination protein composition method that has a natural antibiotic function and an antioxidant function, and the specific composition method is a special component of an organism, that is, enzymes, alkaloids, glycosides, proteins, vitamins, and minerals. By solid-liquid separation and the like, a non-proteinaceous substance (conjugated substance) is bound to a simple protein to obtain a polymer compound in which various amino acids are bound. These compounds have nutritional, chemical, physiological, and pharmacological functions, as well as inhibiting bacterial growth and detoxifying substances.

On the other hand, odors generated from wastewater treatment plants and sewage sludge contain more than 20 kinds of odorous substances such as hydrogen sulfide trimetalamine methylmercaptan. Existing deodorizers only remove one or four kinds of odorous substances, and the remaining odorous substances in the atmosphere It is released and has harmful effects on human body such as headache and nausea.

An object of the present invention is to improve the removal rate of odorous substances and to remove all of the designated odors by the oxidation catalysis, and to develop a deodorant for odor removal and prevention of livestock facilities with extremely low emissions of harmful chemicals. It is done. Another object of the present invention is to develop an eco-friendly biodeodorant that is harmless to humans, animals, industrial equipment, and the like, and has no secondary pollution, and has excellent effects on indoor air clean function, sterilization of bacteria, and antibacterial effects of environmental pollution.

As the deodorizing method of odor (gas), liquid washing method, adsorption method, catalytic combustion method, chemical cleaning method and the like are widely known.

The liquid cleaning method removes odors using a liquid such as water or an alkaline solution. In this method, only ammonia, lower amines, lower fatty acids, hydrogen sulfide and mercaptan can be removed, and the remaining odors are released into the atmosphere.

Adsorption method adsorbs and removes a malodorous substance with activated carbon, zeolite, etc. Alcohols, fatty acids, benzene, mercaptan and the like can be removed.

Catalytic combustion is a method in which an odor component is passed through a catalyst layer such as platinum, cobalt, copper, or nickel to cause an oxidation reaction at a temperature of about 300 ° C. The deodorizing effect is superior to the liquid cleaning method, the adsorption method and the chemical cleaning method, but the operation cost is too high and the economic efficiency is low.

The chemical cleaning method is to remove odors using ozone, sodium hypochlorite, etc. In this method, only unsaturated organic compounds, hydrogen sulfide, mercaptan, aldehydes, and amines are removed. In addition, because of the use of drugs, secondary water pollution and odors are generated, thereby increasing the additional cost burden.

The present invention utilizes proteins, enzymes, alkaloids, allicin, tartaric acid, liqueurine, sesamol, and lipid components in the bio-complex protein composition material according to Patent No. 0515923 (biocombining protein composition method) as an active ingredient.

Hereinafter, the present invention will be described in detail.

In the present invention, the method for preparing the active ingredient is as follows.

Mix the main protein, simple protein material and the side materials. Suitable mixing ratio is 53-68% protein, 9-15% enzyme, 7-18% alkaloid, 3.5-5.7% allicin, 1.8-4.2% tartaric acid, 2-5% liqueurine, sesamol 3 to 6% by weight and 5 to 10% by weight of lipids.

Protein is the main ingredient of the active ingredient can not obtain the desired odor removal effect (deodorant) in less than the above range, if the content exceeds the above range, the content of auxiliary components is reduced and also the desired odor removal effect (deodorant) Can not get

Examples of proteins that can be used include albumin, globulin, proramine, histones, protamine, el-glutamine, flavin, chlorophyll, carotenoids, and the like, as well as those linked to hexoses or nucleic acids that are sugars.

The enzymes that can be used are oxidoreductases and hydrolases, and three types of oxidoreductases are reductases, oxidases and catalases, and hydrolases and two types of peptides are used.

Examples of lipids that can be used include linoleic acid, linolenic acid, and oleic acid, and when the amount of lipids used is less than the above range, there is a problem that the acetaldehyde removal rate is insufficient. The problem that the removal rate of is lowered arises.

If the capacity of the liqueurine is less than the above range, there is a problem that the removal rate of methylmercaptan is lowered, and if it exceeds the above range, there is a problem that the trimetalamine removal rate is lowered.

