KR101071924B1 - Transition metal oxidation catalytic membrane having a multi-porous structure and method for the preparation thereof - Google Patents
Transition metal oxidation catalytic membrane having a multi-porous structure and method for the preparation thereof Download PDFInfo
- Publication number
- KR101071924B1 KR101071924B1 KR1020080114066A KR20080114066A KR101071924B1 KR 101071924 B1 KR101071924 B1 KR 101071924B1 KR 1020080114066 A KR1020080114066 A KR 1020080114066A KR 20080114066 A KR20080114066 A KR 20080114066A KR 101071924 B1 KR101071924 B1 KR 101071924B1
- Authority
- KR
- South Korea
- Prior art keywords
- transition metal
- bis
- metal oxide
- oxide catalyst
- porous
- Prior art date
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- 230000003197 catalytic effect Effects 0.000 title description 2
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- 229920005610 lignin Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
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- 229910021645 metal ion Chemical group 0.000 description 1
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- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- WDVUXWDZTPZIIE-UHFFFAOYSA-N trichloro(2-trichlorosilylethyl)silane Chemical compound Cl[Si](Cl)(Cl)CC[Si](Cl)(Cl)Cl WDVUXWDZTPZIIE-UHFFFAOYSA-N 0.000 description 1
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical group Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 1
- YKTYNRWYBYKDGI-UHFFFAOYSA-N triethoxy-(4-triethoxysilylphenyl)silane Chemical compound C(C)O[Si](C1=CC=C(C=C1)[Si](OCC)(OCC)OCC)(OCC)OCC.C(C)O[Si](C1=CC=C(C=C1)[Si](OCC)(OCC)OCC)(OCC)OCC YKTYNRWYBYKDGI-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ADBMSVFHVFJBFR-UHFFFAOYSA-N triethyl(hexadecyl)azanium Chemical class CCCCCCCCCCCCCCCC[N+](CC)(CC)CC ADBMSVFHVFJBFR-UHFFFAOYSA-N 0.000 description 1
- CENIAFYRIODGSU-UHFFFAOYSA-N triethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](CC)(CC)CC CENIAFYRIODGSU-UHFFFAOYSA-N 0.000 description 1
- JXCCIZBMTUFJKN-UHFFFAOYSA-N triethyl(tetradecyl)azanium Chemical class CCCCCCCCCCCCCC[N+](CC)(CC)CC JXCCIZBMTUFJKN-UHFFFAOYSA-N 0.000 description 1
- IEDVJHCEMCRBQM-UHFFFAOYSA-N trimethoprim Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 IEDVJHCEMCRBQM-UHFFFAOYSA-N 0.000 description 1
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- DJYGUVIGOGFJOF-UHFFFAOYSA-N trimethoxy(trimethoxysilylmethyl)silane Chemical compound CO[Si](OC)(OC)C[Si](OC)(OC)OC DJYGUVIGOGFJOF-UHFFFAOYSA-N 0.000 description 1
- YYAXLPWVTZHBFC-UHFFFAOYSA-N trimethoxy-(5-trimethoxysilylthiophen-2-yl)silane Chemical compound CO[Si](OC)(OC)C1=CC=C([Si](OC)(OC)OC)S1 YYAXLPWVTZHBFC-UHFFFAOYSA-N 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical class CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 description 1
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Abstract
본 발명은 다공성 전이금속 산화촉매 분리막 및 이의 제조방법에 관한 것으로, 구체적으로 1) 나노구조 주형으로서 블록공중합체, 계면활성제, 유기고분자 및 이들의 혼합물 중의 어느 하나, 1종 이상의 전이금속 화합물, 및/또는 실리카 전구체를 상온에서 용매에 혼합하는 단계; 2) 상기 혼합물을 판상 또는 중공사 분리막 형태의 틀에 채운 후 이로부터 용매를 제거하여 나노구조를 형성하고 그 구조 내에 전이금속 및/또는 실리카를 담지시키는 단계; 및 3) 상기 혼합물을 150 내지 1,000℃의 온도에서 1 내지 24시간 동안 소결하여 나노구조 주형을 제거하는 단계에 의해 제조되는 다공성 전이금속 산화촉매 분리막 및 이의 제조방법에 관한 것이다. 본 발명에 따른 다공성 전이금속 산화촉매 분리막은 다양한 크기의 다중 기공구조를 가져 비표면적이 매우 크고 산화효율이 우수할 뿐만 아니라 연속공정으로의 처리가 가능하여 폐수, 특히 난분해성 유기물을 함유한 폐수의 처리에 유용하게 사용될 수 있다.The present invention relates to a porous transition metal oxide catalyst separation membrane and a method for preparing the same, and specifically, 1) any one of block copolymers, surfactants, organic polymers, and mixtures thereof, one or more transition metal compounds as nanostructure templates, and Mixing the silica precursor with the solvent at room temperature; 2) filling the mixture into a mold in the form of a plate or hollow fiber membrane and then removing the solvent therefrom to form a nanostructure and supporting the transition metal and / or silica in the structure; And 3) a porous transition metal oxide catalyst membrane prepared by sintering the mixture at a temperature of 150 to 1,000 ° C. for 1 to 24 hours to remove the nanostructure template, and a method for preparing the same. The porous transition metal oxide catalyst separation membrane according to the present invention has a multi-pore structure of various sizes, has a very large specific surface area and excellent oxidation efficiency, and can be treated in a continuous process to treat wastewater, particularly wastewater containing hardly decomposable organic matter. It can be usefully used for processing.
전이금속, 산화촉매 분리막, 난분해성 유기물, 폐수처리, 나노구조 주형, 다공성 기공구조 Transition Metals, Oxidation Catalyst Separators, Refractory Organics, Wastewater Treatment, Nanostructured Templates, Porous Pore Structures
Description
본 발명은 블록공중합체, 계면활성제, 유기고분자 및 이들의 혼합물을 나노구조 주형으로 사용하여 제조된 다양한 크기의 기공구조를 갖는 다공성 전이금속 산화촉매 분리막, 이의 제조방법, 및 이를 이용한 난분해성 폐수의 처리방법에 관한 것이다.The present invention provides a porous transition metal oxide catalyst membrane having a pore structure of various sizes prepared using a block copolymer, a surfactant, an organic polymer and a mixture thereof as a nanostructure template, a method for preparing the same, and a hardly degradable wastewater using the same. It relates to a treatment method.
