KR100856063B1 - Method for preparation of organic substrate by removing heavy metals and sterilizing pathogenic microorganisms through electric beam and exposing gamma;-ray from livestock - Google Patents

Abstract

A preparation method of eco-friendly organic resources from livestock excretions is provided to construct an efficient system for recycling livestock excretions by removing heavy metal through citric acid and peracetic acid and carrying out disinfection with electron beam and gamma-ray irradiation and to develop an accelerated process for preparation of byproduct fertilizer or soil conditioner by excluding separate composting process. A preparation method of eco-friendly organic resources from livestock excretions comprises steps of: treating citric acid on livestock excretions until obtaining pH of 1-6; treating peracetic acid in the amount of 0.1-50 times by volume to the livestock excretions in order to remove copper and zinc; and irradiating gamma-ray and electron beam in 0.1-100kGy. The acid for adjustment of pH is at least one selected from citric acid, hydrochloric acid, sulfuric acid and nitric acid. The gamma-ray is selected from cobalt(Co, atomic number: 60), krypton(Kr, atomic number: 85), strontium(Sr, atomic number: 90) and cesium(Cs, atomic number: 137).

Description

Method for preparation of organic substrate by removing heavy metals and sterilizing pathogenic microorganisms through electric beam and exposing γ-ray from livestock}

Figure 1: Overall process diagram of a livestock manure-free fermentation fast by-product fertilizer manufacturing system

Figure 2: Process of dehydration filtrate generated in the livestock manure non-fermentation high-speed by-product fertilizer manufacturing system

3. Pellet by-product fertilizer developed in the present invention

* Explanation of symbols for the main parts of the drawings

(1) Vibrating Screen,

(1a) Screen net (1b) Foreign material discharge conveyor

(2) Crusher (2a) Screen Basket

(2b) Cutter (3) # 1st Reactor

(3a) Raw material transfer pump (# 1 reactor) (3b) # 1st stirrer

(3c) Level transmeter

(3d) pH Meter (3e) Densitometer

(4) Raw material storage tank (4a) Raw material transfer pump (raw material storage tank)

(4b) Control valve (4c) Flow meter

(4d) Feeder (5) Circulating water tank

(5a) Circulating water supply pump (6) Citric acid tank

(6a) citric acid feed pump (7) peracetic acid tank

(7a) Peracetic acid supply pump (8) Electron beam reaction part (gamma ray reaction part)

(8a) Scraper

(9) Electron beam irradiation device (gamma ray irradiation device)

(10) Leakage material tank (10a) Leakage material circulation pump

(11) # 2 reactor (11a) raw material transfer pump (# 2 reactor)

(11b) (11c) (11d) # 2nd Stirrer (12) Polymer Coagulant Tank

(12a) Polymer coagulant supply pump (13) Polymer coagulant tank

(13a) Polymer coagulant feed pump (14) Bentonite tank

(14a) Bentonite Supply Pump (15) Dehydrator

(16) Dewatering Cake Discharger

(16a) Dewatering Cake Feed Screw Conveyor

(16b) Dewatering Cake Feeder (17) High Density Blender

(17a) High Concentration Mixer Drive Reducer (17b) Fixed Bar

(17c) Swivel Bar (17d) Screw Feeder

(17e) Screw Feeder Drive Reducer (18) Lime Tank

(18a) Rotary Valve (18b) Lime Supply Screw Conveyor

(18c) Lime Feed Screw Conveyor Drive Reducer

(19) Mixing Cake Discharger

(19a) Mixing Cake Feed Screw Conveyor

(19b) Mixing Cake Feeder (20) Dryer

(21) Dry Cake Discharger

(21a) Dry Cake Feed Screw Conveyor

(21b) Dry Cake Feeder (22) Pellet Maker

(22a) molasses storage tank (22b) molasses supply pump

(23) Pellet Dryer (24) Pellet Weigher

(25) Pellet Packing Machine (26) # 3 Reactor

(26a) Dewatering Filtration Transfer Pump (26b) Dewatering Filtration Agitator

(27) Coagulant Tank (# 3rd Reactor) (27a) Coagulant Supply Pump (# 3rd Reactor)

