KR100481973B1 - Organic and Inorganic Hybrid Media for Microbe Immobilization and Its Producing Method - Google Patents
Organic and Inorganic Hybrid Media for Microbe Immobilization and Its Producing Method Download PDFInfo
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- KR100481973B1 KR100481973B1 KR10-2002-0058493A KR20020058493A KR100481973B1 KR 100481973 B1 KR100481973 B1 KR 100481973B1 KR 20020058493 A KR20020058493 A KR 20020058493A KR 100481973 B1 KR100481973 B1 KR 100481973B1
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- 238000000034 method Methods 0.000 title abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 21
- 238000001179 sorption measurement Methods 0.000 claims abstract description 20
- 244000005700 microbiome Species 0.000 claims abstract description 19
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003463 adsorbent Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910021432 inorganic complex Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical group O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229940080314 sodium bentonite Drugs 0.000 claims description 6
- 229910000280 sodium bentonite Inorganic materials 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 238000009423 ventilation Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 23
- 238000010304 firing Methods 0.000 abstract description 6
- 238000005187 foaming Methods 0.000 abstract description 4
- 230000000813 microbial effect Effects 0.000 abstract description 4
- 238000001599 direct drying Methods 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 description 8
- 239000000356 contaminant Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 229940092782 bentonite Drugs 0.000 description 4
- 229910000278 bentonite Inorganic materials 0.000 description 4
- 239000000440 bentonite Substances 0.000 description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
본 발명은 미생물 고정화 유·무기 복합담체 및 제조방법에 관한 것으로, 더욱 상세하게는 무기흡착소재 30 ∼ 80 중량%, 융점이 200 ℃ 미만인 열가소성수지 20 ∼ 70 중량%, 점결제 1 ∼ 10 중량% 및 수 용출성 탄산염 1 ∼ 20 중량%가 각각함유되어, 종래의 제조공정에서 일반적으로 수행했던 발포과정 및 소성과정 없이 직접 건조과정을 도입하여 다공성 복합담체가 제작됨으로써, 제조공정의 단순화와 원가의 저렴화 뿐만아니라 흡착력을 현저히 증가시키고 개·폐기공을 연결하여 오염물질의 유입 및 접촉을 원활히 하고 미생물의 서식환경에 적합한 구조를 갖는 성능이 우수한 미생물 고정화 유·무기 복합담체 및 이의 제조방법에 관한 것이다. The present invention relates to a microorganism immobilized organic-inorganic composite carrier and a manufacturing method, more specifically 30 to 80% by weight of inorganic adsorption material, 20 to 70% by weight thermoplastic resin having a melting point of less than 200 ℃, 1 to 10% by weight of binder And 1 to 20% by weight of water-elutable carbonate, respectively, and the porous composite carrier is manufactured by introducing a direct drying process without the foaming process and the firing process which are generally performed in the conventional manufacturing process, thereby simplifying the manufacturing process and reducing the cost. The present invention relates to a microorganism-immobilized organic-inorganic composite carrier having excellent structure having a structure suitable for a microbial habitat environment as well as a reduction in cost and a significant increase in adsorption power, and connecting open and closed pores. .
Description
본 발명은 미생물 고정화 유·무기 복합담체 및 제조방법에 관한 것으로, 더욱 상세하게는 무기흡착소재 30 ∼ 80 중량%, 융점이 200 ℃ 미만인 열가소성수지 20 ∼ 70 중량%, 점결제 1 ∼ 10 중량% 및 수 용출성 탄산염 1 ∼ 20 중량%가 각각 함유되어, 종래의 제조공정에서 일반적으로 수행했던 발포과정 및 소성과정 없이 직접 건조과정을 도입하여 다공성 복합담체가 제작됨으로써, 제조공정의 단순화와 원가의 저렴화 뿐만아니라 흡착력을 현저히 증가시키고 개·폐기공을 연결하여 오염물질의 유입 및 접촉을 원활히 하고 미생물의 서식환경에 적합한 구조를 갖는 성능이 우수한 미생물 고정화 유·무기 복합담체 및 제조방법에 관한 것이다. The present invention relates to a microorganism immobilized organic-inorganic composite carrier and a manufacturing method, more specifically 30 to 80% by weight of inorganic adsorption material, 20 to 70% by weight thermoplastic resin having a melting point of less than 200 ℃, 1 to 10% by weight of binder And 1 to 20% by weight of water-elutable carbonate, respectively, and a porous composite carrier is produced by introducing a direct drying process without a foaming process and a firing process, which are generally performed in a conventional manufacturing process, thereby simplifying the manufacturing process and reducing the cost. The present invention relates to a microorganism-immobilized organic-inorganic composite carrier and a manufacturing method which has excellent performance having a structure suitable for the habitat environment of microorganisms by not only reducing the cost but also significantly increasing the adsorption power and connecting open and closed pores to facilitate the inflow and contact of pollutants.