화석연료를 기반으로 하는 고도산업화 및 도시화의 가속화에 따른 수질오염이 날로 심각해지고 있으며, 특히 난분해성 유기물이 함유된 폐수의 처리가 당면한 과제로 대두되고 있다. 난분해성 유기물이란 전통적인 수처리 공정인 미생물에 의한 생물학적 분해가 어려운 물질을 의미하는데, 리그닌, 셀룰로오스 등을 포함하는 유해하지 않은 유기물과, POPs(persistant organic products), 벤젠화합물, 안트라센(anthracene), 크리센(Chrysene), 나프탈렌(naphthalene), 나프타센(naphthacene), 페난트렌(phenanthrene)과 같은 PAHs(polycyclic aromatic hydrocarbon), 설파메톡사졸, 트라이메토프림, 설파클로로피리디진, 설파티아졸, 설파메타진, 설파다이메톡신과 같은 항생제, 아세트아미노펜, 1,7-다이메틸잔틴, 카페인, 카바마제핀, 시메티딘, 딜티아젬과 같은 일반의약품, TCE, PCE, co-PCB와 같은 염소화합물(chlorinated compounds) 등을 포함하는 유해한 물질로 분류된다. 이러한 유해한 난분해성 유기물은 수질오염의 주범일 뿐만 아니라 생태계와 환경 파괴의 주요인이 되고 있다. 최근 난분해성 유기물에 대한 환경오염 배출규제 기준이 강화됨에 따라 기존 폐수 처리방법, 예컨대 응집 및 흡착 처리법이나 활성슬러지법과 같은 생물학적 처리만으로는 상기 기준을 만족할 수 있는 기준으로 난분해성 유기물이 함유된 폐수를 처리하는 것이 불가능하다. 이에 보다 효율적으로 난분해성 유기물을 처리할 수 있는 처리공정의 개발이 시급한 실정이다.Water pollution due to the acceleration of advanced industrialization and urbanization based on fossil fuels is getting serious day by day, and especially the treatment of wastewater containing hardly decomposable organic matters is emerging. Refractory organic material means a material that is difficult to biodegrade by microorganisms, which is a traditional water treatment process, and non-hazardous organic materials including lignin, cellulose, POPs (persistant organic products), benzene compounds, anthracene, chrysene Polycyclic aromatic hydrocarbons (PAHs) such as Chrysene, naphthalene, naphthacene, phenanthrene, sulfamethoxazole, trimethoprim, sulfachloropyridizine, sulfatiazole, sulfamethazine, Antibiotics such as sulfadimethoxin, acetaminophen, 1,7-dimethylxanthine, caffeine, carbamazepine, cimetidine, generic drugs such as diltiazem, and chlorinated compounds such as TCE, PCE, and co-PCB Are classified as hazardous substances, including. These harmful hardly degradable organics are not only the main contributors to water pollution, but also the main cause of ecosystem and environmental degradation. As environmental pollution emission standards for hardly decomposable organic materials have recently been strengthened, existing wastewater treatment methods such as flocculation and adsorption treatment or activated sludge treatment alone can satisfy the above criteria. It is impossible to do. Accordingly, it is urgent to develop a treatment process that can more efficiently treat hardly decomposable organic substances.
난분해성 유기물을 처리하기 위해 다양한 산화처리법이 개발되고 있는데, 이는 일반적으로 화학적 산화처리법과 고도 산화처리법으로 구분된다. 화학적 산화처리법은 오존, 염소, 과망간산칼륨 등의 단일 화학적 산화제를 이용하는 방법으로 난분해성 유기물에 대한 산화력에 한계가 있다. 최근에 산화력을 더욱 향상시키기 위해 오존(O3), 과산화수소(H2O2), UV(ultraviolet), 초음파(US, ultrasonic), 산화촉매(catalyst) 등을 교차 사용하는 O3/H2O2, O3/UV, H2O2/UV, O3/H2O2/UV, H2O2/Fe(펜톤 산화), 고체촉매(SC, solid catalyst)/O3, SC/H2O2 등의 고도 산화처리법이 개발되고 있다.Various oxidation treatments have been developed to treat hardly decomposable organic substances, which are generally classified into chemical oxidation treatment and advanced oxidation treatment. Chemical oxidation treatment is a method of using a single chemical oxidizing agent such as ozone, chlorine, potassium permanganate, etc., there is a limit to the oxidizing power for hardly decomposable organic matter. Recently, O 3 / H 2 O, which cross-uses ozone (O 3 ), hydrogen peroxide (H 2 O 2 ), UV (ultraviolet), ultrasonic (US, ultrasonic), oxidation catalyst (catalyst) 2 , O 3 / UV, H 2 O 2 / UV, O 3 / H 2 O 2 / UV, H 2 O 2 / Fe (Fenton Oxidation), solid catalyst (SC) / O 3 , SC / H Advanced oxidation treatment methods such as 2 O 2 have been developed.
고도 산화처리법에서 주로 활용되고 있는 라디칼은 산화력이 높은 OH 라디칼로서 과산화수소나 오존이 분해되면서 생성되는데, 이를 이용한 H2O2/UV, H2O2/O3, H2O2/O3/UV 등의 방법들은 UV 램프나 오존발생기와 같은 부속장치를 필요로 하기 때문에 초기 설비투자비용이 많이 들고 운전비도 상대적으로 높은 단점을 가지고 있다. Radicals mainly used in advanced oxidation treatment are oxidizing OH radicals, which are generated by the decomposition of hydrogen peroxide or ozone. H 2 O 2 / UV, H 2 O 2 / O 3 , H 2 O 2 / O 3 / Since UV and other methods require accessories such as UV lamps and ozone generators, the initial investment costs are high and the operating costs are relatively high.
산화촉매를 이용하여 산화효율을 높이는 방법으로 상온, 상압 하에서 산화반응을 유지할 수 있도록 H2O2/Fe(펜톤 산화법)와 같은 액상 산화촉매를 이용한 산화법이 현재 많이 사용되고 있다. 그러나 이 방법은 반응 후 촉매를 침전시켜 제거해야 하므로 슬러지 발생량이 많으며 슬러지를 제거하기 위한 추가공정이 요구된다.In order to increase the oxidation efficiency by using an oxidation catalyst, an oxidation method using a liquid oxidation catalyst such as H 2 O 2 / Fe (Fenton oxidation method) has been widely used to maintain an oxidation reaction at room temperature and normal pressure. However, this method has a large amount of sludge generated because the catalyst has to be precipitated and removed after the reaction, and an additional step for removing the sludge is required.
이러한 액상 산화촉매의 단점을 보완하기 위해 고상 산화촉매를 이용하는 다양한 폐수 처리방법들이 개발되었다(Zimmermann 등, J. Chem. Eng. 65: 117, 1959; 原田吉明, 觸媒, 35(5): 289, 1993). 그러나 고상 산화촉매는 액상 산화촉매에 비해 반응성이 낮기 때문에 반응성 증대를 위해 150∼300℃의 고온 및 50 atm 이상의 고압을 요구하고, 이는 처리조건이 매우 복잡하고 초기 설비투자비용이 매우 높아 다량의 폐수를 처리하기에는 경제적이지 못하다는 문제점이 있다. Various wastewater treatment methods using solid oxidation catalysts have been developed to compensate for the disadvantages of the liquid oxidation catalysts (Zimmermann et al. , J. Chem. Eng. 65: 117, 1959; , 1993). However, solid phase oxidation catalysts have lower reactivity compared to liquid phase oxidation catalysts, and therefore require high temperatures of 150 to 300 ° C. and high pressures of at least 50 atm to increase reactivity. There is a problem that it is not economical to deal with.
대한민국 특허공고 제1994-6404호에는 벌집 형태의 TiO2-ZrO2 재질에 다양한 전이금속이 담지된 수처리용 촉매가 개시되어 있다. 그러나 상기 수처리용 촉매는 구조가 벌집 형태로 제한적이며 탈취와 살균이 주목적으로 폐수 처리에는 적합하지 않다. 또한 대한민국 특허공개 제2000-31391호에는 입상이나 분말 활성탄에 TiO2가 담지된 UV 광촉매를 이용한 산화처리법이 개시되어 있으나, 이 방법 역시 미생물이 나 균류를 흡착하여 항균, 살균하는 정도의 미약한 산화반응을 나타낼 뿐, 난분해성 유기물을 함유한 폐수의 처리에는 적합하지 않다.Korean Patent Publication No. 1994-6404 discloses a catalyst for water treatment in which various transition metals are supported on a honeycomb TiO 2 -ZrO 2 material. However, the catalyst for water treatment is limited in the form of honeycomb, and deodorization and sterilization are not suitable for wastewater treatment. In addition, Korean Patent Publication No. 2000-31391 discloses an oxidation treatment method using a UV photocatalyst in which TiO 2 is loaded on granular or powdered activated carbon. It exhibits a reaction and is not suitable for the treatment of wastewater containing hardly decomposable organic matter.