(28) Microcro filter (28a) Sulfur compound mixer

(29) Sulfur Compound Tank (29a) Sulfur Compound Supply Pump

(30) Heavy metal sedimentation tank (30a) Heavy metal sediment transfer pump

(30b) Supernatant water circulation pump (31) Treated water tank

(31a) treated water circulation pump (32) waste tank

(32a) Waste Transfer Pump (33) Waste Transport Vehicle

The present invention relates to a method for producing a high quality organic raw material sterilized pathogenic microorganisms by removing harmful heavy metals of livestock manure and electron beam and gamma irradiation, more specifically,

Extraction and insolubilization of harmful heavy metals (Cu, Zn) derived from livestock manure through treatment of citric acid and peracetic acid from livestock manure, hygienic sterilization of pathogenic microorganisms using electron beam and gamma irradiation, antibiotics, pest control and insecticide The present invention relates to a method for producing high quality organic raw materials, which are environmentally and ecologically superior through decomposition and reduction of chemicals.

After removal of heavy metals, raw materials processed by electron beam or gamma ray are used as raw materials for manure recycling, and do not go through a separate composting process. They are stabilized by adding calcium and adjust the C / N ratio. The purpose of this study was to present a method for preparing a soil modifier.

Cattle manure contains high concentrations of nitrogen, phosphorus and potassium, which are necessary for plant growth, and thus are useful as fertilizer resources, while copper (Cu) supplied through animal feed ), Heavy metals such as zinc (Zn) and various antibiotics (ampicillin + collistin sulfate, sulfachlorpyridatine-Na, trimethoprim, tiamulin hydrogen fumarate) used to suppress livestock diseases, resulting in a qualitative decline in livestock manure resources. It has been an obstacle to the recycling of livestock manure.

In addition, insecticides used to control harmful pests in the barn are Permethrin, which is known as endocrine obstruction, dichlorovinyl phosphate (DDVP) emulsion, organophosphorus insecticide, cyjpermethrin, and DL designated by the Ministry of Environment. Known as dieldrin and chlorpyrifos, the severity of the problem is increasing, such as qualitative declines in livestock manure due to barn disinfectants and pest control agents, and threats to the environmental ecosystem through bioconcentration. Most of the chemicals used as pest control agents mentioned above are endocrine-disrupting substances-like substances or substances with high residual persistence in soil. If they are contained in livestock manure, as well as normal fermentation and delay of fermentation of livestock manure, when the livestock manure is processed in farmland, the residual persistence in the soil is long and affects livestock through the food chain process. Can act as a hazard.

In particular, insecticides have been used to remove harmful insects such as mosquitoes and flies in the barn, but livestock contamination due to insecticides and dead flies are sometimes mixed with feed, and pesticides that have been processed for house hygiene are transferred to livestock manure. It has caused fermentation or secondary contamination of livestock manure. Side effects such as increased resistance to insecticides in flies, and detection of endocrine disruptors in livestock products due to misuse of pesticides

The various problems of livestock manure mentioned so far are urgent problems that must be solved in the future regarding the recycling of livestock manure. Degradation of harmful heavy metals derived from domestic and international manure, antibiotics, insecticides, fungicides and endocrine disruptors. As a result of investigating the prior invention related to the removal and sterilization of pathogenic microorganisms, there is no research on this.

The applicant has applied for a patent for 'reduction of antibiotics, odor-inducing substances and pathogenic microorganisms contained in livestock manure using radioactive irradiation technology and by-product fertilizer manufacturing method using the same (Patent application 10-2005-0127400) In addition, the Republic of Korea Patent (10-0604217) exemplifies a method for producing a soil improved material by the method of extinguishing organic waste, and the Republic of Korea Patent (10-0479836) the water in the process of composting and liquefying livestock manure generated from livestock farms An example of a fertilizer treatment apparatus for livestock manure and a method for obtaining organic fertilizer by a high-temperature fermentation method by aerobic fermentation in a short time without using a sawdust or rice husk, which is a regulating material, and the Korean patent (10-2003- 0028055) ) Shows an example of a livestock waste treatment system that can continuously treat livestock manure with a high quality liquid ratio without limiting the treatment capacity. In Korea Patent (10-0451856), pre-treatment of livestock manure is followed by dehydration to economically compost dehydrated cakes to produce high-quality organic fertilizers. The treatment process which can be treated and discharged is illustrated.

