KR100342925B1 - Polyurethane sorbent for removing oil spills by adsorption and decomposition from water polluted by oil and a method for preparation thereof - Google Patents
Polyurethane sorbent for removing oil spills by adsorption and decomposition from water polluted by oil and a method for preparation thereof Download PDFInfo
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- KR100342925B1 KR100342925B1 KR1019990012955A KR19990012955A KR100342925B1 KR 100342925 B1 KR100342925 B1 KR 100342925B1 KR 1019990012955 A KR1019990012955 A KR 1019990012955A KR 19990012955 A KR19990012955 A KR 19990012955A KR 100342925 B1 KR100342925 B1 KR 100342925B1
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 68
- 239000004814 polyurethane Substances 0.000 title claims abstract description 68
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 26
- 238000002360 preparation method Methods 0.000 title claims description 22
- 238000001179 sorption measurement Methods 0.000 title abstract description 22
- 239000002594 sorbent Substances 0.000 title description 3
- 239000003463 adsorbent Substances 0.000 claims abstract description 68
- 229920002101 Chitin Polymers 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 21
- 229920000570 polyether Polymers 0.000 claims abstract description 21
- 238000005187 foaming Methods 0.000 claims abstract description 14
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 7
- 150000003077 polyols Chemical class 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims description 28
- 235000015097 nutrients Nutrition 0.000 claims description 17
- 229920005903 polyol mixture Polymers 0.000 claims description 15
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- 238000000465 moulding Methods 0.000 claims description 4
- 241000589291 Acinetobacter Species 0.000 claims description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000008213 purified water Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000012778 molding material Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 84
- 230000000052 comparative effect Effects 0.000 description 16
- 239000010779 crude oil Substances 0.000 description 10
- 239000013535 sea water Substances 0.000 description 10
- 239000006260 foam Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 240000000073 Achillea millefolium Species 0.000 description 3
- 235000007754 Achillea millefolium Nutrition 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000003100 immobilizing effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QXKAIJAYHKCRRA-JJYYJPOSSA-N D-arabinonic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C(O)=O QXKAIJAYHKCRRA-JJYYJPOSSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 101000578774 Homo sapiens MAP kinase-activated protein kinase 5 Proteins 0.000 description 2
- 102100028396 MAP kinase-activated protein kinase 5 Human genes 0.000 description 2
- 239000001888 Peptone Substances 0.000 description 2
- 108010080698 Peptones Proteins 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 229940041514 candida albicans extract Drugs 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 235000019319 peptone Nutrition 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000012138 yeast extract Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000186216 Corynebacterium Species 0.000 description 1
- 102100037114 Elongin-C Human genes 0.000 description 1
- 101001011859 Homo sapiens Elongin-A Proteins 0.000 description 1
- 101001011846 Homo sapiens Elongin-B Proteins 0.000 description 1
- 101000881731 Homo sapiens Elongin-C Proteins 0.000 description 1
- 101000836005 Homo sapiens S-phase kinase-associated protein 1 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 241000235013 Yarrowia Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002026 chloroform extract Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- -1 toluene Aromatic hydrocarbons Chemical class 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/341—Consortia of bacteria
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
-
- 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
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Polyurethanes Or Polyureas (AREA)
- Water Treatment By Sorption (AREA)
Abstract
본 발명은 유류에 의해 오염된 환경으로부터 유류를 흡착 및 분해를 통하여 제거하기 위한 폴리우레탄 흡착재 및 이것의 제조방법에 관한 것으로, 구체적으로는 유류화합물 분해균주를 키틴에 고정화 한 후, 이를 폴리에테르 폴리올 혼합액 H-20 및 카보디이미드 변형 D-페닐메탄 디이소시아네이트(Carbodiimide modify Diphenylmethane Diisocynate)D-10과 혼합하여 발포하는 방법에 의해 제조된 폴리우레탄 흡착재에 관한 것이다.The present invention relates to a polyurethane adsorbent for removing oil through adsorption and decomposition from an environment contaminated with oil, and to a method for preparing the same. Specifically, after fixing an oil compound decomposition strain to chitin, the polyether polyol The present invention relates to a polyurethane adsorbent prepared by a method of mixing and foaming a mixture H-20 and carbodiimide modified D-phenylmethane diisocynate D-10.
본 발명의 폴리우레탄 흡착재는 다량의 유류를 흡착할 수 있고, 유류를 흡착한 후에도 변형되거나 침전되지 않으며, 흡착된 유류가 균주에 의해 분해되고, 키틴에 의해 균주의 활성이 장시간 유지되므로, 생분해될 필요없이 반복적으로 유류제거에 사용될 수 있는 장점이 있다.The polyurethane adsorbent of the present invention can adsorb a large amount of oil, does not deform or precipitate even after adsorbing the oil, and since the adsorbed oil is decomposed by the strain and the activity of the strain is maintained by chitin for a long time, it is biodegradable. There is an advantage that can be used for oil removal repeatedly without need.
Description
본 발명은 유류에 의해 오염된 물로부터 유류를 흡착 및 분해를 통하여 제거하기 위한 폴리우레탄 흡착재 및 이것의 제조방법에 관한 것으로, 구체적으로 유류화합물 분해균주를 키틴에 고정화 한 후, 이를 폴리에테르 폴리올 혼합액 H-20 및 카보디이미드 변형 D-페닐메탄 디이소시아네이트(Carbodiimide modify Diphenylmethane Diisocynate) D-10과 혼합하여 발포하는 방법에 의해 제조된 폴리우레탄 흡착재에 관한 것이다.The present invention relates to a polyurethane adsorbent for removing oil from water contaminated with oil through adsorption and decomposition, and specifically to a method for preparing the polyurethane adsorbent. It relates to a polyurethane adsorbent prepared by mixing with H-20 and carbodiimide modify Diphenylmethane Diisocynate D-10 and foaming.
해양 등 개방된 물에 배출된 유류는 피막을 형성하여 산소가 물로 용해되는 것을 차단하며, 유류중의 비중과 점도가 높은 비휘발성 성분은 모래에 축적되어 생태학적 또는 환경학적 피해를 증가시키는 요인이 되므로(Atlas, Microb. Rev., 45, 180, 1981) 환경이나 생태계에 피해를 주기 전에 유류를 제거해야 한다.Oil discharged from open water such as the ocean forms a film to block oxygen from dissolving into water, and non-volatile components with high specific gravity and viscosity in oil accumulate in sand and increase ecological or environmental damage. (Atlas, Microb. Rev., 45, 180, 1981), the oil must be removed before harming the environment or ecosystem.
이러한 유류를 제거하는 방법으로는 유출된 유류를 직접 수집하는 방법, 유류를 분산 또는 중화시켜 제거하는 방법, 흡착재를 사용하는 방법 등이 있다.The oil may be removed by directly collecting the spilled oil, by dispersing or neutralizing the oil, or by using an adsorbent.