대한민국 특허공개 제2002-43946호에는 또한 분말 활성탄의 표면을 주석으로 개질하고 금속이온을 그 표면에 담지시킨 고상 산화촉매와 오존을 이용한 폐수 처리방법이 개시되어 있다. 상기 방법은 펜톤 산화법에서와 같이 2차 오염원이 발생하지 않고 처리효율이 기존 처리방법에 비해 높다는 장점이 있지만, 여전히 장시간의 처리시간이 필요하고 처리공정이 연속적이지 못하여 처리비용이 많이 드는 단점이 있다.Korean Patent Laid-Open Publication No. 2002-43946 also discloses a wastewater treatment method using a solid phase oxidation catalyst and ozone in which a surface of powdered activated carbon is modified with tin and a metal ion is supported on the surface thereof. The method has the advantage that the secondary pollutant is not generated and the treatment efficiency is higher than that of the conventional treatment method, as in the Fenton oxidation method, but it still requires a long treatment time, and the treatment process is not continuous, thus causing a high treatment cost. .
따라서 본 발명의 목적은 기존 촉매 산화법의 문제점을 해결하기 위한 것으로, 다양한 크기의 다중 기공구조를 가져 비표면적이 매우 크고 산화효율이 우수할 뿐만 아니라 연속공정으로의 처리가 가능하여 난분해성 유기물이 함유된 폐수를 효과적으로 처리할 수 있는 산화촉매 분리막을 제공하는 것이다.Therefore, an object of the present invention is to solve the problems of the conventional catalytic oxidation method, and has a multi-pore structure of various sizes, so that the specific surface area is very large, the oxidation efficiency is excellent, and it is possible to process in a continuous process, which contains hardly decomposable organic substances. It is to provide an oxidation catalyst separation membrane that can effectively treat the waste water.
상기 목적을 달성하기 위하여, 본 발명은 하기 단계를 포함하는 다공성 전이금속 산화촉매 분리막을 제조하는 방법을 제공한다:In order to achieve the above object, the present invention provides a method for producing a porous transition metal oxide catalyst membrane comprising the following steps:
1) 나노구조 주형으로서 블록공중합체, 계면활성제, 유기고분자 및 이들의 혼합물 중의 어느 하나, 1종 이상의 전이금속 화합물, 및/또는 실리카 전구체를 상온에서 용매에 혼합하는 단계; 1) mixing any one of the block copolymers, surfactants, organic polymers and mixtures thereof, at least one transition metal compound, and / or silica precursor as a nanostructured template in a solvent at room temperature;
2) 상기 혼합물을 판상 또는 중공사 분리막 형태의 틀에 채운 후 이로부터 용매를 제거하여 나노구조를 형성하고 그 구조 내에 전이금속 및/또는 실리카 전구체를 담지시키는 단계; 및 2) filling the mixture into a mold in the form of a plate or hollow fiber membrane, and then removing solvent therefrom to form a nanostructure and supporting a transition metal and / or silica precursor in the structure; And
3) 상기 혼합물을 150 내지 1,000℃의 온도에서 1 내지 24시간 동안 소결하여 나노구조 주형을 제거하는 단계.3) sintering the mixture at a temperature of 150 to 1,000 ° C. for 1 to 24 hours to remove the nanostructured template.
또한 본 발명은 상기 방법에 의해 제조된 다공성 전이금속 산화촉매 분리막을 제공한다.The present invention also provides a porous transition metal oxide catalyst separator prepared by the above method.
아울러, 본 발명은 상기 다공성 전이금속 산화촉매 분리막을 이용하여 난분 해성 폐수를 처리하는 방법을 제공한다.In addition, the present invention provides a method for treating refractory wastewater using the porous transition metal oxide catalyst membrane.
본 발명에 따른 다공성 전이금속 산화촉매 분리막은 다양한 크기의 기공구조를 가져 비표면적이 크고 우수한 산화효율을 나타낼 뿐만 아니라 연속공정에의 적용이 가능하여 단시간 내에 난분해성 유기물이 함유된 폐수를 처리하는데 효과적으로 사용될 수 있다. 또한 본 발명에 따른 산화촉매 분리막은 고온, 고압의 반응조건을 요구하지 않아 고가의 반응기 설치와 같은 초기 설비투자비용을 줄일 수 있어 매우 경제적이고, 폐수처리 과정에서 2차 오염물을 생성하지 않으며 산화제로 사용된 잔류 오존이나 과산화수소를 효과적으로 제거할 수 있다는 특징을 갖는다.The porous transition metal oxide catalyst separation membrane according to the present invention has a pore structure of various sizes, exhibits a large specific surface area and excellent oxidation efficiency, and can be applied to a continuous process to effectively treat wastewater containing hardly decomposable organic matter within a short time. Can be used. In addition, the oxidation catalyst separation membrane according to the present invention does not require high temperature and high pressure reaction conditions, thereby reducing the initial capital investment cost, such as the installation of expensive reactors, and is very economical, and does not generate secondary pollutants in the wastewater treatment process. It is characterized by effectively removing residual ozone and hydrogen peroxide used.
본 발명은 블록공중합체, 계면활성제, 유기고분자 및 이들의 혼합물을 나노구조 주형으로 사용하여 다양한 크기의 기공구조를 갖는 다공성 전이금속 산화촉매 분리막을 제조하는 것을 특징으로 한다.The present invention is characterized in that a porous transition metal oxide catalyst membrane having a pore structure of various sizes is prepared using a block copolymer, a surfactant, an organic polymer, and a mixture thereof as a nanostructured template.
본 발명에 따른 다공성 전이금속 산화촉매 분리막의 제조방법은Method for producing a porous transition metal oxide catalyst membrane according to the present invention
1) 나노구조 주형으로서 블록공중합체, 계면활성제, 유기고분자 및 이들의 혼합물 중의 어느 하나, 1종 이상의 전이금속 화합물, 및/또는 실리카 전구체를 상온에서 용매에 혼합하는 단계; 1) mixing any one of the block copolymers, surfactants, organic polymers and mixtures thereof, at least one transition metal compound, and / or silica precursor as a nanostructured template in a solvent at room temperature;
2) 상기 혼합물을 판상 또는 중공사 분리막 형태의 틀에 채운 후 이로부터 용매를 제거하여 나노구조를 형성하고 그 구조 내에 전이금속 및/또는 실리카 전구체를 담지시키는 단계; 및 2) filling the mixture into a mold in the form of a plate or hollow fiber membrane, and then removing solvent therefrom to form a nanostructure and supporting a transition metal and / or silica precursor in the structure; And
3) 상기 혼합물을 150 내지 1,000℃의 온도에서 1 내지 24시간 동안 소결하여 나노구조 주형을 제거하는 단계를 포함할 수 있다.3) the mixture may be sintered for 1 to 24 hours at a temperature of 150 to 1,000 ℃ to remove the nanostructure template.
이하, 상기 제조방법을 단계별로 상세히 설명한다.Hereinafter, the manufacturing method will be described in detail step by step.
단계 1)은 다양한 크기의 기공 형성을 위한 나노구조 주형으로서 블록공중합체, 계면활성제, 유기고분자 및 이들의 혼합물 중의 어느 하나, 1종 이상의 전이금속 화합물, 및/또는 실리카 전구체를 상온에서 용매에 혼합하여 촉매 조성물을 제조하는 단계이다. Step 1) is a nanostructured template for forming pores of various sizes, wherein any one of block copolymers, surfactants, organic polymers and mixtures thereof, one or more transition metal compounds, and / or silica precursors are mixed in a solvent at room temperature. To prepare a catalyst composition.
