KR100445642B1 - Method for removing malodor by using activated humic substances - Google Patents

Abstract

According to the present invention, odorous substances generated when organic and organic organic wastes are dried, fermented, decayed and decayed are oxidized and deodorized by their own fluoric acid and their metal complexes. It is an insoluble and non-volatile macromolecule that is insoluble in water by using the activated corrosive which has the catalyst function, the catalyst function to polymerize organic materials to produce corrosive substances, and supply minerals to plants and plants. The objective is to remove odorous substances economically and hygienically by converting them to corrosive precursors.

To this end, a microbial reaction column filled with activated corrosive pellets (5) and luteum rock or dacite pumice (6), which is easily supplied to the soil microbial culture tank (3), which generates corrosive substances. (4) is embedded in the tank as shown in [1] and [3] or installed outside the tank as shown in [2] and [4] to circulate the culture solution in the culture tank (3) and the minerals in soil microorganisms ( With the supply of minerals, oxidase, and physiologically active substances, the metabolic activity of soil microorganisms producing corrosive substances is active, and odor generating substances are converted to corrosive precursors, which are insoluble in water and are non-volatile substances. Odor substances in (Gas) are removed.

In addition, in order for the corrosion reaction to occur actively, it is an optimal condition when the oxidation reduction potential (ORP) value in the system is +350 to +400 mV. Fulvic acid oxidized water obtained by oxidizing the redox potential to +700 to +100 mV by electrolytic oxidation of fulvic acid or oxidized water tank 23 using hydrogen peroxide (H ₂ O ₂ ) and ferrous sulfate (FeSO ₄ ). By supplying minerals from the mineral reaction tank (25), the redox potential is maintained at +350 to +400 mV in the culture tank (3) by activating a liquid activated corrosive, which is a chelate fulvic acid peroxide complex. Supply it.

The present invention has lower operating and facility costs compared to general processes such as adsorption deodorization by activated carbon, zeolite, deodorization by oxidizing agents, deodorization by high temperature pyrolysis, etc., and thus, digestion of manure treatment plants, waste disposal plants, and sewage sludge. It is expected to be applied to various fields such as process and composting process.

Description

Deodorization method using activated corrosive substances {Method for removing malodor by using activated humic substances}

The present invention is ammonia, trimethylamine, isobutylamine, nitrosoamine, indole, Volatile basic nitrogen such as Skatole, hydrogen emulsification (H ₂ S) and mercaptan produced when decomposition of amino acid (Amino acid) And odorous substances such as isobutyl alcohol, acetic acid, butyric acid, phenols, phenols, cresols, pyruvic acid, etc. Fulvic acid and its metal complexes are induced in the free state, and they are insoluble in water due to their oxidative function, catalytic function of oxidative deodorization, and organic materials as polymers. To convert non-volatile stable corrosive materials By using activated corrosive (hereinafter referred to as active corrosive), the above-mentioned odor-causing substances are converted into insoluble and nonvolatile corrosion precursors in water and economically and hygienically. That's how to handle it.

Naturally activated corrosive materials are excavated from the peat of Kago Wetland in Nagasaki Prefecture, Japan. In the case of corrosive substances formed by mixed deposition of marine animals and plants such as marine diatoms, seaweeds, and plankton, and aquatic plants in wetlands, activated silicon oxide (SiO ₂ ) and aluminum oxide in large volcanic ashes. (Al ₂ O ₃ ) and activated minerals (Minerals) were acidified by the release of hydrogen ions (H ⁺ ) by hydrolysis reaction with water.

Si ⁴⁺ + 4H ₂ O ----------> Si (OH) ₄ + 4H ⁺ --- ①

Al ³⁺ + 3H ₂ O ----------> Al (OH) ₃ + 3H ⁺ --- ②

Acidified corrosives lead to the free state of fulvic acid. The free fulvic acid reacts with activated minerals in volcanic ash to form chelate metal complexes.

In addition, the chelating fulvic acid metal complex is present as an active corrosion material which is a metal complex of chelating fulvic acid peroxide reacting with hydrogen peroxide (H ₂ O ₂ ) generated in the corrosive reaction.

The livestock wastewater flowed from the nearby livestock farms in the wetlands, and the odor occurred rapidly due to the rapid self-cleaning action compared to the general rivers and lakes.