Republic of Korea Patent (10-0294742) exemplifies a method for reducing livestock manure using microorganisms, and Republic of Korea Patent (10-0378667) illustrates a rapid deodorizing and composting method and composition of livestock manure using microorganisms , Republic of Korea Patent (10-0250862), using the photosynthetic microorganism to remove odor of livestock manure, classify livestock manure into solid and liquid phase, compost the solid phase and reduce the liquid by heating in a closed and insulated reducing tank An odorless odorless livestock wastewater treatment system and a method of treating the same are illustrated. In addition, the Republic of Korea Patent (10-0451640) is an example of an oil and water sterilizer and sterilization method using microorganisms such as E. coli in the treated water discharged after treatment in sewage treatment terminal or livestock wastewater treatment plant.

Korean patent (20-0164110) exemplifies a wastewater treatment by a constant current type electrolysis method and an advanced treatment device for manure and livestock manure, and Korean patent (10-2005-0052032) shows a metal supplied by a metal ion feeder. By separating the spores of microorganisms such as bacteria in sludge through ions, it is easy to separate urine and sludge by separating water and solids, and the odor generated in the treatment process is purified through air purifier. The method is exemplified, and the Republic of Korea Patent (10-0486775), the manure or livestock manure using advanced oxidation method, hardly decomposable substances, color, residual nutrients and suspended solids, etc. A processing method and apparatus for processing the same are illustrated.

In order to solve various problems related to the reuse of organic waste resources, researches using radiation technology have been actively conducted in advanced foreign countries since the 1990s. Irradiation is a generic term for the use of the effect of causing a chemical reaction, destroying cells of an organism, or killing bacteria by irradiating a very large amount of radiation to a substance. Currently, Gamma rays and electron beam irradiation facilities are established in the United States, Japan, Russia, and Canada to sterilize food and medical devices, remove food containers, sanitary products, imported grains, industrial wastewater and organic toxic substances from polluted soil. .

Irradiating a system produces highly reactive species such as hydrated electrons, H, OH, and hydrogen atoms, which can be contaminated by redox reactions, decomposition of organics, removal of dyes, and formation of deposits. It causes a radiation transition of the material. Based on these mechanisms, methods of purifying and sterilizing liquid, gas, or solid materials have been developed. Early studies of electron beam treatment of waste began in the 1950s and were used to purify underwater pollutants in the 1960s. Areas currently under study or commercialization include surface and groundwater treatment, wastewater purification, sewage sludge and flue gas treatment, and hospital waste and contaminated soil treatment. The world's first wastewater treatment facility using an electronic accelerator is a wastewater treatment plant in Voronezh Synthetic Rubber Plant, Russia, and is also applied to paper wastewater treatment facilities containing a large amount of hardly decomposable organic matter. Research on groundwater and surface water treatment has focused on the treatment of organic chlorine compounds, including the decomposition of aromatic compounds, and also applied to the treatment of phenolic compounds, dyes, and polyvinyl alcohol (Shin, Kyung-Sook, 2002).

Korean Patent (10-0601113) illustrates a method of decomposing antimicrobial agents through radiation irradiation, and Korean Patent (10-1997-0000087) discloses SO _X , NO _X by irradiating an electron beam to combustion exhaust gas generated from a waste incinerator. A method and apparatus for removing harmful compounds in exhaust gas for removing harmful compounds such as HCl and dioxins are illustrated. A Korean patent (20-1998-0020805) suggests a useful method for wastewater treatment using an electron beam, and a Korean patent (10-1996- 0076923) describes a method for removing Cr and Hg from waste water by irradiating an electron beam. Is illustrated. Republic of Korea Patent (10-1996-0057191), there is illustrated a method of removing harmful components by irradiating the power generation exhaust gas with an electron beam. Korean patent (10-1996-0022983) introduces a method and apparatus for removing lead and cadmium in wastewater by irradiating an electron beam.