If the amount of the alkaloid is less than the above range, there is a problem that the removal rate of hydrogen sulfide is lowered, and if it exceeds the above range, there is a problem that the removal rate of toluene is lowered.

If the amount of allicin is less than the above range, there is a problem that the removal rate of trimetalamine is lowered. If the amount of allicin is exceeded, there is a problem that the removal rate of xylene is lowered.

If the amount of tartaric acid is less than the above range, the removal rate of styrene is lowered. If the amount of tartaric acid is exceeded, the problem of lowering the toluene removal rate occurs.

The preparation method of the active ingredient of the present invention is as follows.

The complex protein composition mixed composition is aged for 15 to 17 days to maintain a temperature of 22 ~ 27 ℃. At this time, the maturation is carried out by creating a clean environment without any pollutants that maintain temperature and humidity.

When the aging process is completed, perform hot air drying, and the temperature should be performed at 30 ~ 40 ℃. The dried composition is hydrolyzed and then solid-liquid separated.

That is, after performing the primary vacuum concentration on the basis of 50Brix at a temperature of 60 ℃ ~ 70 ℃ is filtered filtration. And second vacuum concentration is carried out on the basis of 75Brix at a temperature of 80 ℃ ~ 85 ℃. After the second concentration is completed, perform the third vacuum concentration on the basis of 90Brix at a temperature of 98 ℃ ~ 100 ℃.

The concentrate concentrated in vacuo by the vacuum concentration process goes through the following process.

That is, after centrifuging the concentrate

① Low temperature cooling drying → Powdered formulation (powder)

② Viscoelastic material → Store at low temperature.

And the composition of claim 1, 2 is to quality control component analysis test (test score) → screening → packaging → productization.

The product produced by the above manufacturing process is a bio-composite protein provided by the present invention, each of which is a polymer compound to which the composition material is bound, and its molecular weight is large compared to other organic compounds, reaching tens of thousands to millions.

The active ingredient prepared as above is diluted 10 to 2000 times in water and used as an industrial deodorant.

The deodorant of the present invention as described above can be continuously used for 45 to 60 days in a single deodorization tower and atmospheric tower in the sewage sludge treatment process (composting, carbonization, solidification, incineration method, etc.), and recover the waste deodorant after use It is very economical because it can be used as a deodorant in waste landfill, sewage sludge, and sludge storage tank of compost fermentation plant. In addition, it is very effective for worker's hygiene because it shows sterilizing power against pathogens and bacteria in wastewater sewage sludge when it is added at the initial stage, and it does not cause secondary pollution to soil and water because recycling waste deodorant used in deodorization tower. It is environmentally friendly.

Deodorant of the present invention is superior to the conventional deodorant for a variety of odor-causing substances, harmless to humans, animals or industrial equipment, does not cause secondary pollution, and exhibits a bactericidal or antibacterial effect against harmful bacteria do.

(Production Example)

* Preparation of Active Ingredients

A mixture of 55% by weight of protein, 10% by weight of enzyme, 12% by weight of alkaloid, 4% by weight of allicin, 3% by weight of tartaric acid, 4% by weight of liqueurine, 4% by weight of sesamol, and 7% by weight of lipid was used. Aged for 15 to 17 days.

After the maturing process, the mixture was hot air dried at a temperature of 36 to 38 ° C., and the dried mixture was hydrolyzed, followed by solid-liquid separation. That is, after performing the primary vacuum concentration on the basis of 50Brix at 60 ℃ ~ 70 ℃, filtered filtration, and then performing the second vacuum concentration on the basis of 75Brix at 80 ℃ ~ 85 ℃, the concentrate after the completion of the secondary concentration. The third vacuum concentration was carried out at 98 ℃ ~ 100 ℃ based on 90 Brix.

The concentrate concentrated in vacuo by the vacuum concentration was centrifuged and dried at low temperature to obtain an active ingredient powder having a water content of 50%.

The active ingredient thus prepared does not denature at all even at a high temperature of 600 ° C. or more and has an excellent effect of removing 20 or more kinds of complex odors.