그러나, 직접 수거하거나 분산 또는 중화시켜 제거하는 방법은 유류 제거 효율이 낮은 문제점(International Tanker Owners Pollution Federation Ltd., 'Response to marine oil spills', pp. 123, 1987)이 있고, 흡착재를 사용하는 방법은 유류흡착량이 적고, 흡착재가 수거되기 전에 가라앉는 문제점이 있으며, 특히 폴리머폼(polymeric foam)이나 탄화수소계 흡착재를 사용하는 경우에는 생분해가 되지 않아 별도의 처리 공정이 더 요구되는 문제점이 있다(Schatzberg, 'investigation of sorbents for removing oil spills from water', Naval Ship Research and Development Center Report, Ref. No. 724110.1/2/1). 또한, 알진산이나 마이크로캡슐시스템(microcapsule system)과 같은 흡착재는 생분해는 되지만 유류 처리율이 만족스럽지 못한 문제점이 있다(Liet al., Seibutsu Kogaku, 72, 363, 1994; ibid, 73, 295, 1995; Murakamiet al., Hakko Kogaku, 63, 145, 1985).However, there is a problem of low oil removal efficiency (International Tanker Owners Pollution Federation Ltd., 'Response to marine oil spills', pp. 123, 1987). Silver has a small amount of oil adsorption, and there is a problem of sinking before the adsorbent is collected. Especially, when a polymer foam or a hydrocarbon-based adsorbent is used, there is a problem that a separate treatment process is required because it is not biodegradable (Schatzberg). , 'investigation of sorbents for removing oil spills from water', Naval Ship Research and Development Center Report, Ref.No. 724110.1 / 2/1). In addition, adsorbents such as alginic acid and microcapsule systems are biodegradable but have poor oil throughput (Li et al. , Seibutsu Kogaku, 72, 363, 1994; ibid, 73, 295, 1995). Murakami et al. , Hakko Kogaku, 63, 145, 1985).
이에, 본 발명자들은 상기한 문제점을 해결하기 위해서 많은 양의 유류를 흡착할 수 있고, 유류를 흡착한 다음 가라앉지 않으며, 장기간 사용하여도 변형되지 않는 흡착재를 검색하게 되었고, 그 결과 폴리우레탄을 흡착재로 선정하게 되었다.Accordingly, the present inventors have searched for an adsorbent that can adsorb a large amount of oil, and does not sink after absorbing the oil, and does not deform even after long-term use. Was selected.
그러나, 폴리우레탄 흡착재는 생분해되지 않는 흡착재이기 때문에, 이들을 별도로 처리해야하는 문제점이 여전히 존재하였다.However, since the polyurethane adsorbents are biodegradable adsorbents, there is still a problem of treating them separately.
따라서, 이를 해결할 수 있는 방법을 연구하게 되었고, 그 결과, 폴리우레탄 흡착재에 유류화합물 분해능이 있는 균주를 첨가시킨다면, 균주에 의해 흡착된 유류가 분해되므로 흡착재는 적절한 처리 후 반복적으로 사용할 수 있다는 것을 발견하고 본 발명을 완성하게 되었다.Therefore, a study was made to solve this problem. As a result, if a strain capable of decomposing oil compounds is added to the polyurethane adsorbent, the oil adsorbed by the strain is decomposed, so that the adsorbent can be used repeatedly after appropriate treatment. This invention was completed.
그러나, 유류화합물 분해균주를 첨가한 본 발명의 폴리우레탄 흡착재는 많은양의 유류를 흡착할 수 있고, 유류가 흡착한 후에도 변형 및 침전되지 않으며, 흡착된 유류가 균주에 의해 분해되므로 생분해될 필요없이 반복적으로 사용할 수 있는 장점은 있지만, 반복 사용으로 균주의 활성이 저하되고 따라서 유류분해능이 감소되는 문제점이 있다. 또한, 폴리우레탄의 제조에 있어서, 발포온도에 따라 균주의 활성이 영향을 받으며, 고정화 물질이나 미생물 영양제를 첨가하는 것에 의해 폴리우레탄의 발포가 잘 되지 않는 문제점도 있다.However, the polyurethane adsorbent of the present invention to which the oil compound decomposition strain is added can adsorb a large amount of oil, is not deformed and precipitated even after the oil is adsorbed, and since the adsorbed oil is decomposed by the strain, it does not need to be biodegraded. Although there is an advantage that can be used repeatedly, there is a problem that the activity of the strain is reduced by repeated use and thus the oil resolution is reduced. In addition, in the production of polyurethane, the activity of the strain is affected by the foaming temperature, there is also a problem that the foaming of the polyurethane is not well by adding an immobilization material or microbial nutrient.
이에, 본 발명자들은 상기한 문제점을 해결하기 위해서 연구한 결과, 키틴을 사용하여 균주를 고정화한 후, 이를 폴리우레탄 흡착재에 첨가하면, 균주의 활성을 장기간 유지할 수 있고, 저렴하게 폴리우레탄 흡착재를 제조할 수 있다는 것과, 폴리우레탄 흡착재의 재료로서, 폴리에테르 폴리올 혼합액 H-20과 카보디이미드 변형 D-페닐메탄 디이소시아네이트(Carbodiimide modify Diphenylmethane Diisocynate)D-10을 사용하고, 미생물의 성장에 필요한 영양염을 지속적으로 제공할 수 있는 영양제로서 419.7mg-N/제제g의 영양원을 함유하는 요소형 제제와 67.7mg-N/제제g과 50.4mg-P/제제g의 영양원을 함유하는 혼합형 제제를 함유하는 무기영양염 제제를 사용하여 발포를 실온에서 실시한다면 상기한 문제점이 해결될 수 있음을 발견하고 본 발명을 완성하게 되었다.Therefore, the present inventors have studied to solve the above problems, and as a result of immobilizing the strain using chitin, and then adding it to the polyurethane adsorbent, it is possible to maintain the activity of the strain for a long time, and to produce a polyurethane adsorbent inexpensively And the nutrients necessary for the growth of microorganisms by using polyether polyol mixture H-20 and carbodiimide modified D-phenylmethane diisocynate D-10 as the material of the polyurethane adsorbent. Inorganic formulations containing nutrients of 419.7 mg-N / g and nutrients of 67.7 mg-N / g and 50.4 mg-P / g It has been found that the above problems can be solved by carrying out foaming at room temperature using nutrient preparations and completed the present invention.
따라서, 본 발명의 목적은 유류에 의해 오염된 물로부터 유류를 흡착 및 분해를 통하여 제거하기 위한 폴리우레탄 흡착재의 제조방법을 제공하는 것이다.It is therefore an object of the present invention to provide a method for producing a polyurethane adsorbent for removing oil from water contaminated with oil through adsorption and decomposition.
본 발명의 또 다른 목적은 상기한 방법에 의해 제조된 폴리우레탄 흡착재를 제공하는 것이다.Still another object of the present invention is to provide a polyurethane absorbent produced by the above method.
상기한 본 발명의 목적, 그외의 목적, 특징 및 장점은 하기 발명의 상세한 설명으로부터 당업자에게 명백하게 드러날 것이다.The above and other objects, features and advantages of the present invention will become apparent to those skilled in the art from the following detailed description.
도 1은 본 발명의 폴리우레탄 흡착재의 주사 현미경 사진이다.1 is a scanning micrograph of the polyurethane adsorbent of the present invention.
도 2는 본 발명의 폴리우레탄 흡착재에 흡착된 유류의 방출량과 시간과의 관계를 나타내는 그래프이다.2 is a graph showing the relationship between the discharge amount of oil adsorbed on the polyurethane adsorbent of the present invention and time.
도 3은 폴리우레탄 흡착재의 모양에 따른 유류 흡착량(a) 및 물 흡착량(b)의 변화를 나타낸 그래프이다.3 is a graph showing changes in oil adsorption amount (a) and water adsorption amount (b) according to the shape of the polyurethane adsorbent.