지금까지 개발된 고정화 담체는 우선 무기소재와 기공 형성제를 혼합하여 성형하거나 발포시켜 기포를 형성시킨 후 고온으로 열처리하여 제조하는 다공성 세라믹 담체 제조방법이 보고되고 있다. 이 방법은 기계적 강도와 기공율 그리고 함수율이 비교적 높은 담체를 제조할 수 있으나, 오염물질을 화학 흡착하는 산점이 매우 약해 오염물질의 흡착력이 떨어져 오염물질의 부하변동에 따른 일정한 처리효율을 기대하기가 어려우며, 제조과정에서 기공형성제의 산화로 인한 오염물질의 발생과 소성시 많은 에너지가 소모됨으로서 제조원가가 높다는 단점이 있다. 또한 미생물의 탈리현상이 자주 발생하여 일정한 농도의 미생물 개체수를 유지하기가 곤란하다는 문제가 있다.The immobilized carrier developed so far has been reported to produce a porous ceramic carrier prepared by mixing an inorganic material with a pore-forming agent or forming a foam to form a bubble and then heat-treating it at a high temperature. This method can produce a carrier with relatively high mechanical strength, porosity, and moisture content, but the acidity of chemical adsorption of pollutants is very weak, so it is difficult to expect constant treatment efficiency due to fluctuation of pollutant load. In the manufacturing process, a large amount of energy is consumed during generation and firing of pollutants due to oxidation of the pore-forming agent, resulting in high manufacturing costs. In addition, there is a problem that it is difficult to maintain a constant concentration of microorganisms due to frequent desorption of microorganisms.
또 다른 방법으로 실리카, 알루미나, 제올라이트 및 점토 등을 열가소성수지와 혼합한 후 발포제를 첨가하여 120 ℃ 이상의 온도로 사출함으로서, 열가소성수지를 녹여 결합제로 작용하게 하고 발포제의 작용으로 기공을 형성시키는 미생물 고정화 담체를 제조하는 방법이 공지의 방법으로 사용되고 있다. 상기 방법으로 제조한 미생물 고정화용 담체는 폐기공이 많이 형성되어 담체 내부까지 기체 및 액체의 침투가 어렵고, 열가소성수지의 용융으로 인해 형성된 고분자층이 상기의 흡착제와 오염물질의 접촉을 방해하는 작용을 한다. 이로 인해 담체의 흡착력과 함수율이 저하되어 미생물의 부착 능력을 감소시키게 되므로, 처리효율을 높일 수 없으며 또한 세라믹 담체와 같이 미생물의 탈리현상이 자주 발생하여 일정한 처리효율을 유지하기 곤란하다는 단점이 있다.In another method, silica, alumina, zeolite and clay are mixed with thermoplastic resin, and then foaming agent is added and injected at a temperature of 120 ° C. or higher to dissolve the thermoplastic resin to act as a binder and to form pores by the action of the blowing agent. The method of manufacturing a carrier is used by a well-known method. The microorganism-immobilized carrier prepared by the above method has a lot of waste holes, which makes it difficult to penetrate gas and liquid to the inside of the carrier, and the polymer layer formed due to melting of the thermoplastic resin prevents contact between the adsorbent and contaminants. . As a result, since the adsorption power and water content of the carrier are reduced to reduce the adhesion ability of the microorganisms, the treatment efficiency cannot be increased, and the desorption phenomenon of the microorganisms frequently occurs like the ceramic carrier, which makes it difficult to maintain a constant treatment efficiency.