단계 1)에서 나노구조 주형으로 사용되는 블록공중합체는 자기-조립(self-assembly)을 통해 나노구조를 형성할 수 있고 전이금속 화합물 및/또는 실리카 전구체와 잘 혼화될 수 있는 블록공중합체라면 그 종류에 제한 없이 모두 사용될 수 있다. 블록공중합체가 전이금속 화합물 및/또는 실리카 전구체와 잘 혼화되기 위해서는 친수성 고분자 블록과 소수성 고분자 블록을 포함하는 공중합체로서 전이금속 화합물 및/또는 실리카 전구체와의 반응이 친수성 고분자 블록에서만 이루어질 수 있는 것이 바람직하다. 특히 소수성 고분자 블록으로는 PLGA(poly(lactic-co-glycolic acid)), 폴리락타이드(polylactide), 폴리카프로락톤(poly-e-carprolactone), 폴리프로필렌옥사이드(poly(propylene oxide)), 폴리스티렌(polystyrene), 폴리부틸아크릴레이트(polybutylacrylate), 폴리메틸메타크릴레이트(polymethylmethacrylate), 폴리부틸메타크릴레이트 (polybutylmethacrylate), 폴리다이메틸실록산(polydimethylsiloxane), 폴리부타디엔(polybutadiene), 폴리이소프렌(polyisoprene), 폴리에틸렌(polyethlene), 폴리(에틸렌-co-부 텐)(poly(ethylene-co-butene)), 폴리(프로필렌-co-에틸렌)(poly(propylene-co-ethylene)) 등을 포함하고, 친수성 고분자 블록으로는 폴리에틸렌옥사이드(polyethylene oxide), 폴리비닐피리딘(polyvinyl pyridine), 폴리비닐피롤리돈(polyvinyl pyrrolidone), 폴리아크릴산(polyacrylic acid), 폴리아크릴산염, 폴리메타크릴산(polymethacrylic acid), 폴리메타크릴산염, 폴리아크릴아마이드(polyacrylamide), 폴리-N,N-다이메틸아크릴아마이드(poly-N,N-dimethylacrylamide), 폴리-N-아이소프로필아크릴아마이드(poly-N-isopropylacrylamide), 폴리에틸렌이민 (polyethyleneimine) 등을 포함하는 블록공중합체가 유리하게 사용될 수 있다. 본 발명에 적합한 대표적인 블록공중합체로는 폴리스티렌-폴리비닐피리딘 블록공중합체, 폴리에틸렌옥사이드-폴리프로필렌옥사이드 블록공중합체, 폴리에틸렌옥사이드-PLGA 블록공중합체, 폴리부타디엔-폴리아크릴산 블록공중합체, 폴리이소프렌-폴리메타크릴산염 블록공중합체 등을 예로 들 수 있다. 이러한 블록공중합체와 전이금속 화합물 및/또는 실리카 전구체를 용매에 용해시키면 졸 상태의 혼합물이 얻어지고, 이로부터 용매를 제거하면 블록공중합체에 의해 나노구조가 형성되면서 전이금속 및/또는 실리카가 블록공중합체의 친수성 고분자 블록에만 반응하여 담지된다. 이어서 상기 혼합물을 고온에서 소결 처리를 하면 전이금속 및/또는 실리카가 담지된 부분을 제외한 나머지 블록공중합체 부분이 제거되면서 기공 구조가 형성된다. 이렇게 블록공중합체를 이용하여 형성된 기공은 5 내지 100 ㎚ 크기의 직경을 갖는다.The block copolymer used as the nanostructured template in step 1) is a block copolymer capable of forming nanostructures through self-assembly and well blending with transition metal compounds and / or silica precursors. All can be used without limitation. In order for the block copolymer to be well mixed with the transition metal compound and / or the silica precursor, the copolymer including the hydrophilic polymer block and the hydrophobic polymer block can be reacted with the transition metal compound and / or the silica precursor only in the hydrophilic polymer block. desirable. In particular, hydrophobic polymer blocks include PLGA (poly (lactic-co-glycolic acid)), polylactide, poly-e-carprolactone, poly (propylene oxide), polystyrene ( polystyrene, polybutylacrylate, polymethylmethacrylate, polybutylmethacrylate, polydimethylsiloxane, polybutadiene, polyisadiene, polyisoprene, polyethylene hydrophilic polymer block including polyethlene, poly (ethylene-co-butene), poly (propylene-co-ethylene), and the like Examples include polyethylene oxide, polyvinyl pyridine, polyvinyl pyrrolidone, polyacrylic acid, polyacrylic acid, polymethacrylic acid, and polymethacrylic acid. Lylate, polyacrylamide, poly-N, N-dimethylacrylamide, poly-N-isopropylacrylamide, polyethyleneimine Block copolymers) may be advantageously used. Representative block copolymers suitable for the present invention include polystyrene-polyvinylpyridine block copolymers, polyethylene oxide-polypropylene oxide block copolymers, polyethylene oxide-PLGA block copolymers, polybutadiene-polyacrylic acid block copolymers, polyisoprene-polymers Acrylate block copolymers and the like. Dissolving such block copolymers and transition metal compounds and / or silica precursors in a solvent yields a sol mixture, and removing the solvent therefrom results in the formation of nanostructures by the block copolymer, while the transition metal and / or silica blocks. It is supported by reacting only with the hydrophilic polymer block of the copolymer. Subsequently, when the mixture is sintered at a high temperature, the pore structure is formed while removing the remaining portion of the block copolymer except for the portion supporting the transition metal and / or silica. The pores formed using the block copolymer have a diameter of 5 to 100 nm.
단계 1)에서 나노구조 주형으로 사용되는 계면활성제는 자기-조립을 통해 나 노구조를 형성할 수 있고 전이금속 화합물 및/또는 실리카 전구체와 잘 혼화될 수 있는 계면활성제라면 그 종류에 제한 없이 모두 사용될 수 있다. 계면활성제는 용액 내에서 자기-조립에 의해 교질(micelle) 입자를 형성하면서 거대분자 구조를 형성하는 구조 유도체(structure-directing agent)로 작용할 수 있다. 본 발명에 적합한 계면활성제로는 할로겐화 알킬 피리디늄계 물질로서 염화 세틸피리디늄, 염화 도데실피리디늄, 염화테트라데실피리디늄, 염화 옥타데실피리디늄, 브롬화 도데실피리디늄, 브롬화 테트라데실피리디늄, 브롬화 헥사데실트라이메틸암모늄, 브롬화 헥사데실트라이메틸암모늄, 브롬화 테트라데실트라이메틸암모늄, 브롬화 도데실트라이메틸암모늄 등과; 할로겐화 알킬트라이메틸암모늄계 물질로서 할로겐화 옥타데실트라이메틸암모늄, 할로겐화 헥사데실트라이메틸암모늄, 할로겐화 테트라데실트라이메틸암모늄, 할로겐화 도데실트라이메틸암모늄, 할로겐화 옥타데실트라이에틸암모늄, 할로겐화 헥사데실트라이에틸암모늄, 할로겐화 테트라데실트라이에틸암모늄, 할로겐화 도데실트라이에틸암모늄 등을 예로 들 수 있다. 상기한 계면활성제와 전이금속 화합물 및/또는 실리카 전구체를 용매에 용해시키면 계면활성제가 용매 내에서 자기-조립에 의해 교질 입자를 형성하게 되고, 이로부터 용매를 제거하면 계면활성제에 의해 나노구조가 형성되면서 이 교질 입자의 외부 친수성기에 전이금속 및/또는 실리카가 반응하여 담지된다. 이어서 상기 혼합물을 고온에서 소결 처리를 하면 전이금속 및/또는 실리카가 담지된 부분을 제외한 나머지 계면활성제 부분이 제거되면서 기공 구조가 형성된다. 이렇게 계면활성제를 이용하여 형성된 기공은 0.2 내지 3 ㎚ 크기의 직경을 갖는다.The surfactant used as the nanostructured template in step 1) may be any type of surfactant that can form nanostructures through self-assembly and can be well mixed with transition metal compounds and / or silica precursors. Can be. Surfactants can act as structure-directing agents that form macromolecular structures while forming micelle particles by self-assembly in solution. Suitable surfactants for the present invention include halogenated alkyl pyridinium-based materials such as cetylpyridinium chloride, dodecylpyridinium chloride, tetradecylpyridinium chloride, octadecylpyridinium chloride, dodecylpyridinium bromide and tetradecyl bromide. Lidinium, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, dodecyltrimethylammonium bromide and the like; Halogenated octadecyltrimethylammonium, halogenated hexadecyltrimethylammonium, halogenated tetradecyltrimethylammonium, halogenated dodecyltrimethylammonium, halogenated octadecyltriethylammonium, halogenated hexadecyltriethylammonium, Halogenated tetradecyltriethylammonium, halogenated dodecyltriethylammonium and the like. Dissolving the surfactant and the transition metal compound and / or the silica precursor in a solvent causes the surfactant to form colloidal particles by self-assembly in the solvent, and removing the solvent therefrom results in the formation of nanostructures by the surfactant. While the transition metal and / or silica react with the external hydrophilic group of the colloidal particles. Subsequently, when the mixture is sintered at a high temperature, a pore structure is formed while removing the remaining portion of the surfactant except the portion on which the transition metal and / or silica is supported. The pores thus formed using the surfactant have a diameter of 0.2 to 3 nm.
