KR20120130604A - Preparation method for precious metal catalysts by using precious metal extracted organic solvent - Google Patents
Preparation method for precious metal catalysts by using precious metal extracted organic solvent Download PDFInfo
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- 239000003960 organic solvent Substances 0.000 title claims abstract description 55
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- 238000002360 preparation method Methods 0.000 title description 6
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 23
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 14
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
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- 238000001704 evaporation Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
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- 239000004065 semiconductor Substances 0.000 claims description 3
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
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- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
Abstract
Description
본 발명은 귀금속 촉매의 제조방법에 대한 것으로, 특히 귀금속이 함유된 유기용제를 이용해서 귀금속 촉매를 제조하는 것이며, 더욱 상세하게는 귀금속 회수 공정의 중간 생성물로 얻어지는 귀금속 함유 유기용제를 이용해서 귀금속 촉매를 제조하는 것이다.
The present invention relates to a method for producing a noble metal catalyst, and more particularly, to a noble metal catalyst using an organic solvent containing a noble metal, and more particularly to a noble metal catalyst using a noble metal containing organic solvent obtained as an intermediate product of the noble metal recovery process. To prepare.
환경오염 문제에 대한 관심이 늘면서 환경촉매의 수요가 증가하고 있다. 인쇄, 도장 공정 등에 많이 사용되는 휘발성유기화합물(VOC)의 배출에 대한 규제도 강화되고 있다. 낮은 농도의 VOC를 높은 유량으로 배출하는 공정의 경우 촉매연소에 의한 처리방법이 가장 효과적인 것으로 알려져 있다. 특히 Pt, Pd, Rh 등의 귀금속 촉매는 저온 연소 활성이 우수하여 널리 이용되고 있다. 또한, 자동차용 삼원촉매로 사용되고 있는 백금족 귀금속의 수요는 지속적으로 증가하고 있다. As interest in environmental pollution increases, the demand for environmental catalysts is increasing. Regulations on the emission of volatile organic compounds (VOC), which are widely used in printing and painting processes, are also being tightened. Catalytic combustion is known to be the most effective method for discharging low concentrations of VOC at high flow rates. In particular, noble metal catalysts such as Pt, Pd, and Rh are widely used because of their excellent low-temperature combustion activity. In addition, the demand for platinum group precious metals used as three-way catalysts for automobiles continues to increase.
이에 따라 각종 폐촉매나 귀금속을 함유하는 폐기물 중에서 귀금속 성분을 회수하여 재활용하기 위한 연구도 활발히 진행되고 있다.
Accordingly, researches for recovering and recycling precious metal components from various waste catalysts and wastes containing precious metals have been actively conducted.
한편, 귀금속 회수 기술 중에 활발히 연구되고 있는 방법으로 용매추출법이 있다. 귀금속 함유 폐기물에서 용매추출법에 의해 귀금속을 회수하는 공정은, 먼저 귀금속 함유 폐기물을 무기산 용액에 녹인 후에 용매추출법에 의해 귀금속을 유기용제 상으로 추출하고, 이어서 역추출, 정제, 환원, 등의 과정을 반복적으로 수행하여야 한다. On the other hand, there is a solvent extraction method that is actively studied in the precious metal recovery technology. In the process of recovering the precious metal from the precious metal-containing waste by solvent extraction, first, the precious metal-containing waste is dissolved in an inorganic acid solution, followed by extracting the precious metal onto the organic solvent by the solvent extraction method, followed by reverse extraction, purification, reduction, and the like. It must be done repeatedly.
이와 같이, 기존의 귀금속 회수 공정에 의하면 용매추출 공정 이후에도 많은 공정을 반복적으로 거쳐서 분말 또는 시약 등의 형태로 최종 귀금속 제품을 생산하고 있으며, 이렇게 회수된 최종 제품을 다시 촉매 제조 원료로 사용한다. 즉, 종래에는 귀금속 촉매 제조를 위한 원료로 사용되는 귀금속을 얻기 위하여, 용매추출 공정 이후에도 다수의 복잡한 공정을 반복해서 수행해야 하는 문제점이 있었다.