In particular, active ingredients can be diluted up to 10 ~ 2,000 times depending on the use and industrial process conditions, and the dilution ratio is much higher than other products.

(Example 1)

As a result of testing the detection of heavy metals, aromatics and chlorine-based hydrocarbons for the active ingredient prepared by the preparation example, all were not detected as shown in Table 1 below.

* Heavy metal content and aromatics. Chlorine hydrocarbon detection test result Test Items unit Test result Test Methods Copper (Cu)


mg / kg Not detected (detection limit 0.1)


KS M 00 Cadmium (Cd) Not detected (detection limit 0.01) Lead (Pb) Not detected (detection limit 0.1) Arsenic (As) Not detected (detection limit 0.01) Mercury (Hg) Not detected (detection limit 0.01) Chrome (Cr) Not detected (detection limit 0.1) Zinc (Zn) Not detected (detection limit 0.1) Nickel (Ni) Not detected (detection limit 0.1) Volatile Aromatic Hydrocarbons (VACS) mg / kg Not detected KS M 0031: 2002 Polycyclic Aromatic Compounds (PAHS)
% Not detected KS M 0027: 2003 Chlorine Hydrocarbons Not detected KS M 0031: 2002 Methan All Not detected (detection limit 0.001)

(Example 2)

As a result of more precise testing of the detection of chlorine-based hydrocarbons for the active ingredient prepared according to the preparation example, all of them were not detected as shown in Table 2 below.

* Chlorine hydrocarbon precision detection test result Test Items unit Test result


Chlorine Hydrocarbons

Dichloromethane


% Not detected (detection limit 0.0001) chloroform Not detected (detection limit 0.0001) Carbon tetrachloride Not detected (detection limit 0.0001) 1.1.1-trichloroethane Not detected (detection limit 0.0001) 1.1-dichloroethyl Not detected (detection limit 0.0001) Trichlorethylene Not detected (detection limit 0.0001) Tetrachloroethylene Not detected (detection limit 0.0001)

(Example 3)

The test results for the deodorizing power and bactericidal activity of the active ingredient prepared by the preparation example was very good as shown in Table 3 below.

* Deodorization and sterilization test results division Inspection items Judgment(%) Remarks
Deodorization Rate Trimetalamine 97% or more (30 minutes) Test Methods:
KS M 0062: 2003
(Korea Research Institute for Living Environment) ammonia 97% or more (30 minutes) Hydrogen sulfide 96% or more (30 minutes) Methylmercaptan 93% or more (30 minutes)
Bactericidal power Staphylococcus aureus (ATCC 6538) More than 99.9% (30 minutes) Test Methods:
Fixed concentration test method (TI-10-001) Klebsiella pneumoniae (ATCC 4352) More than 99.9% (30 minutes) Escherichia coli (ATCC 8739) More than 99.9% (30 minutes)

* Dilution rate: 200: 1 (purified water: active ingredient) * Deodorization container: 10L * Sample amount: 50mL

(Example 4)

The results of the second deodorant test on the harmful chemicals of the deodorant prepared by the method of Preparation Example are shown in Table 4 below.

Test Items Time (min) BLANK (ppm) Sample concentration (ppm) Deodorization rate (%) Test Methods

ammonia Early 50 50 0

KS I 2218: 2008 60 49 5 90 120 48 4 92 240 46 3 93 360 44 2 95

Hydrogen sulfide Early 50 50 0

KS I 2218: 2008 60 48 5 90 120 46 3 93 240 44 2 95 360 42 One 98

* Deodorization container: 5L * Sample volume: 100g * Dilution rate: 200: 1

(Example 5)

To test the indoor air clean function, the public measures the air quality in a crowded movie theater (195 seats), and dilutes the active ingredient prepared according to the manufacturing example with purified water at a ratio of 250: 1 and sprays it on the walls and floors. After spraying 20Kg on the space area 420㎡, and measuring the indoor air quality after 1 hour, the results are shown in Table 5 below.