단계 1)에서 나노구조 주형으로 사용되는 유기고분자는 자기-조립을 통해 나노구조를 형성할 수 있는 미립자 형태이고 전이금속 화합물 및/또는 실리카 전구체와 잘 혼화될 수 있고 사용되는 용매에 용해되지 않는 유기고분자라면 그 종류에 제한 없이 모두 사용될 수 있다. 본 발명에 적합한 유기고분자로서 폴리스티렌, 폴리아크릴레이트, 폴리메타크릴레이트, 폴리우레탄, 폴리에틸렌, 폴리프로필렌, 멜라닌, 이들의 혼합물, 이들의 유도체 등이 적합하며 특히 용매에 용해되지 않기 위해 가교된 미립자가 더욱 적합하다. 본 발명에 적합한 유기고분자 미립자의 입자경은 50 ㎚ 내지 1 ㎜ 범위인 것이 적당하며, 입자경 크기 분포도(Dw/Dn)가 1.2 이하인 균일한 고분자 비드인 것이 더욱 유리하다. 상기한 유기고분자와 전이금속 화합물 및/또는 실리카 전구체를 용매에 분산시킨 후 용매를 제거하면 유기고분자 미립자에 의해 나노구조가 형성되고, 이어서 상기 혼합물을 고온에서 소결 처리를 하면 전이금속 및/또는 실리카가 담지된 부분을 제외한 나머지 유기고분자 부분이 제거되면서 기공 구조가 형성된다. 이렇게 유기고분자 미립자를 이용하여 형성된 기공은 50 ㎚ 내지 1 ㎜ 크기의 직경을 갖는다.The organic polymer used as the nanostructured template in step 1) is in the form of particulates capable of forming nanostructures through self-assembly and can be well mixed with transition metal compounds and / or silica precursors and insoluble in the solvent used. Any polymer can be used without limitation in its kind. As organic polymers suitable for the present invention, polystyrene, polyacrylate, polymethacrylate, polyurethane, polyethylene, polypropylene, melanin, mixtures thereof, derivatives thereof, and the like are particularly suitable. More suitable. The particle diameter of the organic polymer fine particles suitable for the present invention is suitably in the range of 50 nm to 1 mm, more preferably uniform polymer beads having a particle size distribution (Dw / Dn) of 1.2 or less. After dispersing the organic polymer, the transition metal compound and / or the silica precursor in a solvent, and then removing the solvent, nanostructures are formed by the organic polymer fine particles, and when the mixture is sintered at a high temperature, the transition metal and / or silica Pore structure is formed by removing the remaining organic polymer parts except the supported part. The pores formed using the organic polymer fine particles have a diameter of 50 nm to 1 mm.
단계 1)에서 나노구조 주형으로서 블록공중합체, 계면활성제 및 유기고분자 미립자는 단독으로도 사용될 수 있으나, 다양한 크기의 다중 기공을 형성하기 위해서는 2종 이상의 혼합물 형태로 사용되는 것이 바람직하다. 또한 단계 1)에서 나노구조 주형은 전이금속 화합물 100 중량부를 기준으로 10 내지 1,000 중량부, 바람직하게는 20 내지 100 중량부로 사용되는 것이 유리하다. 나노구조 주형의 사용량이 10 중량부 미만일 경우에는 기공구조가 제대로 형성되지 않는 문제점이 발생 할 수 있는 반면, 이의 사용량이 1,000 중량부를 초과하는 경우에는 제조된 분리막의 기계적 물성이 저하되는 문제점이 발생할 수 있다.In step 1), the block copolymer, the surfactant, and the organic polymer fine particles may be used alone as the nanostructured template, but in order to form multiple pores of various sizes, it is preferable to use the mixture in two or more kinds. In addition, the nanostructure template in step 1) is advantageously used in 10 to 1,000 parts by weight, preferably 20 to 100 parts by weight based on 100 parts by weight of the transition metal compound. If the amount of the nano-structured template is less than 10 parts by weight, the pore structure may not be formed properly. If the amount of the nano-structured template is used more than 1,000 parts by weight, the mechanical properties of the manufactured separator may be deteriorated. have.
단계 1)에서 전이금속은 Pd, Fe, Mn, Ti, Co, Ni, Pt, Au, Ru, Cu, Zn, 및 V로 구성된 군으로부터 선택될 수 있으며, 단독으로 또는 2종 이상의 혼합물 형태로 사용될 수 있다. 본 발명에 바람직한 전이금속 화합물로는 상기한 전이금속 Pd, Fe, Mn, Ti, Co, Ni, Pt, Au, Ru, Cu, Zn 및 V의 가용성 염, 산화물, 합금 등을 사용할 수 있다. The transition metal in step 1) may be selected from the group consisting of Pd, Fe, Mn, Ti, Co, Ni, Pt, Au, Ru, Cu, Zn, and V, which may be used alone or in the form of a mixture of two or more thereof. Can be. As the transition metal compound preferred in the present invention, the soluble salts, oxides, alloys and the like of the transition metals Pd, Fe, Mn, Ti, Co, Ni, Pt, Au, Ru, Cu, Zn and V may be used.
본 발명에 따른 전이금속 산화촉매 분리막에서 전이금속의 함량은 전이금속의 특성에 따라 달라질 수 있는데, 예컨대, 가격이 비교적 저렴하고 물성이 강한 전이금속의 경우에는 용매에 나노구조 주형과 전이금속만을 혼합하여 전이금속 산화촉매 분리막을 제조할 수 있다. 그러나 일반적으로 고가인 전이금속은 그의 함량이 증가할수록 제조비용이 증가하여 경제적이지 못하고, 일부 전이금속, 예컨대, Pd, Ni, Mn와 같은 전이금속은 물성이 약해 이들만으로 분리막을 제조할 경우 분리막 구조가 매우 불안정해지는 문제가 발생할 수 있다. The content of the transition metal in the transition metal oxide catalyst separator according to the present invention may vary depending on the characteristics of the transition metal. For example, in the case of a transition metal having a relatively low price and strong physical properties, only the nanostructure template and the transition metal are mixed in a solvent. To prepare a transition metal oxide catalyst separation membrane. However, in general, expensive transition metals are not economical because their production cost increases as their content increases, and some transition metals, such as Pd, Ni, and Mn, have weak physical properties, and thus, when the membrane is manufactured using only these membrane structures, May cause a problem that becomes very unstable.