As described above, according to the existing noble metal recovery process, the final noble metal product is produced in the form of a powder or a reagent through a plurality of steps repeatedly even after the solvent extraction process, and the final product thus recovered is used as a raw material for preparing the catalyst. That is, conventionally, in order to obtain a noble metal used as a raw material for preparing a noble metal catalyst, there has been a problem that a plurality of complex processes must be repeatedly performed after the solvent extraction process.
상기한 바와 같은 문제점을 해결하기 위한 본 발명은 귀금속 회수 공정을 통해 회수되는 최종 제품이 아닌 중간 생성물을 촉매 제조에 직접 이용함으로써 촉매 제조 원가를 크게 절감할 수 있으며, 기존의 촉매보다도 성능이 우수한 촉매를 제공하는 것이 목적이다.
The present invention for solving the problems described above can significantly reduce the catalyst manufacturing cost by directly using the intermediate product in the preparation of the catalyst, rather than the final product recovered through the precious metal recovery process, the catalyst that is superior to the existing catalyst The purpose is to provide.
상기한 목적을 달성하기 위한 본 발명은, 귀금속이 함유된 폐기물을 무기산과 혼합하여 귀금속 함유 수용액을 준비하는 단계(S10); 상기 준비한 귀금속 함유 수용액을 추출제 및 유기용제와 혼합해서 귀금속 함유 유기용제를 제조하는 단계(S20); 및 상기 제조한 귀금속 함유 유기용제에 지지체를 담근 후, 용제를 증발시켜서 귀금속이 담지된 지지체를 생성하는 단계(S30);를 포함하는 귀금속 촉매의 제조방법이다.The present invention for achieving the above object, the step of preparing a precious metal-containing aqueous solution by mixing the waste containing the precious metal with an inorganic acid (S10); Preparing a noble metal-containing organic solvent by mixing the prepared noble metal-containing aqueous solution with an extractant and an organic solvent (S20); And dipping the support in the prepared noble metal-containing organic solvent, and then evaporating the solvent to generate a support in which the noble metal is supported (S30).
여기서, 상기 귀금속이 함유된 폐기물은, 귀금속이 함유된 폐촉매, 반도체 폐기물 및 의료용 폐기물 중에서 선택된 하나 이상인 것일 수 있다. Here, the waste containing the noble metal may be one or more selected from waste catalyst, semiconductor waste and medical waste containing the noble metal.
그리고, 상기 귀금속 함유된 유기용제는, 용매추출법에 의한 귀금속 회수 공정의 중간 생성물인 것이 바람직하다. The noble metal-containing organic solvent is preferably an intermediate product of the noble metal recovery process by the solvent extraction method.
또한, 본 발명에 따른 귀금속(팔라듐) 촉매의 제조방법은, 팔라듐(Pd)이 함유된 무기산 수용액을 methyltheophylline 및 chloroform와 혼합해서 귀금속 함유 유기용제를 준비하는 단계(S10); 및 상기 귀금속 함유 유기용제에 코디어라이트 허니컴(cordierite honeycomb) 또는 γ-Al2O3 (활성 알루미나)를 담근 후, 용제를 증발시켜서 귀금속이 담지된 지지체를 생성하는 단계(S20);를 포함하는 것이 가능하다.
In addition, the method for preparing a noble metal (palladium) catalyst according to the present invention comprises the steps of preparing a noble metal-containing organic solvent by mixing an aqueous inorganic acid solution containing palladium (Pd) with methyltheophylline and chloroform (S10); And dipping cordierite honeycomb or γ-Al 2 O 3 (active alumina) in the noble metal-containing organic solvent, and then evaporating the solvent to generate a support on which the noble metal is supported (S20). It is possible.
기타 실시예들의 구체적인 사항들은 상세한 설명 및 도면들에 포함되어 있다.
Specific details of other embodiments are included in the detailed description and the drawings.