따라서 이와 같이 종래의 미생물 고정화 담체를 사용하는 처리공정에서는 담체 그 자체로는 고도처리 효율을 유지하기가 힘들기 때문에 이를 보완하기 위한 다양한 처리공법의 개발이 동시에 필요하다는 문제점이 있다. Therefore, in the treatment process using the conventional microorganism immobilization carrier, it is difficult to maintain the high treatment efficiency by the carrier itself, there is a problem in that it is necessary to simultaneously develop various treatment methods to compensate for this.
이에 본 발명자는 상기와 같은 복합담체의 폐기공과 오염물질과의 흡착력저하의 문제점을 해결하기 위하여 무기흡착소재, 점결제 및 양이온 교환제로 작용하는 나트륨 벤토나이트, 기공형성제와 결합제로 작용하는 융점이 200 ℃ 미만인 열가소성수지 그리고 폐기공 간의 연결통로 역할을 하면서 상기 흡착제와 유기물과의 접촉을 도와 흡착력을 증가시키는 수 용출성 탄산염을 일정 함량비로 혼합하여 종래의 발포과정 및 소성과정 없이 직접 건조과정만으로 성능이 우수한 미생물 고정화 유·무기 복합 담체 및 이의 제조방법을 제공하는데 그 목적이 있다. Therefore, the present inventors have solved the problem of lowering the adsorption power between the waste holes and the contaminants of the composite carrier as described above, the melting point of the sodium bentonite acting as an inorganic adsorption material, a caking agent and a cation exchanger, a pore-forming agent and a binder 200 It acts as a connecting passage between the thermoplastic resin and the waste hole below ℃, and the water-elutable carbonate which helps the contact between the adsorbent and the organic material and increases the adsorption power is mixed in a certain content ratio, so that the performance is achieved only by the direct drying process without the conventional foaming and firing process. An object of the present invention is to provide an excellent microorganism-immobilized organic-inorganic complex carrier and a method for producing the same.
본 발명은 무기흡착소재 30 ∼ 78 중량%, 융점이 200 ℃ 미만인 열가소성수지 20 ∼ 68 중량%, 점결제 1 ∼ 10 중량% 및 수 용출성 탄산염 1 ∼ 20 중량% 를 포함하는 유·무기 복합담체 및 제조방법을 그 특징으로 한다.The present invention provides an organic-inorganic composite carrier comprising 30 to 78 wt% of an inorganic adsorbent material, 20 to 68 wt% of a thermoplastic resin having a melting point of less than 200 ° C, 1 to 10 wt% of a binder, and 1 to 20 wt% of a water-elutable carbonate. And a manufacturing method thereof.
이와 같은 발명을 더욱 상세히 설명하면 다음과 같다.When explaining the invention in more detail as follows.
본 발명은 무기흡착소재와 융점이 200 ℃ 미만인 것으로 복합담체의 기공형성과 동시에 결합제로 이용되는 열가소성수지와 점결제 그리고 연속 기공형성 및 상기 흡착제와의 접촉을 증가시키는 수 용출성 탄산염을 포함하는 복합담체를 제조하여 종래기술의 문제점인 폐기공에 기인한 오염물질의 흡착력 저하 문제를 해결하면서, 제조공정을 단순화하고 오염물질의 유입 및 접촉을 원활하게 하는 미생물 서식환경에 적합한 성능이 우수한 오염물질 고도처리용 미생물 고정화 유·무기 복합 담체 및 이의 제조방법에 관한 것이다. The present invention is a composite comprising an inorganic adsorbent material and a melting point of less than 200 ℃ containing a thermoplastic resin and a binder used as a binder at the same time as the pore formation of the composite carrier and continuous pore formation and water-elutable carbonate to increase contact with the adsorbent By preparing a carrier, it solves the problem of lowering the adsorption power of contaminants due to the waste hole, which is a problem of the prior art, and has a high level of contaminant excellent performance for microbial habitat environment, which simplifies the manufacturing process and facilitates the inflow and contact of contaminants The present invention relates to a microorganism-immobilized organic-inorganic composite carrier for treatment and a method of manufacturing the same.