이에 본 발명에서는 이러한 문제점을 보완하기 위하여 전이금속의 지지체(support)로서 실리카 전구체를 첨가하여 안정한 구조의 산화촉매 분리막을 제조한다. 이와 같은 목적으로 단계 1)에 사용하기에 적합한 실리카 전구체로는 메틸트라이메톡시실란(methyltrimethoxysilane), 다이메틸다이메톡시실란(dimethyldimethoxysilane), 트라이메틸메톡시실란(trimethylmethoxysilane), 메틸트라이에톡시실란(methyltriethoxysilane), 다이메틸다이에톡시실 란(dimethyldiethoxysilane), 트라이메틸에톡시실란(trimethylethoxysilane), 메틸트라이클로로실란(methyltrichlorosilane), 다이메틸다이클로로실란(dimethyldichlorosilane), 트라이메틸클로로실란(trimethylchlorosilane), 비스(트라이클로로실릴)메탄(bis(trichlorosilyl)methane), 1,2-비스(트라이클로로실릴)에탄(1,2-bis(trichlorosilyl)ethane), 비스(트라이메톡시실릴)메탄(bis(trimethoxysilyl)methane), 1,2-비스(트라이에톡시실릴)에탄(1,2-bis(triethoxysilyl)ethane), 1,4-비스(트라이메톡시실릴)벤젠(1,4-bis(trimethoxysilyl)benzene), 1,4-비스(트라이메톡시실릴에틸)벤젠(1,4-bis(trimethoxysilylethyl)benzene), 1,4-비스(트라이에톡시실릴)벤젠(1,4-bis(triethoxysilyl)benzene), 1,4-비스(트라이에톡시실릴에틸)벤젠(1,4-bis(triethoxysilylethyl)benzene), 2,5-비스(트라이메톡시실릴)티오펜(2,5-bis(trimethoxysilyl)thiophene), 2,5-비스(트라이에톡시실릴)티오펜(2,5-bis(triethoxysilyl)thiophene), 4,4-비스(트라이메톡시실릴)바이페닐(2,5-bis(trimethoxysilyl)biphenyl), 4,4-비스(트라이에톡시실릴)바이페닐(2,5-bis(triethoxysilyl)biphenyl) 등이 포함된다.Accordingly, in the present invention, in order to compensate for this problem, an oxide catalyst separation membrane having a stable structure is prepared by adding a silica precursor as a support of the transition metal. Suitable silica precursors for use in step 1) for this purpose include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane ( methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, bis Trichlorosilyl) methane, 1,2-bis (trichlorosilyl) ethane, bis (trimethoxysilyl) methane ), 1,2-bis (triethoxysilyl) ethane (1,2-bis (triethoxysilyl) ethane), 1,4-bis (trimethoxysilyl) benzene (1,4-bis (trimethoxysilyl) benzene), 1,4-bis (trimethoxysilicone) Ethyl) benzene (1,4-bis (trimethoxysilylethyl) benzene), 1,4-bis (triethoxysilyl) benzene (1,4-bis (triethoxysilyl) benzene), 1,4-bis (triethoxysilylethyl ) Benzene (1,4-bis (triethoxysilylethyl) benzene), 2,5-bis (trimethoxysilyl) thiophene, 2,5-bis (triethoxysilyl) thiophene Thiophene (2,5-bis (triethoxysilyl) thiophene), 4,4-bis (trimethoxysilyl) biphenyl (2,5-bis (trimethoxysilyl) biphenyl), 4,4-bis (triethoxysilyl) Biphenyl (2,5-bis (triethoxysilyl) biphenyl) and the like.
단계 1)에 전이금속 화합물과 함께 실리카 전구체가 사용되는 경우, 실리카 전구체는 전이금속 화합물 100 중량부를 기준으로 100 내지 100,000 중량부, 바람직하게는 300 내지 10,000 중량부의 양으로 사용될 수 있다. When the silica precursor is used together with the transition metal compound in step 1), the silica precursor may be used in an amount of 100 to 100,000 parts by weight, preferably 300 to 10,000 parts by weight based on 100 parts by weight of the transition metal compound.
단계 1)에서 나노구조 주형, 전이금속 화합물, 및/또는 실리카 전구체를 용해시켜 촉매 조성물의 제조를 위한 용매로는 물, 에탄올, 메탄올, 메틸에틸케톤, 메틸아이소부틸케톤, 아세톤, 에틸아세테이트, 부틸아세테이트, n-헥산, 아이소프로필알코올, 트라이클로로에틸렌, 테트라하이드로퓨란, 톨루엔, 2-부탄올, 벤젠, 에틸벤젠, 트라이메틸벤젠, 자일렌, 등이 사용될 수 있고, 이들은 단독으로 또는 2종 이상의 혼합물 형태로 사용될 수 있다. 단계 1)에서 용매는 전이금속 화합물 100 중량부를 기준으로 100 내지 10,000 중량부, 바람직하게는 500 내지 2,000 중량부의 양으로 사용될 수 있다. Solvents for preparing the catalyst composition by dissolving the nanostructured template, the transition metal compound, and / or the silica precursor in step 1) include water, ethanol, methanol, methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, butyl Acetate, n-hexane, isopropyl alcohol, trichloroethylene, tetrahydrofuran, toluene, 2-butanol, benzene, ethylbenzene, trimethylbenzene, xylene, and the like may be used, and these may be used alone or in mixture of two or more thereof. It can be used in the form. In step 1), the solvent may be used in an amount of 100 to 10,000 parts by weight, preferably 500 to 2,000 parts by weight, based on 100 parts by weight of the transition metal compound.
단계 2)는 단계 1)에서 준비된 혼합물을 판상 또는 중공사 분리막 형태의 틀에 채운 후 이로부터 용매를 제거하여 나노구조를 형성하고 그 구조 내에 전이금속 및/또는 실리카를 담지시키는 단계이다. Step 2) is a step in which the mixture prepared in step 1) is filled into a mold in the form of a plate or hollow fiber membrane and then the solvent is removed therefrom to form a nanostructure and to support the transition metal and / or silica in the structure.
또한 단계 1)에서 각 성분의 균일한 혼합을 위해 사용된 용매는 회전 감압기 또는 이와 유사한 증발장치를 이용하여 혼합물로부터 제거되는데, 이와 같이 용매가 제거됨에 따라 혼합물 내 나노구조 주형의 자기-조립에 의해 나노구조가 형성되고, 이와 동시에 전이금속 및/또는 실리카가 형성된 나노구조의 특정 부분에 담지된다. 이때, 전이금속 화합물 및/또는 실리카 전구체가 나노구조의 어느 부분에 담지되느냐는 사용된 나노구조 주형, 즉 블록공중합체, 계면활성제 및 유기고분자의 특성에 따라 달라질 수 있다. 예를 들어, 나노구조 주형으로 블록공중합체를 사용하는 경우 전이금속 및/또는 실리카는 블록공중합체의 친수성 고분자 블록에 담지되고, 계면활성제를 사용하는 경우 전이금속 및/또는 실리카는 계면활성제 교질 입자의 외부 친수성기에 담지되고, 유기고분자 미립자를 사용하는 경우 미립자에 의해 채워진 구조 밖에 담지된다.In addition, the solvent used for homogeneous mixing of each component in step 1) is removed from the mixture using a rotary pressure reducer or similar evaporator. As the solvent is removed, the solvent is added to the self-assembly of the nanostructured template in the mixture. Thereby forming a nanostructure, and at the same time supported on a specific portion of the nanostructure on which transition metals and / or silica are formed. In this case, which part of the nanostructure is supported by the transition metal compound and / or the silica precursor may vary depending on the characteristics of the nanostructure template used, that is, the block copolymer, the surfactant, and the organic polymer. For example, when the block copolymer is used as a nanostructured template, the transition metal and / or silica are supported on the hydrophilic polymer block of the block copolymer, and when the surfactant is used, the transition metal and / or silica are surfactant colloidal particles. It is supported on the external hydrophilic group of and, when using organic polymer fine particles, it is supported only outside the structure filled with the fine particles.