상기한 본 발명은 귀금속 회수 공정의 중간 생성물로 얻어지는 귀금속 함유 유기용제를 이용해서 귀금속 촉매를 제조하는 것이 특징이며, 이와 같이 본 발명은 귀금속 회수 공정을 통해 회수되는 최종 제품이 아닌 중간 생성물을 촉매 제조에 직접 이용함으로써 촉매 제조 원가를 크게 절감할 수 있으며, 기존의 촉매보다도 성능이 우수한 촉매를 제조할 수 있다.
The present invention described above is characterized in that a noble metal catalyst is prepared using a noble metal-containing organic solvent obtained as an intermediate product of the noble metal recovery process. Thus, the present invention provides a catalyst for preparing an intermediate product, which is not a final product recovered through the noble metal recovery process. By directly using the catalyst, the cost of producing a catalyst can be greatly reduced, and a catalyst having better performance than a conventional catalyst can be manufactured.
도 1은 본 발명에 따라 γ-Al2O3 지지체에 0.1 중량비로 담지된 Pd 촉매의 톨루엔 연소 특성을 나타내는 그래프이고,
도 2는 본 발명에 따라 코디어라이트 허니컴 지지체에 0.1 중량비로 담지된 Pd 촉매의 톨루엔 연소 특성을 나타내는 그래프이고,
도 3은 본 발명에 따라 γ-Al2O3 지지체에 0.1 중량비로 담지된 Pd 촉매의 SEM 사진이다.1 is a graph showing toluene combustion characteristics of a Pd catalyst supported on a γ-Al 2 O 3 support in a weight ratio of 0.1 according to the present invention,
2 is a graph showing toluene combustion characteristics of a Pd catalyst supported on a cordierite honeycomb support in a weight ratio of 0.1 according to the present invention,
3 is a SEM photograph of a Pd catalyst supported on a γ-Al 2 O 3 support in a weight ratio of 0.1 according to the present invention.
이하에서는 본 발명의 바람직한 하나의 실시형태를 첨부된 도면을 참조하여 상세하게 설명하기로 한다.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
본 발명은 귀금속 촉매의 제조방법에 대한 것으로, 상세하게는 귀금속이 함유된 폐기물을 무기산과 혼합하여 귀금속 함유 수용액을 준비하는 단계(S10); 상기 준비한 귀금속 함유 수용액을 추출제 및 유기용제와 혼합해서 귀금속 함유 유기용제를 제조하는 단계(S20); 및 상기 제조한 귀금속 함유 유기용제에 지지체를 담근 후, 용제를 증발시켜서 귀금속이 담지된 지지체를 생성하는 단계(S30);를 포함하는 것이다.The present invention relates to a method for preparing a noble metal catalyst, specifically, mixing a waste containing a noble metal with an inorganic acid to prepare an aqueous solution containing a noble metal (S10); Preparing a noble metal-containing organic solvent by mixing the prepared noble metal-containing aqueous solution with an extractant and an organic solvent (S20); And dipping the support in the prepared noble metal-containing organic solvent, and then evaporating the solvent to generate a support in which the noble metal is supported (S30).
예를 들어, 귀금속(Pt, Pd, Rh, Ru 등)을 함유하는 폐기물(폐촉매, 반도체 폐기물, 의료용 폐기물 등)을 무기산에 용해시킨 수용액에 유기용제를 사용하여 귀금속을 추출한 다음, 그 귀금속이 함유된 유기용제를 사용하여 SiO2, Al2O3, SiO2-Al2O3, TiO2, zeolite, codierite honeycomb 등의 지지체에 상기 귀금속을 담지함으로써, 귀금속 촉매를 제조하는 것이다. 이러한 본 발명은 용매추출법에 의한 귀금속 회수 공정의 초기 단계에 얻어지는 귀금속 함유 유기용제를 귀금속 촉매 제조에 직접 이용한 것이 특징이다.