However, as a result of the review of the prior invention, endocrine disruptors, insecticides, harmful heavy metals, odor-causing substances and antibiotics, etc., which can be derived in connection with the utilization as excellent organic resources of livestock manure, as intended in the present invention. There are no techniques and methods for efficiently controlling the

In addition, marine dumping of livestock manure is scheduled to be banned in 2011. 2005 Ocean tugiryang of reference livestock manure are the only 274 m ³ 5 1000 increased 17% compared to 2004, the proportion of the total volume of ocean dumping manure accounted almost 30%. This amount is about 7,600m ³ per day throughput, it is expected that the existing composting method has a limitation in processing a large amount. Currently, almost all livestock manure is produced by-product fertilizer after the first and second composting process. The purpose of such composting is stabilization by decomposition of organic matter, sterilization of pathogenic microorganisms, improvement of handling and reduction.

Currently, in Korea, the composting reaction using organic waste resources is legalized to produce decomposed soil after 15 days of primary fermentation and 21 days of post-aging process. However, as mentioned earlier, if you can use other advanced techniques to achieve your inherent purpose, you do not have to go through the composting reaction, consuming a lot of work space and energy resources for a long time. It is time to develop an ultra-fast livestock manure treatment system that does not cause the above-mentioned problems even if the livestock manure that occurs at about 7,600 m ³ per day is processed on farmland without composting.

The present invention is to solve the above problems,

The present invention is to provide a method for producing a high quality organic raw material sterilized pathogenic microorganisms by removing harmful heavy metals of livestock manure and electron beam and gamma irradiation.

The animal manure resources obtained above can achieve the purpose of composting without going through a separate composting process, and by-product fertilizer at a very high speed through a stabilization reaction with calcium addition and adjustment of C / N ratio as a post process. Or to suggest a method for producing a soil improver.

The manufacturing method for producing an organic matter resource from livestock manure of the present invention includes the following method.

Treating citric acid in the livestock manure to adjust the pH of the livestock manure to 1 to 6 levels;

Treating peracetic acid with a volume ratio of 0.1 to 50 in said manure to remove copper and zinc; And

Irradiating gamma rays and electron beams at 0.1 to 100 kGy.

In addition, the present invention proposes a method for producing a by-product fertilizer or a soil improver at a very high speed through the stabilization reaction with calcium addition and the adjustment of carbon / minus ratio (C / N ratio).

More specifically, the present invention relates to a method for producing an organic material from livestock manure, comprising the following steps.

Preparing a livestock manure or livestock manure sludge at a concentration of 0.1 to 20 w / v%;

Treating the livestock manure with citric acid to adjust the pH to 1 to 6;

Treating peracetic acid with a volume ratio of 0.1 to 50 in the livestock manure;

Adding bentonite to carry out solid-liquid separation of the livestock manure and stirring to perform solid-liquid separation, and then adding a cationic polymer coagulant to form a large floc; And

Irradiating gamma rays and electron beams at 0.1 to 100 kGy.

The acid added to adjust to pH 1 to 6 in the process is preferably one or more acids selected from the group consisting of citric acid, hydrochloric acid, sulfuric acid, nitric acid and citric acid.

In addition, the treatment to remove copper and zinc is preferably one or more selected from the group consisting of citric acid, nitrilotriacetic acid (NTA), Ca-EDTA, Na-EDTA and peracetic acid. The gamma ray is a gamma ray selected from the group consisting of cobalt (Co, atomic number: 60), krypton (Kr, atomic number: 85), strontium (Sr, atomic number: 90), and cesium (Cs, atomic number: 137). Is preferably.

In the present invention, livestock manure includes dung and urine excreted by livestock such as cattle, pigs and chickens.

In addition, in the above process,

Livestock manure generated in farms was subjected to the implementation, but livestock manure dehydration cake discharged from the livestock manure treatment plant can also be used by the same embodiment.

Also, before forming a giant floc

Hydrogen peroxide or nitric acid may be treated alone or in a mixture of 0.1 to 50 v / v% for structural cleavage, destruction of cell walls and oxidation of organic matter from livestock manure.

