KR20030075829A - The Seed culture delivery system for foul water and wastewater and their manufacturing method - Google Patents

Abstract

PURPOSE: Provided are slow-release bacterial seeding product which is nontoxic when it is used in wastewater treatment process and does not cause secondary pollution since the produce is completely decomposed to carbon dioxide and water. CONSTITUTION: The product comprises 50-70 wt% of biologically degradable aliphatic polyester resin selected from a group being consisted of polybutylene adipate, polybutylene succinate-co-adipate, polybutylene succinate-co-butylene adipate, polybutylene succinate, polybutylene succinate-co-terephthalate and 1 wt% of bacillus subtilis (ATTC 6633) which is thermal resistant strain and immobilized to the polyester resin.

Description

Sustained release wastewater treatment spawning agent and its manufacturing method {The Seed culture delivery system for foul water and wastewater and their manufacturing method}

The present invention relates to a sustained-release wastewater treatment spawn comprising immobilization of a heat-resistant strain Bacillus subtilis ATCC on a biodegradable aliphatic polyester resin. In more detail, the present invention is a heat-resistant strain Bacillus subtilis ATCC 6633 polybutylene adipate, polybutylene succinate-co- adipate, polybutylene succinate-co-butylene adipate, The present invention relates to a sustained-release wastewater treatment seed immobilized on a biodegradable aliphatic polyester resin consisting of polybutylene succinate, polybutylene succinate-co-adipate, and polybutylene succinate-co-telephthalate.

Biodegradable plastic refers to plastic that is completely decomposed into water, carbon dioxide, methane gas within months by the action of microorganisms by simply landfilling the plastic used as a molded product, packaging agent, hygiene product, agricultural product, etc. Currently, biodegradable resins that are already developed include starch-based biodegradable resins chemically synthesized with starch-based biodegradable resins processed by an extruder with additives such as corn, potatoes, which are non-toxic natural products, and biodegradable aliphatic polyester resins.

The present invention is to solve the problem of stable sludge activation and unmanned automatic treatment which is one of the biggest problems that occur in biological treatment of domestic sewage or industrial wastewater. That is, the present invention uses a biodegradable aliphatic polyester resin capable of being slowly decomposed and magnetized by microorganisms extracted and purified from natural resources as a carrier, and the microorganisms or management agent for wastewater treatment are encompassed by immobilization technology. By adding cross-linking or binding carriers, sludge management agents or microorganisms are slowly eluted when they are introduced into biological treatment facilities to enable the treatment of persistent and stable wastewater.

The treatment of industrial wastewater and domestic sewage generated by various industries such as food industry, leather industry and paper industry depends on biological treatment, and it is very important to stably propagate and activate activated sludge in the treatment system. To this end, all existing sewage / treatment spawning agents or management agents are liquid or powdery products, and when they are put into aeration tanks or septic tanks, they have low sustained management and maintenance effects. Continuous input of chemicals or management chemicals was necessary, especially in wastewater treatment facilities with large fluctuations in inflows over time, or in merger septic tanks with low storage tanks for large amounts of inflow. In case of explosion, spawning agent for wastewater treatment in a short time or Rize is a component of the drug leaked into effluent that was more efficient low.

As a solution to this problem, microorganisms have been coated on contact media, and contact media that have adsorbed microorganisms on soil and ceramic carriers have been developed and marketed. However, this has been expensive and costly. The burden of funding on the installation and operation of the treatment facility was large, and there was a problem that the activity of the adherent microorganisms disappeared and the coating had to be recoated when such a facility was used for a long time or shocked by chemicals such as acid and alkali.

On the other hand, the microbial cell or enzyme immobilization technology, such as carrier binding method, crosslinking method or comprehensive method developed as shown in Figure 1 has been developed and applied to the biological industry such as alcohol fermentation, the material of the carrier used in Table 1 There are several kinds of immobilization methods, as in. In other words, activated carbon, diatomaceous earth, kaolin, polyacrylamide, etc. are used in physical adsorption methods, and high-priced devices such as DEAE-cellulose, CM-cellulose, Sephadex, etc. Insoluble polymer resin is used.