For example, a precious metal is extracted using an organic solvent in an aqueous solution in which wastes containing precious metals (Pt, Pd, Rh, Ru, etc.) are dissolved in an inorganic acid. The noble metal catalyst is prepared by supporting the noble metal on a support such as SiO 2 , Al 2 O 3 , SiO 2 -Al 2 O 3 , TiO 2 , zeolite, codierite honeycomb, or the like using an organic solvent contained therein. The present invention is characterized in that the noble metal-containing organic solvent obtained in the initial stage of the noble metal recovery process by the solvent extraction method was used directly in the preparation of the noble metal catalyst.
먼저, 귀금속 함유 수용액을 준비하는 단계(S10)는 귀금속 촉매 제조를 위한 원료물질을 준비하는 것으로, 본 발명에서는 특별히 귀금속이 함유된 폐기물을 이용하는 것이 특징이다. 상기 귀금속이 함유된 폐기물은 귀금속이 함유된 폐촉매, 반도체 폐기물 및 의료용 폐기물 중에서 선택된 하나 이상인 것일 수 있다. First, preparing a precious metal-containing aqueous solution (S10) is to prepare a raw material for preparing a precious metal catalyst, in the present invention is characterized by using a waste containing the precious metal in particular. The precious metal-containing waste may be at least one selected from a spent catalyst containing a precious metal, semiconductor waste, and medical waste.
고체상태인 폐기물에서 귀금속을 직접 유기용제로 추출할 수는 없는 바, 본 발명에서는 특별히 귀금속이 함유된 폐기물을 무기산과 혼합하여 귀금속 함유 수용액을 준비하는 것이다. 여기서, 상기 무기산은 염산, 질산, 황산, 불산, 왕수 등을 이용할 수 있다.
In the present invention, it is not possible to directly extract a noble metal from an organic solid waste. In the present invention, a noble metal-containing aqueous solution is prepared by mixing a waste containing a noble metal with an inorganic acid. The inorganic acid may be hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, aqua regia, or the like.
그런 다음, 본 발명은 귀금속 함유 유기용제를 제조하는 단계(S10)를 거친다. 즉, 상기 준비한 귀금속 함유 수용액을 추출제 및 유기용제와 혼합해서 귀금속 함유 유기용제를 제조하는 것이다. Then, the present invention goes through the step (S10) of preparing a noble metal-containing organic solvent. That is, the noble metal-containing organic solvent is prepared by mixing the prepared noble metal-containing aqueous solution with an extractant and an organic solvent.
본 발명은 기존의 용매추출 방법 중에 귀금속 성분의 선택적 추출이 가능한 방법을 적용하여, 귀금속 성분을 유기용제로 추출하고, 이 용제를 원료물질로 이용하는 것을 특징으로 하는바, 특정 귀금속을 추출하기 위한 추출제 및 유기용제는 특별히 제한되는 일이 없이 이 기술분야에 알려진 모든 것을 포함한다. 예를 들어, 팔라듐을 추출하기 위하여 추출제로 methyltheophylline을 이용할 수 있고, 유기용제로는 Chloroform, Toluene, MIBK, TBP, TOP, ethylhexanol 등을 단독 또는 혼합해서 사용함으로써, 수용액 상의 귀금속을 유기용제 상으로 추출하는 것이 가능하다. The present invention is characterized by extracting a precious metal component with an organic solvent by applying a method capable of selective extraction of the precious metal component in the existing solvent extraction method, using the solvent as a raw material, extraction for extracting a specific precious metal Agents and organic solvents include all known in the art without particular limitation. For example, methyltheophylline may be used as an extractant to extract palladium, and noble metals in an aqueous solution may be extracted onto an organic solvent by using Chloroform, Toluene, MIBK, TBP, TOP, ethylhexanol, or the like as an organic solvent alone or in combination. It is possible to.
또한, 상기 귀금속 함유 유기용제는 종래의 용매추출법에 의한 귀금속 회수 공정에서 얻어지는 중간 생성물일 수 있다. 예를 들어, 귀금속이 함유된 폐기물을 무기산 용액에 녹인 후 용매추출법에 의해 귀금속 성분을 선택적으로 유기용제 상으로 추출한 수용액일 수 있다.