As a result of this phenomenon, the spread of peat (activated corrosive material) from the wetland was reduced to the odor.

By applying such a phenomenon, Japanese Laid-Open Patent Publication No. 62-45321 discloses the mechanism of removing the above-mentioned odor-causing substances by active corrosive soil. In dry deodorization, non-volatile acids are combined and adsorbed. Proton is activated by reducing fulvic acid and humic acid having oxidation function in active corrosive to hydroquinone type, and activated alkali in Alkali and metal or salts thereof. ) Reacts to produce hydrogen peroxide (H ₂ O ₂ ), and volatile acids are combined to oxidize odor-causing substances and decompose into harmless nitrogen (N ₂ ) gas to remove odorous substances. (Pellet) was used in the adsorption tower, but it is a theory contrary to the treatment mechanism of odor-causing substances by active corrosive substances. The efficiency was very low.

Japanese Unexamined Patent Application Publication No. 2-290224 discloses a treatment mechanism by removing an odor-causing substance by contacting waste gas with an aqueous solution containing organic matter using an accelerator which promotes a corrosive reaction such as humic acid or fulvic acid. However, this method also has a poor processing efficiency because it does not understand the exact processing mechanism.

In Japanese Unexamined Patent Publication No. Hei 9-122436, the active corrosive pellets are installed in multiple stages in the packed column, and the circulating solution of the circulating tank at the bottom of the packed column is circulated through the reactor filled with pumice (pumice) to improve treatment efficiency. However, this is also contrary to the actual processing mechanism, which did not improve the processing efficiency significantly.

The prior art in the technical field of the present invention is described that most active corrosion is treated by the oxidation catalyst function of the second active corrosion material after the first physical adsorption, such as activated carbon, the nitrogen compound is nitrogen (N ₂ ) Nitrogen compounds, such as ammonia and volatile amines, are decomposed into gases, and are immobilized to corrosive precursors, which are insoluble in water and large, nonvolatile macromolecules, due to organic corrosion reactions. Removed,

The removal of odorous substances using active corrosive substances is caused by the organic pollutants dissolved in the water by the corrosive reaction of organic wastewater. It is treated by the same mechanism as that which is purified.

The mechanisms by which organic substances and odor-causing substances become corrosion precursors by soil corrosive microorganisms are removed as follows.

Among the primary organic substances, simple proteins, sugars, and starches, which are easily decomposed by soil corrosive microorganisms, include simple minerals such as CO ₂ , H ₂ O, and NH _3, and aromatic substances, metabolites of these microorganisms. Polyphenolic compounds having a polyamide are produced.

Organics + O ₂ - ^{Soil Corrosion Microorganisms-} > Polyphenolic Compounds + Minerals such as CO ₂ , H ₂ O, NH ₃ --- ③

Polyphenolic compounds produced by soil corrosion microorganisms produce quinone compounds and hydrogen peroxide (H ₂ O ₂ ) in the air by oxidase (Polyphenoloxidase) contained in the active corrosion material.

Hydrogen peroxide (H ₂ O ₂ ) is an intermediate in which metabolites of soil microorganisms produce corrosive substances by corrosive reactions (Fulvic acid, hardaroxyl benzoic acid, benzoic acid, vanillinic acid, gurutaic acid, phenolic acetic acid, phenolic lactate It reacts with the back to produce peroxidase, which in turn produces oxidase.

Corrosive intermediate product + H ₂ O ₂ ---> Peroxide- ^{Microorganism-} > Oxidase --- ⑤

The oxidase produced here acts as a catalyst in the reaction ④.

The quinone compound undergoes a polycondensation reaction with lignin, cellulose, tannin, peptide, amino acids, which are difficult to decompose, to produce a corrosive substance that is a macromolecule.

Soil corrosive microorganisms and microorganisms that have mutual symbiosis with these microorganisms are characterized by higher mineral content in the cell nucleus than normal microorganisms, and active metabolism only when sufficient minerals are supplied.

In addition, these microorganisms are aerobic anaerobic microorganisms that metabolize under aerobic and anaerobic conditions, but metabolic mechanisms are different from each other, and the redox potential is aerobic under an aerobic condition in order to excrete polyphenolic compounds as metabolites. Oxidation Reduction Potential (ORP) is active at +350 to + 400mV, increasing the corrosion efficiency.