[Table 1] Immobilization Methods and Types of Carriers Used

Carrier Bonding Method Physical adsorption method Solid catalyst by adsorption on carrier such as activated carbon, acid clay, bleach, Kaolinite, polyacrylamide resin Ion Bonding Solid catalyst by ion bonding to ion exchangers such as DEAE-Cellulose and CM-Cellulose Covalent bonding method Diazo Method: (R-NH₂ → RN = NCI + E-→ RN = NE) Dipeptide Method: (R-CON₃ + E → R-CONH-E) Alkylation Method: (ROC-CH₂BR + E → RC-CH₂-E ∥OO Crosslinking Crosslinking enzymes using two functional reagents to solidify the enzyme (glutaraldehyde, bis-diazo-benzidine, a mixture of maleic anhydride and ethylen) Inclusive Lattice Insolubilized with polyacrylamide gel, dissolved in starch solution and put in urethan form to gel into solid catalyst Capsule Solid catalyst by coating colloid ion membrane

In addition, polyacrylamide, silicon resin, or polyvinyl is used as the immobilization carrier of the comprehensive method. Among them, diatomaceous earth or activated carbon increases the amount of sludge generated when it is added to biological wastewater treatment facilities. The polymer resins used here are not only expensive but also increase the amount of precipitated sludge as in the case of diatomaceous earth.

In particular, all the carriers used above do not have the sustained release biodegradation performance desired in the present invention, and cannot be prepared in the form of granules or styropol in the form of light specific gravity by foam molding, and are completely decomposed and oxidized by microorganisms. Rather, there is a risk of raising the BOD and COD of the effluent.

The present invention solves the above problems and the microorganisms used when the sustained-release wastewater treatment spawning agent of the present invention is injected into a biological wastewater treatment facility, stays for several weeks to several months in the treatment system, and thus the vortex caused by the aeration tank aeration. The purpose is to continuously maintain and manage the wastewater treatment by slowly releasing maintenance agents such as active microorganisms, sediment aids or bulking agents. At this time, the biodegradable aliphatic polyester resin, which is biodegradable and eluted with microorganisms, is a macromolecular substance having the same structure as the non-toxic natural aliphatic macromolecule extracted and manufactured from food raw materials. Finally, since it is decomposed into carbon dioxide and water, its components do not remain in the final discharged water, so there are no side effects such as secondary pollution. The decomposition process is shown in the table below.

[Table 2] Biodegradation Process of Biodegradable Polymer Resin

Hereinafter, the configuration and operation of the present invention.

1 shows several types of carrier binding models.

Figure 2 shows an electron micrograph of the sustained-release wastewater treatment spawn agent combined with the heat-resistant strain to the biodegradable aliphatic polyester resin carrier of the present invention.

Figure 3 shows an apparatus for producing a sustained-release waste water treatment spawn agent used in the present invention.

The present invention provides a sustained-release wastewater treatment spawn agent which immobilizes the heat resistant strain Bacillus subtilis ATCC 6633 on a biodegradable aliphatic polyester resin, and a method for preparing the same.

Biodegradable plastic refers to plastic that is completely decomposed into water, carbon dioxide, methane gas within months by the action of microorganisms by simply landfilling the plastic used as a molded product, packaging agent, hygiene product, agricultural product, etc. Currently, biodegradable resins that are already developed include starch-based biodegradable resins chemically synthesized with starch-based biodegradable resins processed by an extruder with additives such as corn, potatoes, which are non-toxic natural products, and biodegradable aliphatic polyester resins.