In addition, the noble metal-containing organic solvent may be an intermediate product obtained in the noble metal recovery process by a conventional solvent extraction method. For example, it may be an aqueous solution in which the noble metal-containing waste is dissolved in an inorganic acid solution and then the noble metal component is selectively extracted into an organic solvent by a solvent extraction method.
이어서, 본 발명은 상기와 같이 제조된 귀금속 함유 유기용제를 이용해서 귀금속이 담지된 지지체를 생성하는 단계(S30);를 거친다. 즉, 상기 귀금속 함유 유기용제에 지지체를 담근 후, 용제를 증발시켜서 귀금속이 담지된 지지체를 생성하는 것이다. Subsequently, the present invention uses a noble metal-containing organic solvent prepared as described above to produce a support on which the noble metal is supported (S30). In other words, after the support is immersed in the noble metal-containing organic solvent, the solvent is evaporated to produce a support on which the noble metal is supported.
귀금속 촉매의 제조는 주로 금속산화물 계의 지지체(SiO2, Al2O3, SiO2-Al2O3, TiO2, zeolite, codierite honeycomb 등)에 귀금속 촉매 성분(Pt, Pd, Rh, Ru 등)을 수용액 또는 유기용제에 녹인 후에 함침법으로 담지시켜 제조된다. 이 때 사용되는 종래의 귀금속 시약은 대부분 귀금속 자체보다도 오히려 가격이 높은 제품이다. 본 발명은 바로 상기 귀금속 시약 대신에 귀금속 회수 공정에서 얻은 귀금속 함유 유기용제를 이용하는 것이 특징이다. The production of noble metal catalysts mainly consists of metal oxide-based supports (SiO 2 , Al 2 O 3 , SiO 2 -Al 2 O 3 , TiO 2 , zeolite, codierite honeycomb, etc.) and precious metal catalyst components (Pt, Pd, Rh, Ru, etc.). ) Is prepared by dissolving in an aqueous solution or an organic solvent and impregnated with impregnation. Conventional precious metal reagents used at this time are mostly expensive products rather than precious metals themselves. The present invention is characterized by using a noble metal-containing organic solvent obtained in the noble metal recovery process instead of the noble metal reagent.
본 발명에서 사용되는 지지체는 특별히 제한되는 일이 없이 이 기술분야에 알려진 다양한 지지체를 모두 포함하고, 함침법에 의해 귀금속 촉매를 제조하는 방법 또한 특별히 제한되지 않는다. The support used in the present invention includes all the various supports known in the art without particular limitation, and the method for producing the noble metal catalyst by the impregnation method is also not particularly limited.
예를 들어, 상기 귀금속 함유 유기용제에 코디어라이트 허니컴(cordierite honeycomb) 또는 γ-Al2O3 (활성 알루미나)를 담근 후, 용제를 증발시켜서 귀금속이 담지된 지지체를 생성하는 것이 가능하다.
For example, after immersing cordierite honeycomb or γ-Al 2 O 3 (activated alumina) in the noble metal-containing organic solvent, it is possible to evaporate the solvent to produce a support on which the noble metal is supported.
이후에는, 귀금속이 담지된 촉매를 건조하고, 소성하는 단계를 더 포함할 수도 있다.
Thereafter, the method may further include drying and calcining the catalyst on which the noble metal is supported.
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해 될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며, 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.
The present invention may be better understood by the following examples, which are for the purpose of illustrating the invention and are not intended to limit the scope of protection defined by the appended claims.
실시예Example
1: 귀금속 함유 유기용제를 이용한 귀금속 촉매의 제조 1: Preparation of Precious Metal Catalyst Using Precious Metal-Containing Organic Solvent
실시예Example 1-1: 귀금속 함유 유기용제의 준비 1-1: Preparation of Precious Metal-Containing Organic Solvent
1.0~5.0 M PdCl2 및 0.1~0.25 M HCl을 함유하는 수용액 30 ml를 0.1 M methyltheophylline이 녹아 있는 chloroform (0~10 중량%의 ethylhexanol 함유) 30 ml와 섞어서 30분간 교반하였다. 교반 후에 분액깔대기를 사용하여, 유기층과 수용액 층을 분리하였다. 30 ml of an aqueous solution containing 1.0-5.0 M PdCl 2 and 0.1-0.25 M HCl was mixed with 30 ml of chloroform (containing 0-10 wt% ethylhexanol) in 0.1 M methyltheophylline and stirred for 30 minutes. After stirring, a separatory funnel was used to separate the organic layer and the aqueous layer.