When the present invention is described in more detail by process,

The first step is to remove the manure or debris using the livestock manure dehydration cake concentration (10%) and vibrating screen,

In the second process, citric acid is added to livestock manure raw materials that have been transferred into the reaction tank to adjust pH to 3 to 5, and thereafter, peracetic acid is added to wash heavy metals.

The third process is a solid-liquid separation process of livestock manure, adding bentonite and an organic polymer coagulant to form a fine floc, and then adding an organic polymer coagulant to form a macro floc,

The fourth step is an electron beam irradiation step or a gamma ray irradiation step.

Thereafter, the following process may be added.

A dehydration step of the sample in which the electron beam and gamma irradiation are completed;

Shaking by adding livestock manure solids and quicklime, shell shells or Cement kiln dust to stabilize the sample;

Drying process; And

Pellet processing step of adding molasses to the livestock manure.

The dehydration liquid separated in the dehydration process is again subjected to secondary agglomeration (adding a polymer organic coagulant, which is opposite to the + charge of heavy metals for heavy metal removal), and then the solid and liquid are separated through a microfilter. Re-use for concentration adjustment, solids (mostly heavy metals) can be incinerated.

In addition, it is preferable to use the ultrafast centrifugal separation method or a filter press for a dehydration process.

Such a manufacturing process is shown in Table 1.

[Table 1] Removal of harmful components derived from livestock manure and non-fermented high-speed by-product fertilizer production system using the same

Hereinafter, the present invention will be described in detail with reference to FIGS. 1, 2, and 3.

The raw material introduced into the raw material storage tank 4 is operated by the raw material feeder 4d to push the raw material in the direction of the raw material conveying pump 4a, and the raw material is transferred to the vibrating screen 1 using the raw material conveying pump 4a, By operating the vibrating screen 1 while supplying the circulating water to the circulating water supply pump 5a, large foreign substances are discharged to the foreign substance discharge conveyor 1b.

The raw material which has passed through the screen net 1a is transferred to the crusher 2 and crushed to a predetermined size or less by the cutter 2b, and citric acid is supplied to the citric acid feed pump 6a to adjust the pH of the raw material. Thereafter, peracetic acid is introduced into the # 1 reactor 3 with a peracetic acid pump 7a. At this time, the concentration and pH are automatically adjusted by the pH meter (3d) and densitometer (3e) and then stirred with a # 1st stirrer (3b) to give a residence time in the state of easy washing of heavy metals and react.

After the reaction is completed, the raw material is transferred to the electron beam reaction unit or the gamma ray reaction unit 8 through the raw material transfer pump 3a and irradiated with the electron beam irradiation device or the gamma ray irradiation device 9, and then the raw material rolled up with the scraper 8a is It is supplied to # 2 secondary reactor (11). In the secondary reactor 11, the polymer coagulant and bentonite are supplied by the polymer coagulant supply pump 13a and the bentonite supply pump 14a, and the fine particles are first agglomerated by stirring with the second secondary agitators 11b and 11c. After supplying the polymer flocculant to the polymer flocculant supply pump 12a, the mixture is stirred with a # 2 stirrer (11d) to form a large flock, and the final flocculation is completed, and then sent to the dehydrator 15 to perform dehydration.

The dewatered cake dehydrated in the dehydrator 15 is stored in the dewatered cake dispenser 16 and then transferred to the screw feeder 17d by the dewatered cake feed screw conveyor 16a while being pushed to the dewatered cake feeder 16b by a predetermined amount. The screw feeder 17d supplies lime to the lime feeding screw conveyor 18b while mixing the dehydration cake with the high concentration mixer 17 while pushing the dewatering cake into the high concentration mixer 17. The cake mixed in the high concentration mixer 17 is sent to the mixing cake discharger 19 to give a predetermined time to react well.

After completion of the reaction in the mixing cake dispenser 19, the cake is pushed to the mixing cake feeder 19b by a predetermined amount and transferred to the dryer 20 by the mixing cake conveying screw conveyor 19a, and dried to a state suitable for pellet by-product fertilizer processing. It is stored in the cake discharger 21. The dry cake stored in the dry cake dispenser 21 is sent to the pellet-type by-product fertilizer maker 22 by a predetermined amount by the mixing cake feed screw conveyor 21a while being pushed to the mixing cake feeder 21b and processed into by-product fertilizer pellets. The molasses is supplied to the pellet maker through the molasses supply pump 22b in the molasses storage tank 22a to facilitate pellet formation and to reinforce molding strength.