Measurement category
HCHO
(㎍ / ㎥)
VOC
(㎍ / ㎥)
enzene
(㎍ / ㎥)
Toluene
(㎍ / ㎥) Ethyl benzene
(㎍ / ㎥)
Xylene
(㎍ / ㎥)
Styrene
(㎍ / ㎥)
Remarks Recommended Standard 100 500 30 1,000 360 700 300 Before spraying 78.6 3,850.8 6.2 2,633.3 29.6 127.4 7.6 After spraying 59.3 873.5 0.0 408.9 9.5 47.8 3.4

  * Name of Test Equipment * Principle of Measurement

 HCHO: MP-∑100 HPLC Method

TVOC: MP-∑ 30 GC / MS

(Example 6)

In the deodorization tower of livestock and manure treatment plant, the existing hydrochloric acid and the active ingredient (dilution ratio 1,000: 1) obtained by the preparation example were added and tested by air dilution method. It was like The amount was added 10ton by mixing the hydrochloric acid in a ratio of 100: 1 to 10tons (100kg of hydrochloric acid), the deodorant of the present invention was mixed in a ratio of 1,000: 1 was added 10ton (10kg of deodorant of the present invention). . However, in case of hydrochloric acid, the pH of the deodorant should be continuously measured and used. However, the deodorant of the present invention was continuously used for 45 to 60 days by one input, and the waste deodorant recovered after use was sludge and compost fermentation. It could be recycled with deodorant such as intestinal sludge storage tank.

 * Sensory test results by livestock, manure deodorization tower air dilution sensory method division Manure Livestock Remarks IN OUT % IN OUT % 2009.06.12 6,694 3,000 55 10,000 6,694 33 Hypochlorite deodorant 2009.09.29 3,000 1,442 52 10,000 6,694 33 Hypochlorite deodorant 2009.11.30 3,000 1,000 66 6,694 4,481 33 Hypochlorite deodorant 2010.11.23 4,448 2,080 53 4.448 1,442 68 Deodorant of the present invention 2011.03.23 3.000 1,000 66 2,080 1,000 52 Deodorant of the present invention

(Example 7)

The compost manufacturing process of sewage sludge usually consists of the following processes.

In the deodorization tower of the sewage sludge composting plant, the hydrochloric acid and the active ingredient (dilution ratio 1,000: 1) obtained by the preparation example were added and subjected to the sensory test by air dilution sensory method. It was like The amount was added 10ton by mixing the hydrochloric acid in a ratio of 100: 1 to 10tons (100kg of hydrochloric acid), the deodorant of the present invention was mixed in a ratio of 1,000: 1 was added 10ton (10kg of deodorant of the present invention). . However, in case of hydrochloric acid, the pH of the deodorant should be continuously measured and used. However, the deodorant of the present invention was continuously used for 45 to 60 days by one input, and the waste deodorant recovered after use was sludge and compost fermentation. It could be recycled with deodorant such as intestinal sludge storage tank.

* Sensory test results by sludge composting plant air dilution sensory method  division Sludge ( Atmospheric tower ) Adjacent Building Deodorization Tower Remarks IN OUT  % IN OUT % 2010.11.23 4,481 1,000 77 Hypochlorite deodorant 2010.12.02 14,422 669 95 Deodorant of the present application 2010.12.28 2,080 1,000 52 Hypochlorite deodorant 2011.01.05 10,000 3,000 70 10,000 3,000 70 Deodorant of the present invention

※ Sludge Atmosphere Tower is subject to Atmospheric Conservation Regulations.

※ The deodorizing tower for the dormitory is subject to the odor prevention law.

※ The results of the test showed that the deodorizing efficiency was better when the deodorant was used in the present application than when using the conventional hydrochloric acid.

(Example 8)

The odor removal experiment was carried out by putting the hydrochloric acid and the deodorant of the present application into the air tower, the deodorization tower, and the raw material storage hopper using the existing hydrochloric acid and the deodorant of the present application for the complex odor generated in the sewage sludge composting process. It was as Table 8. The dilution ratio and the dosage are the same as in Example 7.