여기서, ICP를 사용하여 수용액 층에 남아 있는 Pd 농도를 분석함으로써, 유기층으로의 추출율을 구한 결과, 상기 실험 조건에서 모두 99% 이상의 Pd 추출율을 나타냈다.
Here, by analyzing the concentration of Pd remaining in the aqueous solution layer using the ICP, the extraction rate into the organic layer was determined, and all showed Pd extraction rate of 99% or more under the experimental conditions.
실시예Example 1-2: 귀금속이 1-2: precious metals 담지된Supported 지지체 생성 Create support
상기 실시예 1-1에서 유기층으로 분리한 Pb 함유 유기용제를 이용하여, 귀금속이 담지된 지지체를 제조하였다. Using a Pb-containing organic solvent separated into an organic layer in Example 1-1, a support on which a noble metal was supported was prepared.
지지체로는 cordierite honeycomb (코디어라이트 허니컴) 또는 γ-Al2O3 (활성 알루미나)를 사용하였다. 지지체에 대한 Pd 성분 담지량이 0.1 wt%가 되도록 계산된 양 만큼의 Pd 함유 유기용제에, 지지체 1 ml를 담근 후에 용제를 증발시켜 Pd 성분을 지지체에 담지하였다. Cordierite honeycomb (cordierite honeycomb) or γ-Al 2 O 3 (active alumina) was used as a support. The Pd component was supported on the support by dipping 1 ml of the support into the Pd-containing organic solvent so that the amount of Pd component supported on the support was 0.1 wt%, and then evaporating the solvent.
그런 다음, Pd가 담지된 촉매를 120℃에서 24시간 건조하고, 550℃에서 1시간 소성하였다.
Then, Pd-supported catalyst was dried at 120 ° C. for 24 hours and calcined at 550 ° C. for 1 hour.
비교예Comparative example
1: One:
PdClPdCl
22
시약을 이용한 귀금속 촉매의 제조 Preparation of Precious Metal Catalysts Using Reagents
본 발명과의 비교를 위하여 PdCl2 시약을 녹인 수용액을 Pb 함유 유기용제로 이용하여, 상기 실시예 1-2와 같은 방법으로 귀금속이 담지된 지지체를 제조하였다.
For comparison with the present invention, a support on which a noble metal was loaded was prepared in the same manner as in Example 1-2 using an aqueous solution in which PdCl 2 reagent was dissolved as a Pb-containing organic solvent.
실험예Experimental Example
1: 톨루엔 연소반응 1: toluene combustion reaction
톨루엔 연소반응을 위하여, 상기 실시예 1 및 비교예 1에 따라 제조된 촉매를 반응에 사용하기 전에 10% 수소, 90% 질소 분위기 가스를 흘려보내면서 400℃에서 1시간 수소환원 처리를 하였다. For the toluene combustion reaction, hydrogen reduction treatment was carried out at 400 ° C. for 1 hour while flowing 10% hydrogen and 90% nitrogen atmosphere gas before using the catalysts prepared according to Example 1 and Comparative Example 1 in the reaction.
그런 다음, 환원처리된 촉매를 사용하여 톨루엔 연소반응을 실시하였다. 반응조건은 톨루엔 농도 약 270 ppm, 공간속도(SV) 50000 h-1로 조절하였으며, 100℃~450℃ 범위에서 50℃ 간격으로 톨루엔 연소반응 결과를 분석하였다.
Then, toluene combustion was carried out using a reduced catalyst. The reaction conditions were adjusted to about 270 ppm toluene concentration, 50000 h -1 of space velocity (SV), and the results of toluene combustion were analyzed at 50 ° C intervals in the range of 100 ° C to 450 ° C.