In the present invention, the mineral supply in the system is activated by installing a bioreactor tower filled with a dilute pumice and an active corrosive pellet of chelate metal complex salt form of free fulbrate peroxide in a soil microbial culture tank. While cultivating soil corrosion microorganisms, by injecting liquid active corrosive material with redox potential of + 700 ~ 1100mV into the culture tank, the redox potential is adjusted to + 350 ~ + 400mV, improving the corrosion reaction efficiency It is a process to remove the generated substances.

An object of the present invention is to use odor-causing substances and pumice as odor-producing substances generated from fermentation, decay, decay, and drying of animal and plant organic waste such as food waste, livestock manure, slaughterhouse waste, agricultural and fishery waste, and phosphorus. It is economical and hygienic.

1 is a process diagram in which a biological reaction tower 4 is installed in a soil microbial culture tank 3 in a process for removing odor of low temperature waste gas.

2 is a process diagram in which the biological reaction tower 4 is installed outside the soil microorganism culture tank 3 in the odor removal process of low temperature waste gas.

3 is a process diagram in which the biological reaction tower 4 is installed inside the soil microbial culture tank 3 in the process of removing odor of high temperature waste gas.

4 is a process diagram in which the biological reaction tower 4 is installed outside the soil microorganism culture tank 3 in the process for removing odor of high temperature waste gas.

5 is a flow chart of the production of activated corrosive substances in the liquid phase by supplying minerals (Minerals) after electrolytic oxidation of Fulvic acid (Fulvic acid)

6 is a manufacturing process diagram of the liquid activated corrosive material by supplying minerals (Minerals) after oxidation of Fulvic acid (Fulvic acid) by the oxidizing agent

[Explanation of symbols on the main parts of the drawings]

1: deodorizing tower 2: filling

3: culture tank 4: biological reaction tower

5: Pellet 6: Active Corrosive Material

7: Culture medium pump 8: Settling tank

9: settling tank scraper 10: sludge return pump

11: treatment tank 12: cooler

13: Fulvic acid storage tank 14: Fulvic acid supply pump

15: electrolytic oxidation tank 16: negative electrode plate

17: bipolar plate 18: rectifier

19: Minerals reaction tank 20: Mineral reaction tower

21: liquid active corrosive feed pump 22: oxidizing tank

23: oxidizer stirrer 24: ferrous chloride storage tank

25: ferrous chloride storage tank stirrer 26: ferrous chloride transfer pump

27: hydrogen peroxide storage tank 28: hydrogen peroxide transfer pump

In order to achieve the above object, it will be described with reference to the drawings.

Ammonia, trimethylamine, isobutylamine, nitrosoamine, indole, skatole, hydrogen sulfide, mercaptan, and volatiles generated during the drying, evaporation, and fermentation of the above-mentioned organic and vegetable organic wastes, and left to rot and decay. When odor generating substances such as alcohols, volatile organic acids, phenols, etc. flow into the bottom of the deodorization tower 1, a falling ring, intalox saddle, raschig ring, Odor generating substances are reacted with the culture medium to remove the odor-producing substances while contacting the soil-eroded microbial culture solution sprayed from the top while passing through a layer of filler (2) such as Lessing ring and Wood grids. The gas is released to the atmosphere.

In the culture tank 3, active corrosive substance having fulvic acid and metal complexes in the state of glass and having self-oxidation function, corrosive organic material to corrosive substance which is a macromolecular substance, mineral supply function to soil microorganism, etc. If a bioreaction tower (4) filled with luteum rock or large-scale pumice (6) containing a large amount of pellets and activated minerals is installed inside the culture tank (3), When the air is injected, the culture solution in the culture tank is air-lifted with the air and passes through the layers of the active corrosive pellets (5) and pumice (6) filled in the bioreaction tower (4) and minerals and oxidation. Soil-causing microorganisms and soil microorganisms that are symbiotic with these microorganisms are activated by enzymes and other active corrosive substances.