[Table 3] Molecular structure diagram of sustained-release (biodegradable) polymer resin (carrier)

The biodegradable aliphatic polyester resin according to the present invention is disclosed in Korean Patent No. 0123895 as "Method for Producing Biodegradable Aliphatic Polyester Resin Composition", and Korean Patent No. 10-0181673 for "Polydegradable Polyester Resin. It is disclosed in the "method of manufacturing" and Korean Patent No. 10-0257828 "method of producing a polyester composite resin having excellent physical properties and compositions thereof," Korean Patent Publication No. 1999-009593 "biodegradable Co-polyester resin composition and its preparation method ".

The biodegradable aliphatic polyester resin according to the present invention was used by purchasing a biodegradable aliphatic polyester resin (trade name: EnPol) manufactured and sold by Chemistry Co., Ltd., and the biodegradable aliphatic polyester resin EnPol is a polybutylene adipate. , Polybutylene succinate-co-adipate, polybutylene succinate-co-butylene adipate, polybutylene succinate, polybutylene succinate-co-adipate or polybutylene succinate-co- It is a biodegradable aliphatic polyester resin composed of telephthalate.

When preparing the sustained-release wastewater treatment spawn agent of the present invention, a heat-resistant strain Bacillus subtilis is a carrier binding method, enclosing method, crosslinking method or microcapsule method, which is a method of immobilizing the cells shown in FIG. Can be immobilized accordingly.

Biodegradable aliphatic polyester resin used as a carrier in the present invention is first heated to 80 to 200 ℃ for foaming, mixing, molding. At this time, since the cells of the microorganisms to be mixed should be instantaneously contacted with high temperature, it is preferable that the used strain is added by culturing in a state of a heat resistant strain or spores.

When preparing the sustained-release wastewater treatment spawn agent of the present invention, a wastewater management agent useful for biological treatment of wastewater can be added by homogeneously mixing a polymer coagulant, a sedimentation aid, a specific gravity enhancer, a nutrient and a pH adjuster. have.

The production apparatus for producing a sustained-release wastewater treatment spawn agent of the present invention can be manufactured by applying ordinary plastic extrusion molding, but the amount of the wastewater management agent, the method of addition, the temperature, the speed at the time of addition, etc. It needs to be supplemented.

In order to prepare a sustained-release wastewater treatment spawn according to the present invention, (A) heat-resistant strain Bacillus subtilis ATCC 6633 is a liquid medium containing 0.0001% to 0.001% of manganese sulfate or zinc sulfate component or the Inoculated into a solid medium containing 1.5 to 1.8% of agar in a liquid medium and incubated for 24 to 96 hours at 30 to 37 ° C to form spores, followed by dehydration drying or centrifugation to recover the cells and spores, The mixture was added and mixed homogeneously, followed by drying to prepare 1% by weight of the raw cell powder containing 10 ¹⁰ to 10 ¹¹ individuals or more per 1 g, and then the raw material cell powder to the raw material injection device (F-3) of FIG. Filling step: (B) Waste and waste water management agent useful for biological treatment of waste and waste water, homogeneous mixture of polymer coagulant, sedimentation aid, specific gravity enhancer, nutrient and PH modifier. 29 to 49% by weight of a wastewater treatment management agent useful for biological treatment of water and filling it into a raw material injection device (F-2): (c) 50 to 70% by weight of biodegradable aliphatic polyester resin Filling the device (F-1): (D) After connecting the power supply to the cylinder 1 and the biodegradable aliphatic polyester resin while adjusting the temperature of the cylinder 1 and cylinder 2 shown in Figure 3 manufacturing apparatus to 80 ~ 200 ℃ And passing through the cylinder 2: (e) the waste water treatment management agent filled in the raw material injection device (F-2) when the biodegradable aliphatic polyester resin passes through the third cylinder shown in FIG. Down-regulating the temperature in the cylinder to 80-120 ° C. while incorporating the biodegradable aliphatic polyester resin by injecting: (F) the biodegradable aliphatic polyester resin incorporating the wastewater treatment agent into the cylinder 4 and the cylinder. When passing through 5, control the temperature to 60 ~ 100 ℃ and inject the microorganism spores of the raw material injection device (F-3) and finally set the temperature to 50 ~ 80 ℃. To produce a wastewater treatment spawn comprising 10 to ⁸ spawns per gram of product, a specific gravity of 0.8 to 1.2, a pH of 6.8 to 8.5, and a biodegradable aliphatic polyester resin of 50 to 70% by weight. .