◆: 큰 정육면체, ■: 작은 정육면체, □; 디스크형, ●: 나선형, ○: 띠형◆: large cube, ■: small cube, □; Disc-shaped, ●: Spiral, ○: Band-shaped
도 4는 유류의 농도에 따라 폴리우레탄 흡착재의 표면적: 무게 비율과 유류 흡착량과의 관계를 나타낸 그래프이다.4 is a graph showing the relationship between the surface area of the polyurethane adsorbent: weight ratio and the amount of oil adsorption according to the concentration of oil.
* 오일 농도* Oil concentration
■: 5, ●: 15, ○: 25, □: 30, △: 40■: 5, ●: 15, ○: 25, □: 30, △: 40
도 5는 폴리우레탄 흡착재로부터 수상으로 방출되는 균주수의 변화를 나타낸 그래프이다.5 is a graph showing a change in the number of strains released into the water phase from the polyurethane adsorbent.
■: 제조예 1, ●: 유리균주, ◆: 비교제조예 1, △: 비교제조예 2■: Production Example 1, ●: Glass strain, ◆: Comparative Production Example 1, Δ: Comparative Production Example 2
도 6은 유리균주와 폴리우레탄 흡착재를 제조한 직후의 유류(지방족 탄화수소(a), 방향족 탄화수소(b)) 분해율을 나타낸 그래프이다.Fig. 6 is a graph showing decomposition rates of oils (aliphatic hydrocarbons (a) and aromatic hydrocarbons (b)) immediately after the production of glass strains and polyurethane adsorbents.
■: 제조예 1, ●: 유리균주, ◆: 비교제조예 1, △: 비교제조예 2■: Production Example 1, ●: Glass strain, ◆: Comparative Production Example 1, Δ: Comparative Production Example 2
도 7은 균주를 고정화한 후, 폴리우레탄 흡착재의 분해능과 시간과의 관계를 나타내는 그래프이다.7 is a graph showing the relationship between the resolution of the polyurethane adsorbent and time after immobilization of the strain.
상기한 목적을 달성하기 위하여, 본 발명에 따른 폴리우레탄 흡착재의 제조방법은In order to achieve the above object, the production method of the polyurethane adsorbent according to the present invention
1) 유류화합물 분해균주 희석액을 제조하는 단계;1) preparing a dilution strain of an oil compound decomposition strain;
2) 상기 1)의 유류화합물 분해균주 희석액을 키틴분말에 분주한 후, 건조하여 유류화합물 분해균주를 키틴에 고정화하는 단계;2) dispensing the dilution of the oil compound decomposition strain of 1) to chitin powder, and then drying to fix the oil compound decomposition strain to chitin;
3) 폴리에테르 폴리올 혼합액 H-20에 상기 2)의 유류화합물 분해균주가 고정된 키틴을 30∼20:1의 무게비율로 혼합하는 단계;3) mixing the chitin in which the oil compound decomposition strain of 2) is fixed to the polyether polyol mixture H-20 at a weight ratio of 30 to 20: 1;
4) 상기 3)단계의 폴리에테르 폴리올 혼합액 H-20에 대하여 무기영양염 제제를 4 : 0.8∼1.0의 무게비율로 혼합하는 단계;4) mixing the inorganic nutrient salt preparation in a weight ratio of 4: 0.8 to 1.0 with respect to the polyether polyol mixture H-20 of step 3);
5) 상기 3)단계의 폴리에테르 폴리올 혼합액 H-20 중의 -OH기와 카보디이미드 변형 D-페닐메탄 디이소시아네이트(Carbodiimide modify Diphenylmethane Diisocynate)D-10 중의 -NCO기의 비율이 1.20∼2.6:1이 되도록 카보디이미드 변형 D-페닐메탄 디이소시아네이트 D-10을 혼합한 후, 25∼30℃ 온도에서 성형틀에 넣고 혼합하여 발포시키는 단계;5) The ratio of the -OH group and the -NCO group in the carbodiimide modify Diphenylmethane Diisocynate D-10 of the polyether polyol mixture H-20 of step 3) is 1.20 to 2.6: 1 Mixing carbodiimide modified D-phenylmethane diisocyanate D-10 as much as possible, and placing the mixture in a mold at 25 to 30 ° C. to foam;
를 포함하는 것을 특징으로 한다.Characterized in that it comprises a.
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 폴리우레탄 흡착재는 다량의 유류를 흡착할 수 있고, 유류를 흡착한 후에도 변형되거나 침전되지 않으며, 흡착된 유류가 균주에 의해 분해되고, 키틴에 의해 균주의 활성이 장시간 유지되므로, 적절한 처리 후 반복적으로 유류제거에 사용될 수 있다.The polyurethane adsorbent of the present invention can adsorb a large amount of oil, do not deform or precipitate even after adsorbing the oil, the adsorbed oil is decomposed by the strain, and the activity of the strain is maintained by chitin for a long time, so that the appropriate treatment It can then be used repeatedly for oil removal.
이하, 본 발명의 제조방법을 공정에 따라 자세히 설명하면 다음과 같다.Hereinafter, the manufacturing method of the present invention in detail according to the process as follows.
1) 유류화합물 분해균주 희석액을 제조하는 단계1) preparing a dilution solution of the oil compound decomposition strain
본 발명에서 사용된 유류 화합물 분해균주로는 시화호로부터 분리된야로위아 리폴리티카(Yarrowia lipolytica)CL180(KCTC 0533BP) 균주 단독 혹은 이 균주의 유류분해능을 향상시킬 수 있는 균주, 예를 들면,아시네토박터(Acinetobacter)속 US1(KCTC 8618P),스핑고모나스(Sphingomonas)속 KH3-2(KCTC 8815P),코리네박테리움 베리아빌리스(Corynebacterium varibilis)IC-10(KCTC 0533BP) 등을 혼합한 혼합균주를 사용할 수 있다.As the oil compound decomposition strain used in the present invention,Yarrowia lipolyticaCL180 (KCTC 0533BP) strain alone or a strain that can improve the oil resolution of the strain, for example,Acinetobacter(Acinetobacter)genus US1 (KCTC 8618P),Sphingomonas(Sphingomonas)Genus KH3-2 (KCTC 8815P),Corynebacterium varibilisMixed strains containing IC-10 (KCTC 0533BP) or the like can be used.
이 유류화합물 분해균주 희석액은 상기 유류화합물 분해균주를 YMG 배지(효모추출물 3g/ℓ, 맥아추출물 3g/ℓ, 펩톤 5g/ℓ 및 포도당 103g/ℓ을 증류수와 숙성해수가 1:1로 혼합된 용매에 용해시킨 배지, pH 7.0)에 접종하여 25℃의 온도에서 24시간 동안 배양한 후, 10,400×g에서 5분동안 원심분리하여 균주를 회수하고, 다시 회수된 균주를 1/10로 희석한 YMG 배지에 현탁하여 균주의 수가 3∼6×106CFU/㎖가 되도록 조절하는 방법에 의해 제조된다.The fuel Compounds strain diluent is the fuel Compounds strain YMG medium (yeast extract 3g / ℓ, malt extract, 3g / ℓ, peptone 5g / ℓ, and glucose 10 3 g / ℓ of 1 distilled water and aged seawater to: mix 1 Inoculated in a medium dissolved in a solvent, pH 7.0) and incubated for 24 hours at a temperature of 25 ℃, to recover the strain by centrifugation for 5 minutes at 10,400 × g, diluting the recovered strain to 1/10 It is prepared by the method of suspending in one YMG medium to adjust the number of strains to 3-6 × 10 6 CFU / ㎖.