The pellet-type by-product fertilizer processed in the pellet form enters into the pellet dryer 23 and is dried to form the pellet form firmly. Molded pellet by-product fertilizer is weighed to a certain weight through a pellet meter (24) and then packaged in a pellet packing machine (25) to complete the product.

The dehydration filtrate treatment will be described with reference to FIG. 2 as follows.

The filtrate from the dehydrator 15 is collected in the # 3rd reactor 26 to agglomerate with a dehydration filtrate stirrer 26b while supplying a coagulant to a coagulant supply pump 27a, followed by agglomeration with a dehydration filtrate transfer pump 26a. Sent to filter (28) to separate treated water and heavy metal precipitates

The treated water is transferred to the treated water tank 31 and transferred to the circulating water tank 5 through the treated water circulation pump 31a for reuse. Heavy metal deposits from the micro filter 28 are stored in the waste tank 32 by the heavy metal deposit transfer pump 30a and then disposed of by the waste transport vehicle 33.

The supernatant of the heavy metal precipitation tank 30 is sent to the treated water tank 31 by the supernatant circulation pump 30b for reuse.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are illustrative of the present invention, and the content of the present invention is not limited to the examples.

<Example 1>

Pig meal (solid concentration: 20-25%) was collected at a large livestock complex in Wanggung-myeon, Iksan-si, Jeollabuk-do. After putting 2 kg of pig meal in a small reactor, the concentration of pig meal was adjusted to 10%. Thereafter, the raw material was passed through a small vibrating screen, and then stored in a small sieve. Citric acid (60w / v%) was added to the small sieve to adjust the pH to 3, and 50 mL of peracetic acid (peracetic acid, 20v / v%) was added to wash the heavy metals. In this embodiment, the concentration of the pig meal is adjusted to 10%, but may be adjusted within the range of 5 to 20% for the optimization of the process. In addition, although not shown in the present embodiment, the drug used for the purpose of pH adjustment is not limited to citric acid, hydrochloric acid, sulfuric acid, nitric acid may be mixed or used alone. In addition, in the present embodiment, hydrogen peroxide or nitric acid may be used for structural cleavage and organic oxidation of livestock manure-derived organic matter, and peracetic acid was used in this embodiment to enhance the cleaning effect of heavy metals. If necessary, citric acid, nitrilotriacetic acid (NTA), Ca-EDTA and Na-EDTA can be treated.

<Example 2>

In order to solid-separate the pig manure prepared in Example 1, first, 100 mL of bentonite (4w / v%) was added and stirred for 20 minutes (120 times) in order to form a more negative charge with the negative (-) charge of the pig manure. / Min). In general, wastewater treatment processes use a lot of aluminum or iron salts, which may accumulate in the soil ecosystem and cause heavy metal contamination. In the present invention, bentonite, which is a montmorilonite series having excellent negative charge ability, is used. Thereafter, 50 mL of a cationic polymer coagulant (0.2v / v%) was added to form a microfloc, followed by stirring. Finally, 50 mL of a cationic polymer flocculant (0.5v / v%) was added to form microflocs into large flocs and allowed to react for 20 minutes. Here too, polymer cations that are highly effective in forming soil incidence or improving soil physical properties when treated with soil, avoiding the use of inorganic coagulants or inorganic coagulants in consideration of the input of agricultural land produced by by-product fertilizer. Agglomeration / coagulant was used.

Example 3

The pig meal samples prepared in Example 2 were irradiated with electron beams and gamma rays at the 5kGy level at the Advanced Radiation Research Institute in Jeongeup, Jeollabuk-do. The electron beam and gamma-irradiated samples were centrifuged in a high-speed centrifuge (2,000 rpm / min) to separate the pig flour dehydrated cake and the dehydrated filtrate. 10 w / w% of quicklime (CaO) was added to the dehydrated cake (20%), followed by shaking for 3 minutes at a speed of 600 rpm / min in a shaker serving as a high concentration mixing reactor. After that, the dehydration cake was placed in a reaction tank and the reaction was allowed to stabilize for 30 minutes. In the present embodiment, the chemical used in the stabilization method is quicklime, but if necessary, calcium-rich resources such as calcium hydroxide [Ca (OH) ₂ ], shell shells, starfish and cement kiln dust may be reused.