본 발명의 무기흡착소재는 다공성으로 평균입자의 크기가 1 ∼ 10 ㎛인 것으로, 예를 들면 실리카겔 분말, A형 제올라이트 분말, 비정질알루미나 분말 및 석탄계 또는 코코넛계 분말 활성탄에서 선택된 1종 또는 2종 이상을 사용한다. 실제로 상기 실리카겔, 제올라이트는 650 ℃ 이상의 온도에서는 그 결정구조가 파괴되어 흡착능 및 기공이 소멸되게 되고, 활성탄은 완전 산화되어 활성이 없어진다.The inorganic adsorption material of the present invention is porous and has an average particle size of 1 to 10 μm, for example, one or two or more selected from silica gel powder, A-type zeolite powder, amorphous alumina powder, and coal-based or coconut-based powdered activated carbon. Use In fact, the silica gel and the zeolite are destroyed at a temperature of 650 ℃ or more, the crystal structure is destroyed and the adsorption capacity and pores disappear, activated carbon is completely oxidized to lose the activity.
그러나 본 발명은 소성과정이 없어 상기와 같은 문제가 없이 우수한 흡착력을 그대로 이용할 수 있다. 상기의 무기흡착소재의 평균입자 크기가 1 ㎛ 미만이면 입자간에 브리지(bridge)가 형성되어 제조공정에서 원료의 이송이 곤란하고, 10 ㎛를 초과하는 경우에는 성형이 곤란한 문제가 발생한다. 이러한 상기 무기흡착제는 30 ∼ 78 중량% 사용하는데, 그 사용량이 30 중량% 미만이면 유기물 흡착능력이 감소하여 미생물의 부착이 곤란하고, 78 중량%를 초과하면 결합제로 작용하는 열가소성수지의 함량이 적어 담체의 기계적 강도가 감소하며, 물 속에서 담체가 붕괴되는 문제가 발생하게된다. However, the present invention does not have a calcination process can use the excellent adsorption power as it is without the above problems. If the average particle size of the inorganic adsorption material is less than 1 μm, a bridge is formed between the particles, which makes it difficult to transfer raw materials in the manufacturing process, and when the average particle size exceeds 10 μm, molding is difficult. The inorganic adsorbent is used in 30 to 78% by weight, when the amount is less than 30% by weight of the organic matter adsorption capacity is reduced and difficult to adhere microorganisms, when the content exceeds 78% by weight of the thermoplastic resin to act as a binder is less The mechanical strength of the carrier is reduced, causing the carrier to collapse in water.
또한 본 발명에서 융점이 200 ℃ 미만인 열가소성수지는 예를들면 폴리에틸렌 왁스를 사용한다. 상기 열가소성수지는 복합담체의 제조과정에서 용융되고 승화하여 담체 내부에 기공을 형성시킴과 동시에 결합제로 사용되며, 융점이 200 ℃를 초과할 경우 에너지 사용량이 증가되어 제조원가가 상승하고 제조시 악취가 발생할 뿐만아니라 발화의 위험이 뒤따른다. 상기 열가소성수지는 20 ∼ 68 중량% 사용하는데, 20 중량% 미만이면 기공의 형성이 어렵고 충분한 기계적 강도의 유지가 곤란하며, 68 중량% 초과할 경우에는 건조과정에서 담체가 서로 고착되어 담체의 제조가 곤란한 문제가 발생한다. In the present invention, the thermoplastic resin having a melting point of less than 200 ° C. uses polyethylene wax, for example. The thermoplastic resin melts and sublimes in the manufacturing process of the composite carrier to form pores in the carrier and is used as a binder.As the melting point exceeds 200 ° C., the energy consumption increases to increase the manufacturing cost and cause odor during manufacturing. In addition, there is a risk of ignition. The thermoplastic resin is used 20 to 68% by weight, less than 20% by weight is difficult to form pores and difficult to maintain sufficient mechanical strength, when the weight exceeds 68% by weight the carriers are fixed to each other in the drying process to produce a carrier Difficult problems arise.