2)유류화합물 분해균주 희석액을 키틴분말에 분주한 후, 건조하여 유류화합물 분해균주를 키틴에 고정하는 단계2) dissolving the dilution strain of oil compound decomposition strain into chitin powder, and then drying to fix the oil compound decomposition strain strain to chitin.
폴리우레탄 흡착재에 유류화합물 분해균주를 첨가하는 경우, 첨가 균주의 생존율을 높이고, 활성을 유지시키기 위해서는 동결건조 과정이 필요하다. 그러나, 동결건조에 의해 균주를 고정화하는 것은 비용이 많이 들고, 시간이 경과함에 따라고정화된 균주의 분해능이 크게 감소하는 문제점이 있다. 따라서, 본 발명에서는 유류화합물 분해균주를 키틴에 고정화하였다. 키틴을 이용하여 유류화합물을 보존하는 방법은 본 출원인이 개발한 방법으로서, 한국특허출원 제 1999-6302호(1999년 2월 25일 출원)로 특허출원한 바 있다.When adding the oil compound decomposition strain to the polyurethane adsorbent, a freeze-drying process is required to increase the survival rate of the added strain and maintain the activity. However, immobilizing the strain by lyophilization is expensive, and there is a problem in that the resolution of the immobilized strain is greatly reduced with time. Therefore, in the present invention, the oil compound decomposition strain was immobilized on chitin. A method for preserving oil compounds using chitin is a method developed by the present applicant and has been filed in Korean Patent Application No. 1999-6302 (filed February 25, 1999).
따라서, 본 발명에서는 유류화합물 분해균주 희석액을 키틴분말에 분주한 다음 15∼20℃에서 18∼30시간동안 건조하는 것에 의해 균주를 키틴에 고정시킨다. 이때, 유류화합물 분해균주 희석액은 키틴분말에 대하여 1.5배 이하의 양으로 분주하는 것이 바람직하다.Accordingly, in the present invention, the strain is fixed to the chitin by dispensing dilution of the oil compound decomposition strain to the chitin powder and then drying at 15 to 20 ° C. for 18 to 30 hours. At this time, the dilute solution of the oil compound decomposition strain is preferably dispensed in an amount of 1.5 times or less with respect to the chitin powder.
3) 폴리에테르 폴리올 혼합액 H-20에 유류화합물 분해균주가 고정된 키틴을 30∼20:1의 무게비율로 혼합하는 단계3) mixing chitin having the oil compound decomposition strain fixed in the polyether polyol mixture H-20 at a weight ratio of 30 to 20: 1.
일반적으로 폴리우레탄은 폴리에테르 폴리올 혼합액에 존재하는 -OH기와 D-메틸 디이소시아네이트에 존재하는 -NCO기의 중부가 반응에 의하여 제조되는 것으로, 통상적인 폴리우레탄의 제조에 사용되는 폴리에테르 폴리올 혼합액을 사용하여 고정화 물질을 첨가하는 경우에는 반응이 잘 이루어지지 않는다. 따라서, 본 발명에서는 89∼92의 폴리에테르 폴리올, 4∼5의 폴리에틸렌글리콜, 1∼1.4의 정제수, 1이하의 실리콘 계면활성제, 약 1정도의 아민 촉매류가 혼합된 폴리에테르폴리올 혼합액 H-20(이하, 'H-20'이라 한다)을 사용한다.Generally, polyurethane is prepared by the polyaddition reaction of -OH present in the polyether polyol mixture and -NCO group present in the D-methyl diisocyanate. When the addition of the immobilized material by using the reaction is not well done. Therefore, in the present invention, polyether polyol mixture H-20 containing 89 to 92 polyether polyol, 4 to 5 polyethylene glycol, 1 to 1.4 purified water, 1 or less silicone surfactant, and about 1 amine catalyst is mixed. (Hereinafter referred to as 'H-20').
H-20에 유류화합물 분해균주가 고정화된 키틴을 첨가할 때, 키틴의 첨가량은 발포가 방해되지 않는 범위내에서 첨가하는 것이 바람직하다. 즉, H-20에 대하여 키틴을 30∼20:1의 무게비율로 첨가하는 것이 바람직하다.When adding chitin which the oil compound decomposition strain is immobilized to H-20, it is preferable to add the amount of chitin in the range which does not prevent foaming. That is, it is preferable to add chitin at the weight ratio of 30-20: 1 with respect to H-20.
4) 상기 3)단계의 폴리에테르 폴리올 혼합액 H-20에 대하여 무기영양염 제제를 4 : 0.8∼1.0의 비율로 첨가하는 단계4) adding the inorganic nutrient salt formulation in the ratio of 4: 0.8 to 1.0 with respect to the polyether polyol mixture H-20 of step 3)
본 발명의 폴리우레탄 흡착재에서 유류화합물 분해균주를 고정화하는 경우, 균주의 성장을 위해서는 성장에 필요한 영양염(질소와 인)을 지속적으로 공급하여야 한다. 그러나, 첨가되는 영양제의 종류에 따라 폴리우레탄의 발포가 잘되지 않으므로, 본 발명에서는 419.7mg-N/제제g의 영양원을 함유하는 요소형 제제와 67.7mg-N/제제g과 50.4mg-P/제제g의 영양원을 함유하는 혼합형 제제를 함유하는 무기영양염 제제(이하, 'SRF'이라 한다.)를 사용한다. SRF의 첨가량은 발포가 방해되지 않는 범위내에서 첨가하는 것이 바람직하다. 즉, H-20에 대하여 SRF를 4:0.8∼1.0의 무게비율로 첨가하는 것이 바람직하다.When immobilizing the oil compound decomposition strain in the polyurethane adsorbent of the present invention, in order to grow the strain it is necessary to continuously supply nutrients (nitrogen and phosphorus) necessary for growth. However, since polyurethane is not foamed well according to the type of nutrient added, the present invention provides urea-type preparations containing 69.7 mg-N / g of nutrient and 67.7 mg-N / g and 50.4 mg-P /. An inorganic nutrient salt formulation (hereinafter referred to as 'SRF') containing a mixed formulation containing a nutrient of Formulation g is used. It is preferable to add the amount of SRF added within a range in which foaming is not hindered. That is, it is preferable to add SRF in the weight ratio of 4: 0.8-1.0 with respect to H-20.