In addition, in the case where the bioreaction tower 4 is installed outside the culture tank 3, an active corrosive pellet filled with the culture solution of the culture tank 3 in the bioreaction tower 4 by the culture solution circulation pump 7 Soil microorganisms, which pass through (5) and pumice (6) layers, receive minerals, oxidases, and other active corrosive substances to produce corrosive substances, and soil microorganisms in mutual symbiosis are activated.

In order to improve the safety and the activation efficiency, the liquid reactive corrosive, which is a chelate metal complex compound of free fulvic acid peroxide having an ORP value of about +700 to +1100 mV, is injected into the culture tank 3 for oxidation. The reduction potential (ORP) is set to +350 to +400 mV.

Liquid active corrosive material is produced by depositing carcasses of marine animals and plants such as marine diatoms, plankton, and seaweeds with high fulvic acid content, and performing acid treatment after alkali treatment (NaOH). Extract

The liquid fulvic acid is applied with a direct current in the electrolytic oxidation tank 15 to produce fulvic acid electrolytic oxidation water having a redox potential of +700 to +1100 mV, and then filled with luteum rock or coarse pumice (6). When the mineral reaction tower 20 is sent to the built-in mineral reaction tank 19, air is injected into the lower portion of the mineral reaction tower 20 to circulate and agitate to obtain a liquid active corrosive material which is a metal complex salt of fulvic acid peroxide.

Alternatively, the liquid fulvic acid is sent to the oxidizing tank 22, and hydrogen peroxide (H ₂ O ₂ ) and ferrous sulfate (FeSO ₄ ) are injected in the ratio of equivalent to equivalent while stirring with the oxidizing tank stirrer 23 to reduce the redox potential (ORP). ) Is adjusted to +700 to +1100 mV to produce fulvic acid oxidized water, which is a liquid fulvic acid peroxide.

The fulvic acid oxidized water is sent to the mineral reaction tank (19) in which the mineral reaction tower (20) filled with luteum rock or large-scale pumice (6) is injected, and air is injected into the lower portion of the mineral reaction tower (20) for circulation stirring. The liquid active corrosive, which is a metal complex salt of fulvic acid peroxide, is formed.

In order to cultivate soil microorganisms that corrode organic materials in the culture tank (3), the feed of these microorganisms is supplied to the culture tank (3) with organic wastewater or an aqueous solution containing organic matter.

In the culture tank (3), air is injected so that the dissolved oxygen (DO) concentration is 2 mg / l or more.

When air is injected into the lower part of the bioreactor 4, the aeration is carried out through the layers of the active corrosive material pellets (5) and pumice (6). Get an active substance.

In order to stably progress the growth and corrosion reaction of soil microorganisms in the culture tank 3, the above-mentioned liquid active corrosive material is injected in the culture tank 3 such that the redox potential is about +350 to +400 mV. .

Soil microorganisms and culture medium cultured in the culture tank (3) are sent to the upper portion of the deodorization tower (1) by the culture medium circulation pump (7) and reacts in the layer of the malodor-causing substance and the filler (2) in the waste gas flowing in from the bottom. This removed purified gas passes through an eliminator above the deodorization tower 1 and is exhausted to the atmosphere.

Odors such as ammonia, volatile amines, hydrogen sulfide, mercaptans, volatile organic acids, and volatile alcohols are polyphenolic compounds with aromatic essences, which are metabolites of corrosive microorganisms in soil microorganisms, and oxygen and polyphenoloxidases in the air. It undergoes a polycondensation reaction with the quinones produced by oxidization and is insoluble in water and is removed as a nonvolatile corrosion precursor.

The concentration of the solids (MLSS: Mixed Liquid Suspended Solid) in the culture tank 3 is adjusted in the settling tank 8 so as to be maintained at 2000 to 4000 mg / l.

The culture solution of the culture tank (3) is sent to the settling tank (8), and the supernatant from which the solids have been removed is sent to the treatment tank (11) and discharged, and the precipitated sludge is soiled by the sludge return pump (10) for seed sludge. It returns to the microorganism culture tank 3.

Surplus sludge is sent to a dehydrator system for dewatering.

In the case of the hot waste gas discharged from the drying process, a cooler 12 is installed on the discharge side of the culture circulation pump 7 so as not to interfere with the soil microbial culture. The layer of the filler 2 is made into two stages.

Example 1

Results of performing a pilot test (Pilot-Test) as shown in FIG. 1 for the malodor treatment disorder malodor gas 150 l / min are shown in Table 1.