Example 4

The dehydrated cake (water content: 70%) prepared in Example 3 was dried in a dry oven to adjust the water content to 35%. To the dried dehydrated cake was added 25 mL of molasses (a light yellow, transparent, viscous sugar solution) and stirred well. The stirred sample was put into a pelletizer to prepare a circular pellet by-product fertilizer to complete the invention (see FIG. 3). Although not listed in the present embodiment, the present invention can be used to develop products as well as by-product fertilizers, but also in mature soil, seedling soil and soil improver.

Example 5

The dehydration liquid separated in Example 3 (150 mg / L level based on COD _Mn ) is expected to have eluted a significant amount of heavy metal components (Cu, Zn) by the process in Example 1. In order to effectively flocculate the positively charged heavy metals, 50 mL of a polymer anionic coagulant (0.2v / v%) was added thereto and stirred (120 times / min) for 20 minutes. 50 mL of anionic polymer flocculant (0.5v / v%) was added and reacted for 20 minutes in order to form a microfloc in which heavy metal was condensed into a large floc. The residue filtered out when the floc formed dehydration liquid was passed through a micro filter system was collected and disposed of, and the liquid was reused in the raw material circulation process of Example 1.

Example 6

The pellet by-product fertilizer and livestock manure (pig meal) by-product fertilizers prepared in Example 4 were investigated for the reduction of harmful components by gamma ray and electron beam irradiation and the reduction of heavy metal by heavy metal cleaning.

As a control, the pig powder samples collected directly from pig farms in Wanggung-myeon, Iksan-si, Jeollabuk-do, were investigated to reduce the effects of by-product fertilizers and pig powder samples, heavy metal washes and antibiotics, E. coli and pesticides. It was.

Investigation items included organic, total nitrogen, ammonia nitrogen, nitrogen nitrate, hydrochloric acid insolubles, total phosphorus, kali, salt, moisture, total heavy metal content, heavy metal content by type, coliform group, and indicators of pathogenic microorganisms. Most commonly used ampicillin + collistion sulfate (trade name: ampicoli) and pesticides (Dichlorvos, DDVP). Each test method was in accordance with the Ministry of Environment's water pollution test method, waste process test method, Korea Pharmacopoeia, fertilizer process test method and pesticide residue analysis method.

The results of investigating the reduction effect of heavy metal washing and antibiotics, E. coli and insecticides according to the embodiment of the present invention compared to pig powder sample directly collected from pig farms in Wanggung-myeon, Iksan-si, Jeollabuk-do, Korea.

The organic matter content in the control group decreased by about 14.26%, gamma-irradiated 25.80% and 27.27% by electron beam. Total nitrogen decreased by 8.09%, gamma-irradiation 47.66%, and electron beam irradiation 51.49% compared to livestock manure, but ammonia nitrogen and nitrogen nitrate tended to increase slightly. This may be due to the conversion of some organic nitrogen to inorganic nitrogen by decomposing some organic matters by peracetic acid and gamma rays / electron beams, which were added for cleaning heavy metals in the embodiment compared to livestock manure. This means that the increase of nitrogen component that can be used as plant nutrients as the plant grows, and it is judged that the gamma-ray irradiation is useful for the degradation and ripening of organic materials with slow decomposition rate in soil.

Compared with livestock manure, the effect of hydrochloric acid insolubles and salinity was remarkable by gamma ray and electron beam irradiation, which is also attributed to the detergent and concentration dilution added to heavy metal cleaning process.

As a result of investigating the reduction effect of livestock manure, the heavy metals copper and zinc, which are known to be contained in animal manure,

In the case of zinc, the experimental group showed 3.33%, gamma irradiation 71.88%, electron beam irradiation 71.76%, and in the case of copper 8.27%, gamma irradiation 72.10%, electron beam irradiation 71.19%, citric acid and peracetic acid treated in the present invention It has been shown to be a very efficient method for cleaning and removing heavy metals such as copper and zinc in livestock manure.