5) H-20 중의 -OH기와 카보디이미드 변형 D-페닐메탄 디이소시아네이트 D-10 중의 -NCO기의 비율이 1.20∼2.6:1이 되도록 카보디이미드 변형 D-페닐메탄 디이소시아네이트 D-10을 혼합한 후, 25∼30℃ 온도에서 성형틀에 넣고 혼합하여 발포시키는 단계5) Carbodiimide modified D-phenylmethane diisocyanate D-10 so that the ratio of -OH group and -NCO group in carbodiimide modified D-phenylmethane diisocyanate D-10 in H-20 is 1.20 to 2.6: 1. After mixing, placing in a mold at a temperature of 25 ~ 30 ℃ mixed by foaming
본 발명의 폴리우레탄 흡착재의 제조시 H-20을 사용하는 것과 마찬가지로, 반응이 잘 되도록 하기 위하여 D-메틸 디이소시아네이트 대신에 변형 D-페닐메탄 디이소시아네이트(Modify Diphenylmethan Diisocyanate) 50이하와 D-페닐메탄 디이소시아네이트 50이상을 혼합한 카보디이미드 변형 D-페닐메탄 디이소시아네이트 D-10(이하, 'D-10'라 한다)을 사용한다.As in the case of using H-20 in the preparation of the polyurethane adsorbent of the present invention, in order to ensure the reaction, 50 or less modified D-phenylmethan diisocyanate and D-phenylmethane instead of D-methyl diisocyanate. Carbodiimide modified D-phenylmethane diisocyanate D-10 (hereinafter referred to as 'D-10') in which 50 or more diisocyanates are mixed is used.
한편, 일반적인 폴리우레탄의 경우 폴리에테르 폴리올 혼합액에 존재하는 -OH기와 D-메틸 디이소시아네이트 경화제에 존재하는 -NCO기의 비가 1:1.02가 되도록 폴리우레탄 폴리올 혼합액과 D-메틸 디이소시아네이트 경화제를 혼합하여 -OH기와 -NCO기가 완전히 가교결합된 중합체를 제조한다. 그러나, 본 발명에서는 완전한 가교 결합을 방지하고 팽윤성이 높은 폴리머 폼(polymeric foam)을 제조하여 흡유능을 극대화시켜야 하므로, D-10의 첨가량은 -OH기: -NCO기의 비가 1.20∼2.6:1.0이 되도록 첨가하는 것이 바람직하다.Meanwhile, in the case of general polyurethane, the polyurethane polyol mixture and the D-methyl diisocyanate curing agent are mixed so that the ratio of the -OH group present in the polyether polyol mixture solution and the -NCO group present in the D-methyl diisocyanate curing agent is 1: 1.02. A polymer is prepared in which -OH and -NCO groups are fully crosslinked. However, in the present invention, it is necessary to maximize the oil absorption capacity by preventing the complete crosslinking and preparing a high-swelling polymer foam, so that the amount of D-10 is -20 to 2.6: 1.0 ratio of -OH group to -NCO group. It is preferable to add so that it may become.
D-10를 첨가한 후, 원하는 모양의 성형틀에 넣고 혼합하여 발포시키는 것에 의해 본 발명의 폴리우레탄 흡착재를 제조한다. 한편, 발포는 발포온도가 높아지면 고정화된 균주의 활성이 저하되므로 25∼30℃에서 발포시키는 것이 바람직하다. 즉, 본 발명에서 사용하는 균주는 저온성 또는 중온성 균주로 높은 온도에 노출되면 활성이 저하되기 때문에, 활성이 최대로 유지될 수 있도록 25∼30℃에서 발포시키는 것이 바람직하다.After adding D-10, it puts into the shaping | molding die of a desired shape, mixes, and foams and manufactures the polyurethane adsorption material of this invention. On the other hand, the foaming is preferably foamed at 25 ~ 30 ℃ because the activity of the immobilized strain is reduced when the foaming temperature is increased. That is, the strain used in the present invention is a low-temperature or mesophilic strain, the activity is reduced when exposed to high temperature, it is preferable to foam at 25 ~ 30 ℃ so that the activity can be maintained to the maximum.
이하, 제조예 및 시험예를 들어 폴리우레탄 흡착재의 제조방법을 상세히 설명한다. 그러나, 본 발명이 이들 예에만 한정되는 것은 아니다.Hereinafter, the production method of the polyurethane adsorption material will be described in detail for production examples and test examples. However, the present invention is not limited only to these examples.
[제조예 1][Production Example 1]
1)야로위아 리폴리티카CL180(KCTC 0533BP)를 YMG 배지(효모추출물 3g/ℓ, 맥아추출물 3g/ℓ, 펩톤 5g/ℓ 및 포도당 103g/ℓ을 증류수와 숙성해수가 1:1로 혼합된 용매에 용해시킨 배지, pH 7.0)에 접종하여 25℃의 온도에서 24시간 동안 배양한 후, 10,400×g에서 5분동안 원심분리하여 균주를 회수하고, 다시 회수된 균주를 1/10로 희석한 YMG 배지에 현탁하여 5×106CFU/㎖가 되도록 조절하였다.1) Yarrow subtotal Li poly urticae CL180 (KCTC 0533BP), a YMG medium (yeast extract 3g / ℓ, malt extract, 3g / ℓ, peptone 5g / ℓ, and glucose 10 3 g / ℓ of a 1 distilled water and aged seawater: mix 1 Inoculated in a medium dissolved in a solvent, pH 7.0) and incubated for 24 hours at a temperature of 25 ℃, to recover the strain by centrifugation for 5 minutes at 10,400 × g, diluting the recovered strain to 1/10 Suspended in one YMG medium was adjusted to 5 × 10 6 CFU / ㎖.
2) 키틴분말과 상기 균주 희석액을 2:3의 비율로 혼합한 후, 20℃에서 24시간 동안 건조하여 균주를 키틴에 고정하였다.2) The chitin powder was mixed with the strain diluent at a ratio of 2: 3, and dried at 20 ° C. for 24 hours to fix the strain on chitin.
3) 상기 균주가 고정된 키틴과 폴리에테르 폴리올 혼합액 H-20(송원산업 제품)을 1: 20의 비율로 혼합하였다.3) The chitin and polyether polyol mixture solution H-20 (product of Songwon Industrial Co., Ltd.) fixed with the strain were mixed at a ratio of 1:20.
4) 상기 3)단계의 폴리에테르 폴리올 혼합액에 대하여 무기영양염 제제(SRF; 조비(주) 제품)를 4:1의 비율로 첨가하였다.4) An inorganic nutrient salt preparation (SRF; manufactured by Jobi Co., Ltd.) was added to the polyether polyol mixture solution of step 3) in a ratio of 4: 1.
5) 상기 폴리에테르 폴리올 혼합액 H-20 10중량부에 대하여 카보디이미드 변형 D-페닐메탄 디이소시아네이트 D-10(송원산업 제품) 2중량부를 27℃에서 나선형(0.5㎝×1㎝×30㎝) 성형틀에 넣고 혼합하여 발포시켜 폴리우레탄 흡착재를 제조하였다.5) 2 parts by weight of carbodiimide modified D-phenylmethane diisocyanate D-10 (produced by Songwon Industry) with respect to 10 parts by weight of the polyether polyol mixed solution H-20 (0.5 cm x 1 cm x 30 cm) Polyurethane adsorbent was prepared by mixing in a mold and foaming.
제조된 폴리우레탄 흡착재를 주사 현미경으로 분석한 결과, 제재 내부에 다량의 기공이 관찰되었으며, 기공의 크기는 약 80∼150㎛이었다(도 1).As a result of analyzing the prepared polyurethane adsorbent under a scanning microscope, a large amount of pores were observed inside the material, the pore size was about 80 ~ 150㎛ (Fig. 1).