In addition, in order to prepare a sustained-release wastewater treatment spawn according to the present invention (A) heat-resistant strain Bacillus subtilis ATCC 6633 inoculated in a solid or liquid nutrient medium containing manganese or zinc and 30 After incubation at -37 ℃ for 24 to 96 hours to form spores, the cells and spores are recovered by dehydration drying or centrifugation, and diatomaceous earth is added to the obtained cells, mixed homogeneously, and dried to obtain ¹⁰ 10-10 ¹¹ After preparing 1% by weight of the raw cell powder containing the above, and filling the raw material powder in the raw material injection device (F-3) of Figure 3 manufacturing apparatus: (b) the drain device, the stirring device and the temperature control device 50 to 70% by weight of a biodegradable aliphatic polyester resin was added to a hopper-type mixing device provided, and the temperature was adjusted to 80 to 200 ° C. while stirring to sufficiently dissolve the polyester resin. Steps to increase: (C) The composition ratio of the wastewater treatment management agent, including crystal copolysaccharide: polymer coagulant, sedimentation aid, chitosan, specific gravity enhancer, nutrient and PH adjuster, is 1: 1 while stirring the dissolved polyester resin. To a homogeneous encapsulation of the polyester resin by adding 29 to 49% by weight of crystalline glucose and a wastewater treatment management agent, which are configured as a 2: 1 ratio, and then slowly adjusting the temperature to 60 to 80 ° C: ( D) When the temperature is sufficiently low and the physical properties of the mixture are maintained in the liquid phase, the microbial cell powder prepared in step (a) is added, and then rapidly mixed and stirred, and then ejected and formed by a suitable capacity through a drain apparatus to form microbial nutrients and settling aids. It characterized by the step of preparing a sustained-release wastewater treatment containing the containing.

In addition, the sustained-release wastewater treatment spawn according to the present invention is formed into a powder pack, granular or solid mass by enclosing or carrier-binding the cells or spores of strains useful for the treatment of wastewater and biodegradable aliphatic polyester resin. Can be prepared.

Example 1

Solid nutrition medium containing 1.8% of agar in liquid medium containing manganese sulfate and zinc sulfate 0.001% in culture medium consisting of heat-resistant strain Bacillus subtilis ATCC 6633 and 0.25% yeast extract and 0.1% tryticase Inoculated in the incubation for 96 hours at 37 ℃ to form a spore and then centrifuged for 30 minutes at 15,000rpm to recover the cells and spores. 1 kg of diatomaceous earth was mixed with 1 kg of diatomaceous earth, mixed, dried and homogenized to prepare 1 kg of raw cell powder containing 10 ¹⁰ to 10 ¹¹ or more per g, and the raw cell powder injection device of FIG. (F-3) A wastewater treatment management agent homogeneously mixed with 1 kg of cationic polymer coagulant, 10 kg of powdered chitosan sedimentation aid, 10 kg of clay, and 8 kg of powder yeast as useful management agents for biological treatment of wastewater. Kg is prepared and filled in the raw material injection device (F-2). After filling 70 kg of polybutylene succinate-co-butylene adipate (EnPol, manufactured by Chemistry Co., Ltd.) as a biodegradable aliphatic polyester resin in a raw material injection device (F-1), After connecting, the biodegradable aliphatic polyester resin was passed through the temperature of cylinders 1 and 2 at 80 ° C to 200 ° C. When the biodegradable aliphatic polyester resin passes through the third cylinder, the wastewater treatment management agent stored in the raw material injection device (F-2) is injected into the cylinder 3 and combined with the biodegradable aliphatic polyester resin in the cylinder. Adjust the temperature down to 80 ° C. When the biodegradable aliphatic polyester resin mixed with the wastewater treatment management agent passes through the cylinders 4 and 5, the temperature is controlled to 100 ° C and the microorganism spores stored in the raw cell powder injection device (F-3). After the final temperature was set to 80 ° C. and passed through the adapter, it was injected into a mold and molded to contain 10 ⁸ or more spawns per 1 g of product, specific gravity 0.8 to 1.2, pH 6.8 to 8.5, and biodegradable aliphatic poly. 100 kg of the sustained-release wastewater treatment spawn containing 70% of the ester resin was prepared.