그 결과는 도 1 ~ 도 3에 나타낸 바와 같다. The results are as shown in Figs.
도 1은 γ-Al2O3 지지체에 0.1 중량비로 담지된 Pd 촉매의 톨루엔 연소 특성을 나타내고 있고, 여기서 (가)는 본 발명에 따라 Pd 추출 유기용제를 이용한 촉매이고, (나)는 비교예에 따라 PdCl2 수용액을 이용한 촉매의 경우이다. 도 1에 나타난 바와 같이, Pd 추출 유기용제를 사용하여 촉매를 제조한 경우가 PdCl2 수용액을 사용한 경우에 비하여 월등히 높은 촉매 활성을 나타냈다. 1 shows toluene combustion characteristics of a Pd catalyst supported on a γ-Al 2 O 3 support in a 0.1 weight ratio, wherein (a) is a catalyst using a Pd-extracted organic solvent according to the present invention, and (b) is a comparative example. This is the case with a catalyst using an aqueous PdCl 2 solution. As shown in FIG. 1, the catalyst prepared using the Pd-extracted organic solvent showed significantly higher catalytic activity than the case of using the aqueous PdCl 2 solution.
도 2는 코디어라이트 허니컴 지지체에 0.1 중량비로 담지된 Pd 촉매의 톨루엔 연소 특성을 나타내고 있고, 여기서 (가)는 본 발명에 따라 Pd 추출 유기용제를 이용한 촉매이고, (나)는 비교예에 따라 PdCl2 수용액을 이용한 촉매의 경우이다. 도 2에 나타난 바와 같이, 전체적으로 γ-Al2O3 지지체에 비하여 톨루엔 연소 성능이 우수했으며, 코디어라이트 허니컴의 경우에도 Pd 추출 유기용제를 사용하여 촉매를 제조한 경우에 더 높은 연소촉매 활성을 나타냈다. Figure 2 shows the toluene combustion characteristics of the Pd catalyst supported by 0.1 weight ratio on the cordierite honeycomb support, wherein (a) is a catalyst using a Pd extraction organic solvent according to the present invention, (b) according to a comparative example This is the case with a catalyst using an aqueous PdCl 2 solution. As shown in FIG. 2, the toluene combustion performance was superior to the γ-Al 2 O 3 support as a whole, and even in the case of cordierite honeycomb, when the catalyst was prepared using Pd-derived organic solvent, higher combustion catalyst activity was observed. Indicated.
도 3은 γ-Al2O3 지지체에 0.1 중량비로 담지된 Pd 촉매의 SEM 사진이고, 여기서 (가)는 본 발명에 따라 Pd 추출 유기용제를 이용한 촉매이고, (나)는 비교예에 따라 PdCl2 수용액을 이용한 촉매의 경우이다. 주사전자현미경(SEM)을 사용하여 Pd/γ-Al2O3 촉매 표면의 형태를 관찰한 결과, PdCl2 수용액을 사용한 (나)의 경우에는 지지체 표면에 Pd로 추정되는 상당히 큰 입자가 관찰되었으나, Pd 추출 유기용제를 사용하여 제조된 (가) 촉매의 경우에는 부분적으로 응집 현상은 보이지만 매우 작은 입자가 담지되어 있었다. 부분적으로 응집되어 있는 입자도 완전히 뭉쳐진 것이 아니라 작은 입자들이 스펀지 형태로 존재하고 있었다. 이와 같이 본 발명에 따른 Pd 추출 유기용제를 사용한 경우 Pd 입자의 응집을 억제하고 분산성을 유지함으로써 높은 촉매 활성을 나타내고 있음을 다시 한번 확인할 수 있다.