Example 2

When the waste gas discharged from the pre-treatment drying process to feed and compost food waste was treated by the treatment process as shown in FIG. 3, the sensory test resulted in almost perfect deodorization.

As is apparent from the foregoing description, odor generating substances such as ammonia, volatile amines, hydrogen sulfide, mercaptan, volatile alcohol, and volatile organic acids in waste gases generated during drying, fermentation, decay and deterioration of organic wastes are treated with active corrosive substances. The process of using pumice to remove insoluble in water and non-volatile corrosion precursors is compared with the oxidizing agent, alkali and acid absorption deodorization, adsorption deodorization with activated carbon, and deodorization by high temperature pyrolysis. It has the following features.

① Advanced processing.

② No secondary pollutant is discharged after treatment.

③ There is no need for additional absorbents and adsorbents, and the operating cost is low because energy costs are consumed less.

④ When used in combination with wastewater treatment facilities, the facility is simple, so the facility cost is low and operation and maintenance are easy.

Since the present invention has the characteristics as described above, odor is generated in various fields such as animal husbandry farm, food waste treatment process, manure treatment plant, surplus sludge treatment process of sewage treatment plant, slaughterhouse waste treatment process, food processing plant waste treatment process, etc. It is expected to be applied to material removal.

Claims (4)

An aqueous solution containing organic wastewater or organic matter was placed in a culture tank (3) incorporating a bioreactor (4) filled with a pellet (5) of active corrosive material and a luteum rock or dacite stone (6). Air-lifting by injecting air from the bottom of the bioreaction tower (4) while passing through the layers of the active corrosive pellet (5) and pumice (6), minerals, oxidases and bioactive substances Air is also aerated in the culture tank 3 while being circulated through the culture tank 3, and corrosive microorganisms and microorganisms having mutual symbiosis with these microorganisms under aerobic conditions in which dissolved oxygen (DO) concentration is 2 mg / l or more. When the culture solution was cultured and sent to the upper portion of the deodorization tower (1) by the culture solution circulation pump (7) and sprayed, the odor generating substances in the waste gas were brought into contact with the culture solution in the packing (2) layer in the deodorization tower (1) and the quinone compound in the culture solution Insoluble in water due to heavy and condensation reaction After the odor generating material is removed, the odor generating material is discharged to the atmosphere through the upper portion of the deodorizing tower (1), and the culture solution absorbed and reacted with the odor generating material is returned to the culture tank (3) and corroded in the culture tank (3). In order to stably cultivate chemicals and microorganisms having mutual symbiosis with these microorganisms, in order to improve the reaction efficiency, electrolytic oxidation of fulvic acid (Fulvic acid) in the electrolytic oxidation tank (15) or electrolytic oxidation tank (22) Fulbrate-oxidized water reacted with hydrogen peroxide (H ₂ O ₂ ) and ferrous sulfate (FeSO ₄ ) is sent to the mineral reaction tank (19) containing the mineral reaction tower (20) filled with pumice (6) to air stirring. By supplying liquid active corrosive substance, fulvic acid peroxide metal complex compound, and injecting redox potential at + 350 ~ 400mV, and solids concentration (MLSS) of culture tank 3 can be maintained at 2000 ~ 4000mg / l. (8) The sludge sludge settled down The sludge return pump (10) is returned to the culture tank (3), and the culture solution of the culture tank (3) is sent to the settling tank (8), and the supernatant from which the solids are precipitated is sent to the treatment tank (11) and discharged. Is a method for removing odor generating substances in the waste gas by the process to send to the dehydration system (Dehydration process). The method according to claim 1, wherein the biological reaction tower (4) is installed outside the culture tank (3) to remove odor generating substances in the waste gas while circulating by the circulation pump (7). 2. The method of claim 1, wherein when the waste gas temperature is high, the deodorization tower 1 is provided with two layers of the packing material 2, and a cooler 12 is installed on the discharge side of the culture circulation pump 7 to control the temperature of the culture solution. While removing the odor generating substances in the hot waste gas. 4. The method according to claim 3, wherein the biological reaction tower (4) is installed outside the culture tank (3) to remove odor generating substances in the hot waste gas while circulating by the circulation pump (7).