* Sludge Compost Plant Air Tower Design Odor Device Analysis Test Result

exam  standard

Atmospheric tower hydrochloric acid  input
Atmospheric tower  Deodorant input of the invention
Sludge Storage Tank  Deodorant input of the present invention
Sludge Storage Tank ,versus Tower pattern  Deodorant input of the invention
Sludge Storage Tank  Deodorant input of the present invention

Other regional standards
(Emission allowance standard: ppb Below)
 Sample collection date 2010.11.23 2011.1.07 2011.2.18 2011.3.23 2011.4.12 Hydrogen sulfide  10.58 16.10 15.05 25.22 9.61 20 Methylmercaptan  60.52 N.D.  2.62 3.15 N.D. 2 Dimethylselphide  77.57 N.D.   N.D.   N.D. N.D. 10 Dimethyl diesel 15.22 N.D. N.D. N.D. N.D. 9 ammonia 298.60 189.20 510.04 991.8 718.6 1,000 Trimetalamine 10.01 1.74 1.58 4.8 0.47 5 Acetaldehyde 30.58 24.72 39.79 25.09 2.00 50 Propionaldehyde 0.52 3.30 6.14 0.19 0.37 50 Beautialdehyde 37.02 38.80 8.61 7.83 0.64 29 iso- valeleraldehyde N.D. 4.22 7.51 11.59 N.D. 3 n-valeraldehyde N.D. 2.08 3.65 5.54 N.D. 9 Styrene 50.96 46.45 1.57 1.05 0.65 400 toluene 165.55 20.98 - - - 10,000 Xylene  10.95 6.50 - - - 1,000 Methyl ethyl ketone N.D. N.D. - - - 13,000 Methyl anisobutyrone N.D. N.D. - - - 1,000 Beautire Acetate N.D. N.D. - - - 1,000 Propionic acid N.D. N.D. - - - 30 n-butyric acid N.D. N.D. - - - One n-valeric acid N.D. N.D. - - - 0.9 i- valeric acid N.D. N.D. - - - One i-butyr alcohol N.D. N.D. - - - 900

※ The analysis of designated tower odor equipment is the result of taking samples from the atmosphere tower outlet to measure the deodorization efficiency more accurately. The place to collect samples prescribed by the odor prevention law is required to be collected from the site boundary line.

※ Test Result When considering the dilution rate of the deodorant of the present invention in the air tower, sludge storage tank, air tower sludge storage tank at the same time, considering the dilution rate, the deodorizing effect was found to be the best deodorizing effect.

(Example 9)

The deodorant used in the deodorization tower of Example 7 was collected and reused in the sewage sludge storage tank. One dose was charged at a rate of 5kg per ton of sewage sludge (a ratio of 200,000: 1 to the crude liquid), and the test results are shown in Table 9 below.

※ The air tower (IN-1) is the measurement result before the input of the waste deodorant and the air tower (IN-2) is the measurement result after the addition of the waste deodorant. The deodorization efficiency of the sludge storage tank is 79.19%.

※ Even when a waste deodorant was added, it was confirmed that the deodorant removal rate used in Example 7 was sufficiently recovered even if the deodorant removal rate was high.

Claims (4)

53-68% protein, 9-15% enzyme, 7-18% alkaloid, 3.5-5.7% allicin, 1.8-4.2% tartaric acid, 2-5% liqueurine, 3-6% sesamol %, 5-10% by weight of the active ingredient for deodorant.
The components of claim 1 are maintained at a temperature of 22-27 ° C. and aged for 15-17 days, then dried at a temperature of 30-40 ° C., after hydrolysis of the dried composition, followed by solid-liquid separation and vacuum. Method for producing an active ingredient for deodorant, characterized in that the step of concentration.
According to claim 2, wherein the vacuum concentration process is carried out by the first vacuum concentration on the basis of 50Brix at 60 ℃ ~ 70 ℃ temperature filtered filtration, and then the second vacuum concentration on the basis of 75Brix at 80 ℃ ~ 85 ℃ temperature , After the secondary concentration is completed, the method of producing the active ingredient for deodorant, characterized in that the third vacuum concentration on the basis of 90Brix at 98 ℃ ~ 100 ℃ temperature.
An industrial deodorant in which the active ingredient of claim 1 is diluted 10 to 2000 times in water.