3 is a SEM photograph of a Pd catalyst loaded on a γ-Al 2 O 3 support in a 0.1 weight ratio, wherein (A) is a catalyst using a Pd-extracted organic solvent according to the present invention, and (B) is PdCl according to a comparative example. It is the case of the catalyst using 2 aqueous solution. As a result of observing the morphology of the surface of the Pd / γ-Al 2 O 3 catalyst using a scanning electron microscope (SEM), in the case of (b) using an aqueous PdCl 2 solution, a considerably large particle of Pd was observed on the surface of the support. In the case of the (a) catalyst prepared using the Pd-extracted organic solvent, agglomeration was partially observed but very small particles were supported. Partially agglomerated particles were not completely agglomerated, but small particles were present in the form of sponges. As such, when the Pd-extracted organic solvent according to the present invention is used, it can be confirmed that the catalyst exhibits high catalytic activity by suppressing aggregation of Pd particles and maintaining dispersibility.
한편, 상기에서는 본 발명을 특정의 바람직한 실시예에 관련하여 도시하고 설명하였지만, 이하의 특허청구범위에 의해 마련되는 본 발명의 기술적 특징이나 분야를 이탈하지 않는 한도 내에서 본 발명이 다양하게 개조 및 변화될 수 있다는 것은 당업계에서 통상의 지식을 가진 자에게 명백한 것이다.
On the other hand, while the present invention has been shown and described with respect to certain preferred embodiments, the invention is variously modified and modified without departing from the technical features or fields of the invention provided by the claims below It will be apparent to those skilled in the art that such changes can be made.
본 발명에서와 같이 용매추출법으로 회수되는 최종 제품이 아닌 중간 제품을 촉매 제조에 직접 이용함으로써 촉매 제조 원가를 크게 절감할 수 있으며, 기존의 촉매보다도 성능이 우수한 촉매를 제조할 수 있는 새로운 촉매의 제조 방법을 제공할 수 있다. 이와 같이 제조된 촉매는 VOC 연소촉매, 자동차촉매, 석유화학공업용 촉매 등에 적용될 수 있을 것으로 기대된다.
As in the present invention, by directly using the intermediate product, which is not the final product recovered by the solvent extraction method, in the production of the catalyst, it is possible to greatly reduce the cost of producing the catalyst, and to prepare a new catalyst that can produce a catalyst having better performance than the existing catalyst. It may provide a method. The catalyst thus prepared is expected to be applicable to VOC combustion catalysts, automotive catalysts, petrochemical industry catalysts and the like.
Claims (4)
상기 준비한 귀금속 함유 수용액을 추출제 및 유기용제와 혼합해서 귀금속 함유 유기용제를 제조하는 단계(S20); 및
상기 제조한 귀금속 함유 유기용제에 지지체를 담근 후, 용제를 증발시켜서 귀금속이 담지된 지지체를 생성하는 단계(S30);를 포함하는 귀금속 촉매의 제조방법.
Preparing a precious metal-containing aqueous solution by mixing the waste containing the precious metal with an inorganic acid (S10);
Preparing a noble metal-containing organic solvent by mixing the prepared noble metal-containing aqueous solution with an extractant and an organic solvent (S20); And
And dipping the support in the prepared noble metal-containing organic solvent, and then evaporating the solvent to generate a support in which the noble metal is supported (S30).
The method of claim 1, wherein the noble metal-containing waste is at least one selected from noble metal-containing waste catalyst, semiconductor waste, and medical waste.
The method for producing a noble metal catalyst according to claim 1, wherein the noble metal-containing organic solvent is an intermediate product of the noble metal recovery step by a solvent extraction method.
상기 귀금속 함유 유기용제에 코디어라이트 허니컴(cordierite honeycomb) 또는 γ-Al2O3 (활성 알루미나)를 담근 후, 용제를 증발시켜서 귀금속이 담지된 지지체를 생성하는 단계(S20);를 포함하는 팔라듐 촉매의 제조방법.
Preparing a noble metal-containing organic solvent by mixing an aqueous inorganic acid solution containing palladium (Pd) with methyltheophylline and chloroform (S10); And
Palladium comprising; immersing cordierite honeycomb or γ-Al 2 O 3 (active alumina) in the noble metal-containing organic solvent, and then evaporating the solvent to generate a support in which the noble metal is supported (S20). Method for preparing a catalyst.
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