[비교제조예 1][Comparative Production Example 1]
1) 폴리에테르 폴리올 혼합액 H-20(송원산업 제품) 10중량부에 대하여 카보디이미드 변형 D-페닐메탄 디이소시아네이트(송원산업 제품) 2중량부를 27℃에서 나선형(0.5㎝×1㎝×30㎝) 성형틀에 넣고 혼합하여 발포시켜 폴리우레탄 흡착재를 제조하였다.1) 2 parts by weight of carbodiimide modified D-phenylmethane diisocyanate (product of Songwon Industry) per 10 parts by weight of polyether polyol mixed solution H-20 (product of Songwon Industry) spiral (0.5 cm × 1 cm × 30 cm) at 27 ° C. Polyurethane adsorbent was prepared by mixing into a mold and foaming.
2) 제조된 폴리우레탄 흡착재에 상기 제조예 1의 균주 희석액(4.0×107CFU/g-흡착재)을 완전히 흡수시킨 후, 이것을 Lyph-lock 6(Labconco사 제품)을 사용하여 72시간동안 동결건조하여 흡착재를 제조하였다.2) After completely absorbing the strain dilution (4.0 × 10 7 CFU / g-adsorbent) of Preparation Example 1 to the prepared polyurethane adsorbent, it was lyophilized for 72 hours using Lyph-lock 6 (manufactured by Labconco) To prepare an adsorbent.
[비교제조예 2][Comparative Production Example 2]
1) 균주 희석액을 무기영양염 제제(SRF, 조비(주) 제품)에 2.95×107CFU/g-SRF로 첨가한 후, 20℃에서 24시간 동안 건조하여 SRF에 균주를 고정화하였다.1) The strain dilution was added to the inorganic nutrient salt preparation (SRF, manufactured by Jobi Co., Ltd.) at 2.95 × 10 7 CFU / g-SRF, and then dried at 20 ° C. for 24 hours to fix the strain on SRF.
2) 상기 균주가 고정화된 SRF와 폴리에테르 폴리올 혼합액 H-20(송원산업 제품)을 1: 4의 비율로 혼합하였다.2) The SRF immobilized with the strain was mixed with a polyether polyol mixture H-20 (from Songwon) at a ratio of 1: 4.
3) 상기 폴리에테르 폴리올 혼합액 H-20 10중량부에 대하여 카보디이미드 변형 D-페닐메탄 디이소시아네이트 D-10(송원산업 제품) 2중량부를 27℃에서 나선형(0.5㎝×1㎝×30㎝) 성형틀에 넣고 혼합하여 발포시켜 폴리우레탄 흡착재를 제조하였다.3) 2 parts by weight of carbodiimide modified D-phenylmethane diisocyanate D-10 (product of Songwon Industrial Co.) with respect to 10 parts by weight of the polyether polyol mixed solution H-20 (0.5 cm x 1 cm x 30 cm) Polyurethane adsorbent was prepared by mixing in a mold and foaming.
[시험예 1] 카보디이미드 변형 D-페닐메탄 디이소시아네이트 D-10의 첨가량에 따른 유류 흡착율의 변화[Test Example 1] Change in oil adsorption rate according to the amount of carbodiimide modified D-phenylmethane diisocyanate D-10
카보디이미드 변형 D-페닐메탄 디이소시아네이트 D-10의 첨가량을 3∼7중량부로 변화시켜 -OH기와 -NCO기의 당량비를 2.40∼0.69:1로 변화시킨다는 것을 제외하고는 제조예 1과 동일한 방법으로 폴리우레탄 흡착재를 제조하였다.The same method as in Preparation Example 1, except that the amount of carbodiimide-modified D-phenylmethane diisocyanate D-10 was changed to 3 to 7 parts by weight to change the equivalent ratio of -OH and -NCO groups to 2.40 to 0.96: 1. To prepare a polyurethane adsorbent.
상기 폴리우레탄 흡착재 각각을 숙성해수 100㎖, 아라비안산 원유 1g, 또는 이들의 혼합액을 첨가한 비이커에 1시간 동안 부유시킨 후, 폴리우레탄 흡착재를 회수하여 물과 유류를 흡수하기 전과 후의 무게를 측정하여 흡수된 물과 유류의 무게를 측정하였다.Each of the polyurethane adsorbents was suspended in a beaker to which 100 ml of aged seawater, 1 g of arabian acid crude oil, or a mixture thereof was added for 1 hour, and then the polyurethane adsorbents were recovered to measure the weight before and after absorbing water and oil. The weight of water and oil absorbed was measured.
여기서, 폴리우레탄 흡착재에 흡착된 유류의 양은 클로로포름을 수차 반복하여 가하여 유류를 추출한 다음, 이를 증발시킴으로써 클로로포름이 제거된 순수한 유류를 얻고, 그 무게를 측정하는 방법으로 측정하고, 흡수된 물의 양은 폴리우레탄 흡착재 초기 무게에서 흡착된 유류의 양을 뺀 값으로 산출하였다. 각각의 폴리우레탄 흡착재에 대하여 동일 실험을 1회 더 실시한 후, 그 평균값을 표 1에 나타내었다.Here, the amount of oil adsorbed to the polyurethane adsorbent is extracted by repeatedly adding chloroform several times, and then evaporated to obtain pure oil from which chloroform has been removed, and the weight of the absorbed water is measured by measuring the weight of polyurethane. The initial weight of the adsorbent was calculated by subtracting the amount of oil adsorbed. After the same experiment was performed once more for each polyurethane adsorbent, the average value is shown in Table 1.
상기 표 1에서 알 수 있는 바와 같이, 사용된 D-10의 양이 증가함에 따라 유류나 물의 흡착율이 감소하는 것으로 보아 발포가능한 범위내에서 D-10의 비가 최저일 때, 결국 최소의 가교결합을 포함하는 폴리머폼의 흡유능이 우수하다는 것을 알 수 있다. 따라서, 흡유능을 극대화시키기 위해서는 반응에 관여하지 않는 자유-OH기가 존재하도록 -OH기: -NCO기가 1.20∼2.6:1.0의 비율이 되도록 D-10을 첨가하는 것이 바람직한다.As can be seen in Table 1, as the amount of D-10 used increases, the adsorption rate of oil or water decreases, so that when the ratio of D-10 is the lowest within the foamable range, a minimum crosslinking is achieved. It can be seen that the oil absorption ability of the polymer foam is excellent. Therefore, in order to maximize the oil absorption ability, it is preferable to add D-10 such that a -OH group: -NCO group is in a ratio of 1.20 to 2.6: 1.0 so that a free-OH group does not participate in the reaction.
[시험예 2][Test Example 2]
제조예 1의 폴리우레탄 흡착재에 아라비안산 원유를 5g/g-흡착재의 비율로 흡착시킨 후, 해수에 10일 동안 부유시켰을 때, 해수로 방출되는 원유의 양을 시험예 1과 동일한 방법으로 측정하여 그 결과를 도 2에 나타내었다.After adsorbing arabic acid crude oil at the ratio of 5g / g-adsorbent to the polyurethane adsorbent of Preparation Example 1 and suspending it in seawater for 10 days, the amount of crude oil released into the seawater was measured in the same manner as in Test Example 1 The results are shown in FIG.
도 2로부터, 해수로 방출되는 원유의 양은 폴리우레탄 흡착재에 흡착된 원유의 양의 5이하였으며, 방출된 기름의 양은 시간에 따라 증가하지 않는다는 것을 알 수 있다. 즉, 본 발명의 폴리우레탄 흡착재는 오염수계로부터 유류를 흡착한 후, 이를 다시 수계로 방출하는 양이 매우 적으므로, 유류를 효과적으로 제거할 수 있음을 알 수 있다.From Figure 2, it can be seen that the amount of crude oil discharged into the seawater is less than 5 of the crude oil adsorbed to the polyurethane adsorbent, and the amount of released oil does not increase with time. That is, since the polyurethane adsorbent of the present invention adsorbs oil from the contaminated water system and then releases it back into the water system, it can be seen that the oil can be effectively removed.