Example 2

A polybutylene succinate-co-butylene adipate, a biodegradable aliphatic polyester resin, in a hopper-type mixing device equipped with a drain device, a stirring device, and a temperature control device. 70 kg), while stirring, the temperature is adjusted from 80 ° C to 200 ° C to sufficiently dissolve the biodegradable aliphatic polyester resin. While continuously stirring the dissolved biodegradable aliphatic polyester resin, 20 kg of crystal glucose and 9 kg of powder sedimentation aid were added slowly to homogeneously encompass and bind the crystal glucose and powder sedimentation aid to the biodegradable aliphatic polyester resin. Slowly adjust to 80 ° C. When the temperature is sufficiently low and the physical properties of the mixture are maintained in the liquid phase, 1 kg of the microbial microbial powder of Example 1 is added, and then rapidly mixed through the drainage apparatus while being rapidly mixed and stirred to form a sustained release containing microbial nutrients and sedimentation aids. The wastewater treatment spawn 100 kg was prepared.

In the case of using the sustained-release wastewater treatment spawn according to the present invention in a biological wastewater treatment facility, the microorganisms contained in the sustained-release wastewater treatment spawn in the treatment system stay for several weeks to several months in the aeration tank. It circulates along the vortices and slowly releases active microorganisms, and it is effective in steadily maintaining and managing wastewater treatment by releasing wastewater treatment management agents such as precipitation aids and bulking inhibitors. At this time, biodegradable aliphatic polyester resin, which is biodegradable and eluted with microorganisms, is a macromolecular substance having the same structure as non-toxic natural aliphatic polymer material extracted and manufactured from food raw materials. Finally, since it is decomposed into carbon dioxide and water, its components do not remain in the final discharged water, so there are no side effects such as secondary pollution. In addition, the conventional wastewater treatment spawn agent which is not bound to biodegradable aliphatic polyester resin is a liquid or powder product, and when it is added to an aeration tank or a septic tank, the microbial strain may not have activity after 3 to 5 days. The sustained-release wastewater treatment spawn is a breakthrough invention that can be used as a wastewater treatment agent for a long time because the biodegradable aliphatic polyester resin is gradually biodegraded and microorganisms grow for more than 1 to 2 months when it is added to an aeration tank or a septic tank. to be.

Claims (4)

1% by weight of the heat resistant strain Bacillus subtilis is polybutylene adipate, polybutylene succinate-co-adipate, polybutylene succinate-co-butylene adipate, polybutylene succinate, Sustained release characterized in that it is immobilized in 50 to 70% by weight of at least one biodegradable aliphatic polyester resin selected from the group consisting of polybutylene succinate-co-adipate or polybutylene succinate-co-telephthalate Wastewater treatment spawning agent. The sustained-release wastewater treatment spawning agent according to claim 1, wherein the heat resistant strain Bacillus subtilis is ATCC 6633. The sustained-release wastewater according to claim 1, wherein the wastewater treatment management agent including the polymer coagulant, the sedimentation aid, the specific gravity-enhancing agent, the nutritional agent and the pH adjusting agent and the crystal glucose are respectively added or added together. Treatment spawn. The method of claim 1, wherein the cells or spores of the heat-resistant strain Bacillus subtilis is immobilized on a biodegradable aliphatic polyester resin to be produced in a powder pack, granule, or solid mass form. Wastewater treatment spawning agent.