본 발명의 점결제는 몬모릴로나이트계 점토를 사용하며 바람직하기로는 나트륨계 벤토나이트를 사용한다. 본 발명에서 사용된 나트륨계 벤토나이트는 성형시 가소성 및 점결성을 부여하여 원활한 성형체 제조를 가능하게 하고, 처리과정에서 양이온 교환제로 작용하여 오염물질을 화학 흡착하는 작용을 한다. 일반적으로 층간거리가 10 Å 정도되는 층상구조의 팽창성 나트륨계 벤토나이트는 500 ℃ 이상의 온도에서는 결정수의 이탈로 층 간 간격이 줄어들고 이후 다시는 늘어나지 않아 이온교환이 불가능하게 된다. 본 발명은 소성을 하지 않아 나트륨계 벤토나이트의 결정구조가 붕괴되지 않기 때문에 양이온교환 특성을 그대로 이용할 수 있는 장점이 있다. 이러한 상기 나트륨계 벤토나이트는 1 ∼ 10 중량%를 사용하며, 1 중량% 미만이면 성형이 불가능하고, 10 중량% 초과시에는 물 속에서 벤토나이트의 팽윤특성에 기인한 담체의 균열 및 붕괴 현상이 초래된다.The binder of the present invention uses montmorillonite clay and preferably sodium bentonite. The sodium bentonite used in the present invention provides plasticity and cohesiveness during molding to enable the production of a smooth molded body, and acts as a cation exchanger during the process to chemisorb contaminants. In general, the expandable sodium-based bentonite having a layered structure having a distance of about 10 Å is reduced at the temperature of 500 ° C. or higher due to the separation of the crystal water, and thus does not increase again, thus making ion exchange impossible. The present invention has the advantage that the cation exchange characteristics can be used as it is because the crystal structure of sodium bentonite does not collapse because it is not calcined. The sodium-based bentonite is used in the 1 ~ 10% by weight, if less than 1% by weight is impossible to form, when it exceeds 10% by weight cracking and collapse of the carrier due to the swelling characteristics of the bentonite in water.
본 발명에서 사용되는 수 용출성 탄산염은 알칼리 금속 및 알칼리 토금속중 선택된 것으로 예를들면 탄산일수소나트륨이 사용된다. 상기의 수 용출성 탄산염은 온수에서 탄산을 용출시켜 폐기공 간의 연결통로 역할을 하여 담체 내에 연속기공이 형성되게 하고, 오염물질과 담체에 포함된 무기흡착소재와의 접촉이 원활하도록 하는 작용을 하는데, 본 발명에서는 1 ∼ 20 중량%가 사용된다. 상기 사용량이 1 중량% 미만이면 온수 용출에 기인한 폐기공 간의 연결통로 역할을 하지 못하고, 20 중량% 초과시에는 탄산염의 완전한 용해가 곤란하며 탄산염의 과도한 확산저항에 기인한 담체 내부의 압력 증가로 담체가 붕괴되는 문제점이 있다. The water-elutable carbonate used in the present invention is selected from alkali metals and alkaline earth metals, for example sodium hydrogen carbonate. The water-elutable carbonate dissolves carbonic acid in hot water to serve as a connecting passage between the waste holes to form continuous pores in the carrier, and to facilitate contact between the pollutant and the inorganic adsorption material contained in the carrier. In the present invention, 1 to 20% by weight is used. If the amount is less than 1% by weight, it does not act as a connecting passage between the waste holes due to hot water elution, and when it exceeds 20% by weight, it is difficult to completely dissolve the carbonate, and the carrier is increased due to an increase in pressure inside the carrier due to excessive diffusion resistance of the carbonate. There is a problem that collapses.
한편 본 발명은 상기한 조성물을 이용한 유·무기 복합담체의 제조방법을 포함하는 바, 제조단계는 다음의 4 단계로 이루어진다.On the other hand, the present invention includes a method for producing an organic-inorganic composite carrier using the composition described above, the production step consists of the following four steps.
제 1 단계 과정은 무기흡착소재, 융점이 200 ℃ 미만인 열가소성수지, 점결제 및 수 용출성 탄산염을 물과 잘 혼합하여 적당한 가소성을 부여한 후 혼합성형 또는 압출성형으로 직경 2 ∼ 20 ㎜의 원통형이나 구형 또는 튜브형 1차 성형체를 제조한다. In the first step, the inorganic adsorbent material, the thermoplastic resin having a melting point of less than 200 ° C., the binder and the water-elutable carbonate are well mixed with water to impart proper plasticity, and then mixed or extruded into a cylindrical or spherical shape having a diameter of 2 to 20 mm. Or a tubular primary molded object is manufactured.