The coliform group contained in livestock manure contained about 25,000 MPN / mL in general pig meal, but it was reduced by 98.58% by control, and completely 100% sterilized by gamma ray and electron beam irradiation. The high E. coli killing rate in the control group was judged to have been killed by self-heating (about 100 to 125 degrees) in the stabilization method treated with lime, and completely sterilized by gamma ray and electron beam irradiation. Gamma rays and electron beam irradiation can be an effective means to control.

[Table 2] Effect of changes in phytonutrients and removal of harmful components according to the embodiment of the present invention

^* 본 발명에 사용된 가축분뇨 원료는 전라북도 익산시 왕궁면 양돈농가에서 직접 채취한 시료

^* Livestock manure raw material used in the present invention is a sample directly collected from pig farms in Wanggung-myeon, Iksan-si, Jeollabuk-do

^** Pellet by-product fertilizer prepared by the same process as in Example without irradiating gamma rays or electron beams and removing heavy metals

The antimicrobial ampicillin + collistion sulfate (trade name: ampicoli) contained in livestock manure was tested for control effect by control, gamma ray and electron beam irradiation. All of the methods showed positive reactions, but the antibiotics were completely decomposed by gamma-ray and electron beam treatments.

Dichlorvos (DDVP), a pesticide treated for livestock farms to eliminate flies and various pests, was investigated for 29.50% in the control compared to livestock (pig meal). Gamma-rays and electron beams were found to be very useful in reducing degradation of persistent organic pollutants with 100% irradiation and 100% electron beam irradiation.

According to the present invention, citric acid and peracetic acid treatment has been shown to be very effective in cleaning and removing heavy metals such as copper and zinc contained in livestock manure, and the electron beam or cobalt (Co, atomic Number: 60) When gamma rays emitted from radioisotopes were irradiated at 5kGy level, they showed excellent effects such as complete decomposition and removal of antibiotics and insecticides derived from livestock manure and complete sterilization of pathogenic microorganisms. Using this excellent organic resources, a system was developed to produce high quality by-product fertilizers quickly through the stabilization reaction with calcium addition and the adjustment of C / N ratio without the need for a separate composting process. .

Claims (6)

Method for producing an organic material from livestock manure, characterized in that it comprises the following steps: Treating citric acid in the livestock manure to adjust the pH of the livestock manure to 1 to 6 levels; Treating peracetic acid with a volume ratio of 0.1 to 50 in said manure to remove copper and zinc; And Irradiating gamma rays and electron beams at 0.1 to 100 kGy. The method of claim 1, comprising the following steps: Preparing a livestock manure or livestock manure sludge at a concentration of 0.1 to 20 w / v%; Treating the livestock manure with citric acid to adjust the pH to 1 to 6; Treating peracetic acid with a volume ratio of 0.1 to 50 in the livestock manure; Adding bentonite to carry out solid-liquid separation of the livestock manure and stirring to perform solid-liquid separation, and then adding a cationic polymer coagulant to form a large floc; And Irradiating gamma rays and electron beams at 0.1 to 100 kGy. [Claim 3] The method of claim 2, further comprising the step of adding 0.1 to 50 volume ratios of hydrogen peroxide or nitric acid alone or in combination for structural cleavage, cell wall destruction and organic oxidation of the prepared organic resources. Manufacturing method. The organic material resource according to claim 1 or 2, wherein the acid added for adjusting to pH 1 to 6 is one or more acids selected from the group consisting of citric acid, hydrochloric acid, sulfuric acid, nitric acid and citric acid. Manufacturing method. The method according to claim 1 or 2, wherein the treatment to remove copper and zinc is performed in the group consisting of citric acid, nitrilotriacetic acid (NTA), Ca-EDTA, Na-EDTA, and peracetic acid. Method for producing an organic material from livestock manure, characterized in that one or more selected. The method of claim 1 or 2, wherein the gamma rays are cobalt (Co, atomic number: 60), krypton (Kr, atomic number: 85), strontium (Sr, atomic number: 90) and cesium (Cs, atomic number: 137 And a gamma ray selected from the group consisting of).

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