단계 3)은 단계 2)에서 블록공중합체, 계면활성제 및/또는 유기고분자에 의해 형성된 나노구조에 전이금속 및/또는 실리카가 담지되어 있는 상태의 혼합물을 150 내지 500℃의 온도에서 1 내지 24 시간 동안 소결하여 상기 나노구조 주형을 제거하는 단계이다. 이 단계에서 150 내지 1,000℃의 고온으로 상기 혼합물을 처리하면, 혼합물 내 나노구조 주형은 열분해에 의해 제거되지만, 나노구조 내에 담지되어 있던 전이금속 및/또는 실리카는 그대로 남게 되면서 나노구조 주형이 있던 자리에 기공이 형성된다. 이때 사용된 나노구조 주형의 종류 및 특성에 따라 다양한 크기의 기공이 형성되어 다공성 전이금속 산화촉매 분리막이 제조된다. 이렇게 최종적으로 얻어진 다공성 전이금속 산화촉매 분리막은 0.2 ㎚ 내지 1 ㎜의 직경 크기의 멀티-모달(multi-modal)한 기공 분포를 갖는 다공성 구조가 형성되고 10 내지 1,000 ㎡/g의 비표면적을 갖는 것을 특징으로 한다.Step 3) is a mixture of a transition metal and / or silica supported on the nanostructure formed by the block copolymer, the surfactant and / or the organic polymer in step 2) at a temperature of 150 to 500 ° C. for 1 to 24 hours. Sintering during the step of removing the nanostructure template. In this step, if the mixture is treated at a high temperature of 150 to 1,000 ° C., the nanostructured template in the mixture is removed by pyrolysis, but the transition metal and / or silica supported in the nanostructure remain intact while the nanostructured template is present. Pores are formed in the. In this case, pores of various sizes are formed according to the type and characteristics of the nanostructured template used to prepare a porous transition metal oxide catalyst separator. The finally obtained porous transition metal oxide catalyst separation membrane has a porous structure having a multi-modal pore distribution having a diameter size of 0.2 nm to 1 mm, and has a specific surface area of 10 to 1,000 m 2 / g. It features.
상기 방법에 따라 제조된 다공성 산화촉매 분리막은 전이금속만으로 구성되거나 전이금속과 실리카 전구체의 2가지 성분으로 구성될 수 있다. 전이금속과 실리카 전구체로 구성되는 경우, 본 발명에 따른 다공성 전이금속 산화촉매 분리막은 그의 총 중량을 기준으로 0.1 내지 50 중량%의 전이금속 및 50 내지 99.9 중량%의 실리카 전구체를 포함할 수 있다. The porous oxidation catalyst separator prepared according to the above method may be composed of only a transition metal or two components of a transition metal and a silica precursor. When composed of a transition metal and a silica precursor, the porous transition metal oxide catalyst separation membrane according to the present invention may include 0.1 to 50 wt% of the transition metal and 50 to 99.9 wt% of the silica precursor based on the total weight thereof.
본 발명에 따른 다공성 전이금속 산화촉매 분리막은 다양한 크기의 기공구조를 가져 비표면적이 크고 우수한 산화효율을 나타낼 뿐만 아니라 연속공정에의 적용이 가능하여 단시간 내에 난분해성 유기물이 함유된 폐수를 처리하는데 효과적으로 사용될 수 있다. 또한 본 발명에 따른 다공성 전이금속 산화촉매 분리막은 고 온, 고압의 반응조건을 요구하지 않아 고가의 반응기 설치와 같은 초기 설비투자비용을 줄일 수 있어 매우 경제적이고, 폐수처리 과정에서 2차 오염물을 생성하지 않으며 산화제로 사용된 잔류 오존이나 과산화수소를 효과적으로 제거할 수 있다는 특징을 갖는다. 본 발명에 따른 다공성 전이금속 산화촉매 분리막은 또한 펜톤(Fenton) 산화와 같은 기존의 복잡한 다단계 처리공정(도 1a)과는 달리 단일 처리공정(도 1b)의 연속공정에 의해 쉽고 효율적으로 난분해성 유기물을 다량 함유한 폐수를 처리할 수 있다. 연속공정이란 유체의 흐름이 연속적임을 의미한다.The porous transition metal oxide catalyst separation membrane according to the present invention has a pore structure of various sizes, exhibits a large specific surface area and excellent oxidation efficiency, and can be applied to a continuous process to effectively treat wastewater containing hardly decomposable organic matter within a short time. Can be used. In addition, the porous transition metal oxide catalyst separation membrane according to the present invention does not require high temperature and high pressure reaction conditions, thereby reducing the initial capital investment cost, such as the installation of expensive reactors, and is very economical and generates secondary pollutants in the wastewater treatment process. It has a characteristic that it can effectively remove residual ozone or hydrogen peroxide used as oxidant. The porous transition metal oxide catalyst membrane according to the present invention is also easily and efficiently hardly decomposable organic material by a continuous process in a single processing process (FIG. 1B), unlike the conventional complex multi-stage processing process (FIG. 1A) such as Fenton oxidation. Wastewater containing a large amount can be treated. Continuous process means that the flow of fluid is continuous.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하기로 한다. 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 요지에 따라 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 당업계에서 통상의 지식을 가진 자에게 자명할 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention more specifically, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention.
실시예 1Example 1
나노구조 주형으로서 폴리스티렌-폴리비닐피리딘 블록공중합체 4 g 및 입자경이 300 ㎚인 폴리스티렌 비드 10 g, 전이금속 화합물로서 FeSO4 0.5 g, 실리카 전구체로서 트라이에톡시실란(triethoxysilane) 10 ㎖을 THF 100 ㎖에 상온에서 혼합한 후 이를 중공사 분리막 형태의 틀에 채웠다. 상기 혼합물로부터 용매 THF를 제거하고 서서히 승온하여 500℃에서 10시간 동안 소결하였다. 고온에서의 소결 처리에 의해 폴리스티렌-폴리비닐피리딘 블록공중합체 및 폴리스티렌 비드가 제거되 고 Fe 및 실리카 성분이 포함된 기공구조의 분리막을 제조하였다. 4 g of polystyrene-polyvinylpyridine block copolymer as a nanostructure template, 10 g of polystyrene beads having a particle diameter of 300 nm, 0.5 g of FeSO 4 as a transition metal compound, 10 ml of triethoxysilane as a silica precursor, and THF 100 ml After mixing at room temperature, it was filled in the form of hollow fiber membrane. Solvent THF was removed from the mixture and gradually heated to sintering at 500 ° C. for 10 hours. By sintering at high temperature, the polystyrene-polyvinylpyridine block copolymer and polystyrene beads were removed, and a separator having a pore structure containing Fe and silica components was prepared.
이로부터 제조된 다공성 전이금속 산화촉매 분리막은 분리막의 총 중량을 기준으로 5 중량%의 Fe 성분 및 95 중량%의 실리카 성분을 함유하고 있고, 30 ㎡/g의 비표면적 및 20 ㎚ 직경과 300 ㎚ 직경의 바이모달(bimodal)한 기공 분포를 갖는 것으로 확인되었다.The porous transition metal oxide catalyst membrane prepared therefrom contains 5% by weight of Fe and 95% by weight of silica based on the total weight of the membrane, and has a specific surface area of 30 m 2 / g and a diameter of 20 nm and 300 nm. It was found to have a bimodal pore distribution in diameter.
실시예 2Example 2
폴리스티렌-폴리비닐피리딘 블록공중합체를 사용하지 않는 것을 제외하고는 실시예 1과 동일한 방법으로 Fe 및 실리카 성분이 포함된 기공구조의 분리막을 제조하였다. Except not using a polystyrene-polyvinylpyridine block copolymer, a separator having a pore structure including Fe and silica components was prepared in the same manner as in Example 1.