제 2 단계는 상기에서 제조한 1차 성형체를 열가소성수지 분말과 다시 혼합하여 2차 성형을 실시한다. 이는 성형체 표면에 무기재료분말 피막이 형성되어 기공 막힘 현상이 일어나기 때문에 이를 보완하여 표면기공을 많이 형성시키기 위한 것이다.In the second step, the primary molded body prepared above is mixed with the thermoplastic resin powder to perform secondary molding. This is because an inorganic material powder coating is formed on the surface of the molded body, so that pore clogging occurs to compensate for this, thereby forming a lot of surface pores.
제 3 단계는 상기의 2차 성형체를 강제통풍식 건조기에서 100 ∼ 150 ℃의 온도로 5 ∼ 10시간 건조하여 수분을 제거한 다음, 150 ∼ 200 ℃의 온도로 1 ∼ 7시간 처리함으로써 열가소성수지 분말이 용융되도록 하여, 성형체를 지지하는 결합제로 작용하게 한다. 상기의 연속적인 건조과정으로 열가소성수지분말 일부를 승화시켜 미생물의 서식환경에 적합한 직경 50 ∼ 1,000 ㎛ 크기의 기공이 형성되도록 하였다. In the third step, the secondary molded body is dried in a forced ventilation dryer at a temperature of 100 to 150 ° C. for 5 to 10 hours to remove moisture, and then treated with a temperature of 150 to 200 ° C. for 1 to 7 hours to obtain a thermoplastic resin powder. The melt is allowed to act as a binder for supporting the molded body. Subsequent sublimation of the thermoplastic resin powder by the continuous drying process to form pores having a diameter of 50 ~ 1,000 ㎛ suitable for the microbial habitat environment.
제 4 단계는 상기의 건조된 성형체를 냉각한 후 60 ∼ 100 ℃의 온수용액 내에서 1 ∼ 10시간 유지하여 탄산염을 용출 시킨 다음, 물로 수세하고 100 ∼ 120 ℃의 온도로 5 ∼ 20시간 건조시켰다. 상기 단계에서 온수에 담겨졌던 담체의 표면은 친수화 되어 유기물 흡착력은 증가하지만, 내마모도를 감소시키는 원인으로 작용하게 된다. 따라서 상기 재건조 과정을 도입하여 담체 표면에 열가소성수지의 미세한 피막을 형성시킴으로써 담체의 내 마모도를 증가시켰다. In the fourth step, the dried molded body is cooled and then maintained in a warm water solution at 60 to 100 ° C. for 1 to 10 hours to elute carbonate, washed with water, and dried at a temperature of 100 to 120 ° C. for 5 to 20 hours. . The surface of the carrier contained in the hot water in this step is hydrophilized to increase the organic adsorption power, but acts as a cause of reducing the wear resistance. Accordingly, the wear resistance of the carrier was increased by introducing the redrying process to form a fine film of the thermoplastic resin on the surface of the carrier.
이하, 본 발명을 다음의 실시예에 의하여 더욱 상세하게 설명하겠는 바, 본 발명이 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention.
실시예 1 ∼ 4Examples 1-4
1 단계 : 하기 표 1에 나타낸 조성의 원료를 쟁기형 고속혼합믹서에서 3분 동안 충분히 혼합하였다. 이 혼합분말에 사출에 적합한 정도의 물을 첨가하여 계속 혼합한 다음, 사출기(후지파우다사)에서 직경 7 mm의 원통형으로 사출하여 1차 성형체를 제조하였다. Step 1: The raw materials of the composition shown in Table 1 were sufficiently mixed in a plow type high speed mixer for 3 minutes. Water was added to the mixed powder to the extent suitable for injection and continued mixing, and then injected into a cylindrical shape with a diameter of 7 mm in an injection machine (Fuji Powder Co., Ltd.) to prepare a primary molded body.