한편, 원유가 흡착된 폴리우레탄 흡착재를 해수를 첨가한 비이커에 넣고, 교반하며 6개월 동안 관찰한 결과, 폴리우레탄 흡착재의 외형적 변화를 관찰할 수 없었으며, 그 부유능 또한 감소하지 않았다.On the other hand, the crude oil-adsorbed polyurethane adsorbent was placed in a beaker with seawater, and stirred for 6 months. As a result, the external appearance of the polyurethane adsorbent could not be observed, and its floating capacity did not decrease.
[시험예 3][Test Example 3]
폴리우레탄 흡착재의 표면적에 따른 흡착량을 측정하기 위하여, 하기 모양을 갖는 성형틀을 사용하여, 제조예 1과 동일한 방법으로 폴리우레탄 흡착재를 제조하였다.In order to measure the adsorption amount according to the surface area of a polyurethane adsorption material, the polyurethane adsorption material was manufactured by the same method as the manufacture example 1 using the molding die which has the following shape.
·큰 정육면체: 2㎝×2㎝×2㎝ ·작은 정육면체: 1㎝×1㎝×1㎝Large cube: 2 cm × 2 cm × 2 cm Small cube: 1 cm × 1 cm × 1 cm
·띠 모양: 0.5㎝×0.5㎝×6㎝ ·디스크형: 직경 5㎝× 높이 0.5㎝Strip shape: 0.5 cm x 0.5 cm x 6 cm Disk type: Diameter 5 cm x Height 0.5 cm
숙성 해수 100부에 대하여 아라비안 원유를 0에서 100부까지 변화시킨 비이커에 제조예 1 및 상기한 폴리우레탄 흡착재들을 1시간 동안 부유시킨 다음, 원유 첨가량에 따른 흡착재 1g당 흡착되는 유류 흡착량(a) 및 물 흡착량(b)를 측정하고, 그 결과를 도 3에 나타내었다.Production Example 1 and the above-mentioned polyurethane adsorbents were suspended for 1 hour in a beaker in which the Arabian crude oil was changed from 0 to 100 parts with respect to 100 parts of aged seawater, and the amount of oil adsorbed per 1 g of adsorbent according to the amount of crude oil added (a) And the amount of water adsorption (b) were measured and the results are shown in FIG. 3.
도 3에서 알 수 있는 바와 같이, 원유의 양이 3에서 30까지 증가할 때 모든 폴리우레탄 흡착재의 유류 흡착량은 직선적으로 증가하다가, 7∼9g oil/g 흡착재로 포화되었다. 동일시료에서 흡수된 물의 양은 첨가된 원유의 양이 증가할 수 록 감소하는 양상을 나타낸다. 따라서, 본 발명의 폴리우레탄 흡착재는 유류로 오염된 수계에서 유류를 효과적으로 흡착할 수 있다는 것을 알 수 있다.As can be seen in Figure 3, when the amount of crude oil increased from 3 to 30, the oil adsorption amount of all the polyurethane adsorbents linearly increased, then saturated with 7 to 9 g oil / g adsorbent. The amount of water absorbed in the same sample decreases as the amount of crude oil added increases. Therefore, it can be seen that the polyurethane adsorbent of the present invention can effectively adsorb oil in an oil contaminated water system.
한편, 제조예 1과 상기한 폴리우레탄 흡착재들의 표면적:무게의 비율과 유류흡착량과의 관계를 보면, 도 4에서 알 수 있는 바와 같이, 표면적:무게 비율이 증가함에 따라 유류의 흡착량이 증가한다는 것을 알 수 있다. 따라서, 폴리우레탄 흡착재는 표면적이 가장 넓은 형태로 제조하는 것이 바람직하다.On the other hand, when looking at the relationship between the surface area: weight ratio and the oil adsorption amount of the manufacturing example 1 and the above-mentioned polyurethane adsorbents, as shown in Figure 4, the adsorption amount of oil increases as the surface area: weight ratio is increased It can be seen that. Therefore, it is preferable to prepare a polyurethane adsorbent in the form with the largest surface area.
[시험예 4][Test Example 4]
폴리우레탄 흡착재에 고정화된 균주는 오염된 수계에 노출되었을 때 수층으로 방출된다. 이는 고정화방법의 불안정성외에도 유류의 분해에 관여하는 균주의 수가 감소되어 분해능이 저하될 수 있음을 의미한다. 따라서, 가능한 한 최소한의 균주가 수층으로 방출되어야 한다. 이에, 수층으로 방출되는 균주의 수를 하기 방법으로 측정한다. 즉, 숙성해수 100㎖에 아라비안 원유 1g을 첨가한 비이커에 제조예 1, 비교제조예 1, 비교제조예 2의 폴리우레탄 흡착재 및야로위아 리폴리티카CL180(KCTC 0533BP) 균주 1.5×107CFU/㎖를 첨가한 후, 5일 동안 수층으로 유출되는 균주의 수를 계수한다. 균주의 계수는 비이커로부터 시료를 채취한 후, 적절히 희석하여 YMG배지에 도말한 다음, 30℃에서 3일 동안 배양하여 형성된 콜로니의 수를 측정한다. 그 결과는 도 5와 같다.Strains immobilized on polyurethane adsorbents are released into the aqueous layer when exposed to contaminated water. This means that in addition to the instability of the immobilization method, the number of strains involved in the degradation of oil can be reduced, thereby reducing the resolution. Therefore, as few strains as possible should be released into the aqueous layer. Thus, the number of strains released into the aqueous layer is measured by the following method. That is, manufacturing in a beaker by the addition of Arabian crude oil 1g in aged seawater 100㎖ Example 1, Comparative Preparation 1 and Comparative Preparation Example 2 Polyurethane adsorbent and Yarrow subtotal Li poly urticae CL180 (KCTC 0533BP) strain of 1.5 × 10 7 CFU / After the addition of ml, the number of strains flowing into the aqueous layer for 5 days is counted. The count of the strain is obtained by taking a sample from the beaker, diluted appropriately, plated on YMG medium, and then cultured at 30 ° C. for 3 days to measure the number of colonies formed. The result is shown in FIG.
도 5로부터, 유리균주의 경우, 균주에 의해 유류가 분해되는 기간(5일)동안 뚜렷한 증가 양상을 보이지 않고, 일정한 수준으로 유지되는 양상을 보였지만, 고정화된 균주의 경우에는, 시간이 경과할수록 수층으로 유출되는 균주의 수가 증가하는 양상을 나타내었다. 그러나, 유출되는 균주의 수는 1미만이며, 특히 키틴에 고정화한 제조예 1의 경우, 유출되는 균주의 수가 매우 적음을 알 수 있다.From Figure 5, in the case of the free strain, the oil was degraded by the strain (5 days) did not show a significant increase, but maintained a constant level, in the case of the immobilized strain, the water layer as time passes The number of strains leaked out was increased. However, the number of outflow strains is less than one, and especially in Preparation Example 1 immobilized on chitin, it can be seen that the number of outflow strains is very small.