이로부터 제조된 다공성 전이금속 산화촉매 분리막은 분리막의 총 중량을 기준으로 5 중량%의 Fe 성분 및 95 중량%의 실리카 성분을 함유하고 있고, 0.1 ㎡/g의 비표면적 및 300 ㎚ 직경의 단분산 기공 분포를 갖는 것으로 확인되었다. The porous transition metal oxide catalyst membrane prepared therefrom contains 5% by weight of Fe and 95% by weight of silica based on the total weight of the membrane, and has a specific surface area of 0.1 m 2 / g and monodispersion of 300 nm in diameter. It was found to have a pore distribution.
실시예 3Example 3
전이금속 화합물로 FeSO4 대신에 PtCl2를 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 Pt 및 실리카 성분이 포함된 기공구조의 분리막을 제조하였다.A separator having a pore structure including Pt and silica components was prepared in the same manner as in Example 1 except that PtCl 2 was used instead of FeSO 4 as the transition metal compound.
이로부터 제조된 다공성 전이금속 산화촉매 분리막은 분리막의 총 중량을 기 준으로 2 중량%의 Pt 성분 및 98 중량%의 실리카 성분을 함유하고 있고, 20 ㎡/g의 비표면적 및 20 ㎚ 직경과 300 ㎚ 직경의 바이모달한 기공 분포를 갖는 것으로 확인되었다. The porous transition metal oxide catalyst membrane prepared therefrom contains 2 wt% Pt component and 98 wt% silica component based on the total weight of the separator, and has a specific surface area of 20 m 2 / g and a diameter of 20 nm and 300 nm. It was found to have a bimodal pore distribution of nm diameter.
비교예 1Comparative Example 1
FeSO4를 사용하지 않는 것을 제외하고는 실시예 1과 동일한 방법으로 분리막을 제조하였다. A separator was prepared in the same manner as in Example 1 except that FeSO 4 was not used.
실험예 1Experimental Example 1
상기 실시예 1 내지 3에서 제조된 전이금속 산화촉매 분리막의 폐수 처리효율을 조사하기 위하여, 난분해성 유기물이 다량 함유된 원폐수에 산화제로서 오존 및 과산화수소를 첨가한 후 이를 실시예 1 내지 3에서 제조된 전이금속 산화촉매 분리막과 비교예 1에서 제조된 분리막에 각각 투과시키면서 연속적으로 폐수를 처리하였다. In order to investigate the wastewater treatment efficiency of the transition metal oxide catalyst membrane prepared in Examples 1 to 3, ozone and hydrogen peroxide were added to the raw wastewater containing a large amount of hardly decomposable organic substances as oxidants, and then prepared in Examples 1 to 3. The wastewater was continuously treated while permeating through the transition metal oxide catalyst membrane and the membrane prepared in Comparative Example 1.
구체적으로, 하기 표 1에서 시료 1은 난분해성 유기물이 다량 함유된 원폐수 자체를 나타내며, 시료 2는 상기 원폐수에 산화제로 오존과 과산화수소를 첨가한 후 이를 실시예 1에서 제조된 실리카 전구체에 5 중량%의 Fe를 포함하고 비표면적이 30 ㎡/g인 전이금속 산화촉매 분리막을 이용하여 처리한 처리수를 나타내며, 시료 3은 상기 원폐수에 산화제로 오존과 과산화수소를 첨가한 후 이를 실시예 2에서 제조된 실리카 전구체에 5 중량%의 Fe를 포함하고 비표면적이 0.1 ㎡/g인 전이금속 산화촉매 분리막을 이용하여 처리한 처리수를 나타내며, 시료 4는 상기 원폐수에 산화제로 오존과 과산화수소를 첨가한 후 이를 실시예 3에서 제조된 실리카 전구체에 2 중량%의 Pt를 포함하는 전이금속 산화촉매 분리막을 이용하여 처리한 처리수를 나타내며, 시료 5는 상기 원폐수에 산화제로 오존과 과산화수소를 첨가한 후 이를 비교예 1에서 제조된 실리카 분리막을 이용하여 처리한 처리수를 나타낸다. 이때, 산화제로서 오존은 약 0.05 ㎏/ℓ의 양으로, 과산화수소는 3 g/ℓ의 양으로 원폐수에 주입되었다. 또한 수리학적 체류시간은 약 1시간이었고 처리온도는 60℃를 유지하였다.Specifically, in Table 1, Sample 1 represents raw wastewater itself containing a large amount of hardly decomposable organic matter, and Sample 2 was added to the silica precursor prepared in Example 1 after adding ozone and hydrogen peroxide as an oxidizing agent to the raw wastewater. The treated water was treated using a transition metal oxide catalyst membrane containing 30% by weight of Fe and having a specific surface area of 30 m 2 / g, and Sample 3 was added to the raw waste water after adding ozone and hydrogen peroxide as an oxidizing agent. Indicated the treated water using a transition metal oxide catalyst membrane containing 5% by weight of Fe and a specific surface area of 0.1 m 2 / g to the silica precursor prepared in the above, and Sample 4 is ozone and hydrogen peroxide as an oxidant to the raw wastewater. After addition, this was treated water using a transition metal oxide catalyst membrane containing 2 wt% of Pt to the silica precursor prepared in Example 3, and Sample 5 was a phase. After the addition of ozone and hydrogen peroxide as oxidizing agent in the wastewater by using a silica membrane prepared in this Comparative Example 1 shows a number of treatment processes. At this time, ozone as an oxidant was injected into the raw wastewater in an amount of about 0.05 kg / l and hydrogen peroxide in an amount of 3 g / l. In addition, the hydraulic retention time was about 1 hour and the treatment temperature was maintained at 60 ℃.
상기 표 1에 나타난 바와 같이, 본 발명에 따른 다공성 전이금속 산화촉매 분리막은 산화제의 존재 하에서 연속공정에 의해 난분해성 유기물을 다량 함유한 폐수를 효과적으로 처리함을 알 수 있다. 구체적으로, 실시예 1 내지 3에서 제조된 다공성 전이금속 산화촉매 분리막을 이용한 폐수 처리 결과, 원폐수나 비교예 1에서 제조된 실리카 분리막에 비해 화학적 산소요구량(chemical oxygen demand, COD), 생물학적 산소요구량(biological oxygen demand, BOD), 총 유기탄소(total organic carbon, TOC) 및 색도가 현저히 개선되었음을 확인하였다. 특히 본 발명에 따른 다공성 전이금속 산화촉매 중에서도 상대적으로 비표면적이 큰 분리막(실시예 1 및 3)이 보다 우수한 처리효율을 나타내었다. As shown in Table 1, it can be seen that the porous transition metal oxide catalyst membrane according to the present invention effectively treats wastewater containing a large amount of hardly decomposable organic matter by a continuous process in the presence of an oxidizing agent. Specifically, as a result of wastewater treatment using the porous transition metal oxide catalyst membrane prepared in Examples 1 to 3, chemical oxygen demand (COD), biological oxygen demand compared to raw wastewater or silica membrane prepared in Comparative Example 1 (biological oxygen demand, BOD), total organic carbon (TOC) and chromaticity were found to be significantly improved. In particular, among the porous transition metal oxidation catalysts according to the present invention, the separation membranes (Examples 1 and 3) having a relatively large specific surface area showed better processing efficiency.
이상으로 본 발명 내용의 특정 부분을 상세히 기술하였는바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.The specific parts of the present invention have been described in detail, and it is apparent to those skilled in the art that such specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. something to do. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
도 1a는 고도 산화처리법인 펜톤 산화처리에 의해 폐수를 처리하는 과정을 나타낸 모식도이고, 1A is a schematic diagram showing a process of treating wastewater by Fenton oxidation treatment, which is an advanced oxidation treatment,
도 1b는 본 발명에 따른 전이금속 산화촉매 분리막을 이용한 단일 공정에 의해 폐수를 처리하는 과정을 나타낸 모식도이다.1B is a schematic diagram showing a process of treating wastewater by a single process using a transition metal oxide catalyst separation membrane according to the present invention.
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