2 단계 : 상기의 1차 성형체를 일정한 길이로 절단하고 끝 모서리 부분을 둥글게 하기 위해 회전원판 제환기(후지파우다사)에 넣고 1분간 회전시켰으며, 이 과정에서 담체 표면에 많은 기공을 형성시키기 위해 폴리에틸렌 왁스 분말을 상기 혼합분말의 5 중량% 첨가하고 혼합하여 2차 성형체를 제조하였다.Step 2: The above primary molded body was cut to a constant length and placed in a rotating disc changer (Fuji Powder Co., Ltd.) for 1 minute to round the end edge portion, and rotated for 1 minute. Polyethylene wax powder was added by 5% by weight of the mixed powder and mixed to prepare a secondary molded body.
3 단계 : 상기의 제조된 2차 성형체를 회분식 열풍건조기에 넣고 100 ℃로 5시간 건조하여 수분을 제거한 다음, 170 ℃로 5시간 건조하여 폴리에틸렌왁스 분말을 용융시키고 일부는 승화시켜 담체를 지지하는 결합제와 기공형성제로 작용하게 하였다. Step 3: Put the prepared secondary molded product in a batch hot air dryer to dry at 100 ℃ for 5 hours to remove water, and then dried at 170 ℃ for 5 hours to melt the polyethylene wax powder and sublimate some of the binder to support the carrier And pore-forming agent.
4 단계 : 상기의 건조된 성형체를 냉각하여 95 ℃의 온수에 5시간 침지하여 탄산일수소나트륨을 용출시킨 후 이를 물로 잘 수세한 다음, 회분식 열풍건조기에 다시 넣고 100 ℃ 온도로 12시간 건조하여 유기·무기 복합 담체의 제조를 완료하였다. 상기 제조된 유기·무기 복합 담체의 물리적 특성을 표 2에 나타내었다.Step 4: The dried molded body was cooled and immersed in hot water at 95 ° C. for 5 hours to elute sodium hydrogen carbonate, washed well with water, and then put back into a batch hot air dryer and dried at 100 ° C. for 12 hours to be organic. Preparation of the inorganic composite carrier was completed. Table 2 shows the physical properties of the organic-inorganic composite carrier prepared above.
비교예Comparative example
나트륨 벤토나이트 25 중량%, 제올라이트 4A 분말 25 중량%, 코코넛 활성탄 분말 15 중량%, 실리카겔 분말 10 중량%, 폴리에틸렌 왁스 분말 25 중량%를 실시예 1과 동일한 방법으로 혼합하고 성형하여, 60 ℃에서 12시간 건조한 다음, 회전식 로타리킬른에서 질소분위기를 유지하면서 700 ℃ 온도로 2시간 소성하여 세라믹 담체를 제조하였으며 이에 대한 물리적 특성은 표 2에 나타낸 바와 같다.25% by weight of sodium bentonite, 25% by weight of zeolite 4A powder, 15% by weight of coconut activated carbon powder, 10% by weight of silica gel powder, and 25% by weight of polyethylene wax powder were mixed and molded in the same manner as in Example 1, and 12 hours at 60 ° C. After drying, the ceramic carrier was prepared by firing at a temperature of 700 ° C. for 2 hours while maintaining a nitrogen atmosphere in a rotary rotary kiln, and physical properties thereof are shown in Table 2.
상기 표 2에서 나타난 바와 같이, 본 발명으로 제조된 유·무기 복합담체는 비교예의 세라믹 담체와 비교하여 물성에서는 큰 차이가 없었지만 도 4에서 보여지는 바와 같이 시간의 경과에 따른 미생물 고정화 능력은 세라믹 담체와 비교하여 매우 우수하였고, 미생물의 탈리현상이 발생하지 않는 장점이 있다. As shown in Table 2, the organic-inorganic composite carrier prepared by the present invention had no significant difference in physical properties compared to the ceramic carrier of the comparative example, but as shown in FIG. Compared with the very excellent, there is an advantage that does not occur desorption of microorganisms.