[시험예 5][Test Example 5]
제조예 1, 비교제조예 1 및 비교제조예 2의 흡착재를 제조한 직 후 이들 흡착재와,야로위아 리폴리티카CL180(KCTC 0533BP) 균주의 유류분해능을 TLC/FID분석법(Gotoet al., J. Mar. Biotech., 2, 45, 1994)을 이용하여 측정하고, 그 결과를 도 6에 나타내었다. 즉, 숙성해수 50㎖와 아라비안산 원유 0.1g을 첨가한 비이커에 각각의 흡착재 1,825±0.25g를 첨가하여 200rpm, 25℃에서 5일간 진탕시킨 후, 스테아린산을 1.25g/ℓ가 되도록 첨가하였다. 그 다음, 100㎖의 클로로포름으로 유류를 추출하였다. 클로로포름 추출물 1㎕를 TLC/FID용 전개 유리막대 Chomarod Ⅲ(SⅢ, Iatron Lab. Inc., Japan)에 로딩한 후, n-헥산을 전개용매로 하여 지방족 탄화수소를 분리하고, n-헥산:톨루엔이 1:4의 비로 혼합된 혼합액을 전개용매로 하여 방향족 탄화수소를 분리한 다음, 염화메틸렌:메탄올이 19:1의 비로 혼합된 혼합액을 전개용매로 하여 레진을 분리한 후, 분리된 지방족 탄화수소, 방향족 탄화수소, 레진 및 아스팔텐(asphaltene)을 이야트로스캔 MK-5(Iatroscan MK-5; Iatron Lab. Inc., 일본)를 사용하여 스캐닝하여 상대면적을 계산하였다. 이때 캐리어 기체로서 수소를 160㎖/분으로 흘려주었다.Preparation Example 1, Comparative Production Example 1 and Comparative immediately after the manufacture of the sorbent material of Preparation Example 2 The adsorbent and, Yarrow subtotal Li poly urticae CL180 (KCTC 0533BP) of oil resolution TLC / FID analysis of the strain (Goto et al., J Mar. Biotech., 2, 45, 1994) and the results are shown in FIG. That is, 1,825 ± 0.25 g of each adsorbent was added to a beaker to which 50 ml of aged seawater and 0.1 g of arabic acid were added, shaken at 200 rpm and 25 ° C. for 5 days, and then stearic acid was added to 1.25 g / L. The oil was then extracted with 100 ml of chloroform. 1 μl of chloroform extract was loaded on a developing glass rod Chomarod III (SIII, Iatron Lab. Inc., Japan) for TLC / FID, and aliphatic hydrocarbons were separated using n-hexane as a developing solvent, and n-hexane: toluene Aromatic hydrocarbons were separated using a mixed solution mixed at a ratio of 1: 4 as a developing solvent, and resins were separated using a mixed solution mixed with a methylene chloride: methanol ratio at a ratio of 19: 1, and then separated aliphatic hydrocarbons and aromatics were used. Hydrocarbons, resins and asphaltenes were scanned using Iyatroscan MK-5 (Iatroscan MK-5; Iatron Lab. Inc., Japan) to calculate the relative area. At this time, hydrogen was flowed at 160 ml / min as a carrier gas.
도 6으로부터, 유리균주나 고정화된 균주 모두 폴리우레탄 흡착재를 제조한 직후에는 유류분해능에 있어서 현저한 차이가 없는 것으로 나타났다. 따라서, 고정화방법들은 균주의 활성에 영향을 미치지 않는 다는 것을 알 수 있다From Fig. 6, both glass strains and immobilized strains showed no significant difference in oil resolution immediately after preparing the polyurethane adsorbent. Therefore, it can be seen that the immobilization methods do not affect the activity of the strain.
또한, 제조예 1, 비교제조예 1 및 비교제조예 2의 흡착재를 15일, 1개월, 2개월 동안 보관한 후 이들 흡착재의 유류분해능을 상기에서와 동일한 방법으로 측정하고, 그 결과를 표 2 및 도 7에 나타내었다.In addition, after storing the adsorbents of Preparation Example 1, Comparative Preparation Example 1 and Comparative Preparation Example 2 for 15 days, 1 month, 2 months, the oil resolution of these adsorbents was measured by the same method as above, and the results are shown in Table 2 And FIG. 7.
상기 표 2 및 도 7로부터, SRF에 고정화한 비교제조예 2의 경우 15일이 지난후에는 분해능이 급격히 감소하여 초기 분해능의 53를 나타내었고, 동결건조한 비교제조예 1의 경우에는 15일 후에는 초기 분해능의 75를 나타내었으나, 2달이 지난후에는 초기분해능의 20를 유지하였다. 반면, 키틴에 고정화한 제조예 1은 15일이 지난후에는 초기 분해능의 89, 2개월이 지난 후에는 76를 유지하므로, 키틴에 고정화한 균주를 이용한 본 발명의 폴리우레탄 흡착재는 장시간 동안 균주의 유류분해능이 유지되므로, 적절한 처리후 반복사용이 가능하다.From Table 2 and FIG. 7, in case of Comparative Production Example 2 immobilized on SRF, resolution decreased rapidly after 15 days, and 53 of initial resolution was shown, and in case of Comparative Preparation Example 1 lyophilized, after 15 days The initial resolution of 75 was shown, but after 2 months, the initial resolution of 20 was maintained. On the other hand, Preparation Example 1 immobilized on chitin retained 89 after 2 days of initial resolution after 76 days, and therefore, the polyurethane adsorption material of the present invention using a strain immobilized on chitin was used for a long time. Since oil resolution is maintained, it can be used repeatedly after appropriate treatment.
이상에서 설명한 바와 같이, 본 발명의 폴리우레탄 흡착재는 유류에 대한 흡착능이 우수하고, 흡착된 유류에 대한 분해능 또한 우수하며, 아울러 분해능이 장시간 동안 유지되므로, 효과적으로 유류에 의해 오염된 물로부터 유류를 제거할 수 있다.As described above, the polyurethane adsorbent of the present invention has excellent adsorption capacity for oil, excellent resolution for adsorbed oil, and also maintains resolution for a long time, thus effectively removing oil from water contaminated by oil. can do.
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| US8034605B2 (en) | 2003-03-26 | 2011-10-11 | Kyu-Jin Yum | Microbial materials for degradation of oils and toxic chemicals |
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| KR920701053A (en) * | 1989-04-10 | 1992-08-11 | 제라드 피. 루우니 | How to remove organic contaminants from wastewater |
| US5342525A (en) * | 1991-10-28 | 1994-08-30 | Rowsell Farrell D | Method for aiding microbial degradation of spilled oil |
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| KR20000003149A (en) * | 1998-06-26 | 2000-01-15 | 이정일 | Method for manufacturing microbe seed for processing sewage and waste water fixed on nontoxic natural carrier |
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| KR850001529A (en) * | 1983-08-10 | 1985-03-30 | 칼 에이·쿠즈바취 | Method of Fixing Biocatalyst |
| KR920701053A (en) * | 1989-04-10 | 1992-08-11 | 제라드 피. 루우니 | How to remove organic contaminants from wastewater |
| US5342525A (en) * | 1991-10-28 | 1994-08-30 | Rowsell Farrell D | Method for aiding microbial degradation of spilled oil |
| JPH07222988A (en) * | 1994-02-15 | 1995-08-22 | Shikoku Chem Corp | Waste water treatment method |
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