또한 실시예 4는 실시예 1의 조성으로 사출과정에서 직경을 10 mm로 하여 유·무기 복합담체를 제조한 것으로, 표 1의 물성 결과를 비교하면 그 차이가 없는 것으로 나타났다. 따라서 본 발명의 유·무기 복합담체의 물성과 그에 따른 효과는 담체의 직경과는 차이가 없었다. In addition, Example 4 is to prepare an organic-inorganic composite carrier having a diameter of 10 mm in the injection process with the composition of Example 1, it was found that there is no difference when comparing the results of the physical properties of Table 1. Therefore, the physical properties of the organic-inorganic composite carrier of the present invention and the effects thereof did not differ from the diameter of the carrier.
본 발명은 무기흡착소재와 융점이 200 ℃ 미만인 열가소성수지를 기본성분으로 하고, 점결제 및 수 용출성 탄산염을 이용하여 종래 제조공정에서의 발포과정과 소성과정을 없애고 건조공정만으로 미생물 담체를 제조함으로써, 제조공정의 단순화와 원가의 저렴화 뿐만아니라 흡착력을 증가시키고 개·폐기공을 연결하여 오염물질의 유입 및 접촉을 원활히 하고 미생물의 서식환경에 적합한 구조를 형성하는데 효과가 있다.The present invention is based on the inorganic adsorption material and the thermoplastic resin having a melting point of less than 200 ℃ as a base component, by eliminating the foaming process and the firing process in the conventional manufacturing process using a binder and a water-elutable carbonate, by producing a microorganism carrier only by drying In addition, it is effective to simplify the manufacturing process and reduce the cost, as well as to increase the adsorption power, to connect the open and closed pores to facilitate the inflow and contact of contaminants and to form a structure suitable for the microbial habitat environment.
도 1 은 본 발명의 유·무기 복합 담체의 제조공정도이다.1 is a manufacturing process chart of the organic-inorganic composite carrier of the present invention.
도 2 는 본 발명의 유·무기 복합 담체의 파단면을 조사한 전자현미경사진이다.2 is an electron micrograph of the fracture surface of the organic-inorganic composite carrier of the present invention.
도 3 은 본 발명의 실시예 1의 유·무기 복합 담체 및 비교예의 세라믹 담체를 이용하여 7일 동안 미생물 고정화 실험을 한 후, 복합 담체 표면의 미생물 고정화 상태(A)를 세라믹 담체(B)와 비교한 전자현미경 사진이다.3 is a microorganism immobilization experiment for 7 days using the organic-inorganic composite carrier of Example 1 of the present invention and the ceramic carrier of Comparative Example, and then the microorganism immobilization state (A) of the surface of the composite carrier is combined with the ceramic carrier (B). Comparison of electron micrographs.
도 4 는 본 발명의 실시예 1의 유·무기 복합 담체 및 비교예의 세라믹 담체를 이용하여 21일 동안 미생물 고정화 실험을 한 후, 복합 담체 표면의 미생물 고정화 상태(A)를 세라믹 담체(B)와 비교한 전자현미경 사진이다.4 is a microorganism immobilization experiment for 21 days using the organic-inorganic hybrid carrier and the ceramic carrier of Comparative Example 1 of the present invention, the microorganism immobilized state (A) of the surface of the composite carrier and the ceramic carrier (B) Comparison of electron micrographs.
도 5 는 본 발명의 실시예 1의 유·무기 복합 담체를 이용하여 21일 동안 미생물 고정화 실험을 한 후, 담체 내부(A) 및 측면(B)의 미생물 고정화 상태를 조사한 전자현미경 사진이다.5 is an electron micrograph of the microorganism immobilization state of the inside (A) and side (B) of the carrier after 21 days of the microorganism immobilization experiment using the organic-inorganic complex carrier of the present invention.
Claims (8)
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| KR102555248B1 (en) * | 2022-07-19 | 2023-07-14 | 주식회사 디에이치 | Wasterwater treatment apparatus Using Adulteration disposal equipment having a separating waste oil |
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| KR100912050B1 (en) * | 2008-02-13 | 2009-08-12 | 한양대학교 산학협력단 | Zeolite support for microorganism fixing and method for producing the same |
| KR101928628B1 (en) | 2016-11-04 | 2019-03-12 | 한국과학기술연구원 | Porous fluidized bed media and Method of manufacturing the same |
| KR102435314B1 (en) | 2022-01-10 | 2022-08-23 | 주식회사 디에이치 | Organic and inorganic hybrid media for microbe immobilization and process for preparing the same |
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