WO2015194758A1 - Method for molding multipurpose catalyst having bar shape, and catalyst prepared by method - Google Patents

Method for molding multipurpose catalyst having bar shape, and catalyst prepared by method Download PDF

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WO2015194758A1
WO2015194758A1 PCT/KR2015/004710 KR2015004710W WO2015194758A1 WO 2015194758 A1 WO2015194758 A1 WO 2015194758A1 KR 2015004710 W KR2015004710 W KR 2015004710W WO 2015194758 A1 WO2015194758 A1 WO 2015194758A1
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catalyst
slurry
deionized water
molding method
molding
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PCT/KR2015/004710
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French (fr)
Korean (ko)
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김정현
강인용
김병준
조성원
박아름
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한밭대학교 산학협력단
에이치앤파워(주)
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Publication of WO2015194758A1 publication Critical patent/WO2015194758A1/en

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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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J37/04—Mixing
    • 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
    • B01J37/08—Heat treatment

Definitions

  • the present invention relates to a method for forming a catalyst having a variety of shapes, such as a rod, more specifically using a mold Versatile for making ceramic thick films such as jelly into plates, cutting catalysts into various shapes and sizes, and then molding them quickly and in large quantities to desired sizes and shapes through two stages of sintering. It relates to a method for producing a catalyst.
  • a fuel cell is a power generation system that converts chemical energy directly into electrical energy by using a fuel of carbon hydrogen contained in a hydrocarbon-based material such as methanol, ethanol, and natural gas, and an oxidant of oxygen or air.
  • a fuel cell basically includes a stack, a fuel processor, a fuel tank, a fuel pump, and the like to form a system.
  • the fuel in the fuel tank is supplied to the fuel processing device with a fuel pump, and the fuel processing device reforms and converts the supplied fuel to generate hydrogen and supply the hydrogen to the stack.
  • the stack receives the hydrogen and reacts with oxygen electrochemically to generate electrical energy.
  • TBM tertiary butyl meraptan
  • THT Tetrahydrothiophene
  • a fuel cell in order to remove sulfur present in a small amount in a hydrocarbon, a fuel cell must be provided with a desulfurization catalyst.
  • a carrier of various materials such as Korean Patent Publication No. 10-2013-0072520 (2013.07.02), was formed.
  • a porous metal filter that can be used at high temperatures, or to manufacture a porous microbial ceramic carrier including fly ash and diatomaceous earth as in Korea Patent Publication No. 1999-014412 (1999.02.25) to remove odors, Japan Patent Publication No.
  • 9-164334 (1997.06.24) contained molybdenum as an oxide on a carrier of an inorganic oxide, dried, calcined, and then calcined again by adding other materials such as nickel, but used as a catalyst for desulfurization. Since they are manufactured using a press method during molding, there is a limit in shape and size thereof.
  • the shape and size of the catalyst are generally manufactured by using a press method, but in this case, it is not easy to control the size of the prepared catalyst.
  • press working there is a problem in that it is difficult to produce a catalyst having a small or complicated shape.
  • the present invention is to produce a ceramic thick film that is soft and flexible, such as jelly in the shape of a plate having a bar shape chocolate bar It is intended to provide a catalyst having a certain hardness through the heat treatment such as sintering after cutting into various shapes and sizes.
  • the method for forming a multi-purpose catalyst having a chocolate bar form for realizing the above object, after adding a metal oxide powder, a catalyst support oxide powder, a sintering accelerator and deionized water, Mixing to prepare a slurry; Adjusting the amount of deionized water and powder added to the slurry to adjust the pH and slurry viscosity, after mixing the slurry in a mixer, to remove the deionized water to form a semi-dry state of jelly form, the semi-dry Maintaining the slurry in a state in a dryer for 2 to 5 hours at 50 ⁇ 70 °C drying, characterized in that the multi-purpose catalyst molding method consisting of the step of sintering the dried catalyst through the first, second heat treatment.
  • the present invention relates to a multipurpose catalyst molding method characterized by further comprising the step of cutting with punching or knife before the drying step.
  • the step of adjusting the viscosity relates to a multi-purpose catalyst molding method characterized in that the pH is in the range of 6 to 8.
  • the metal oxide powder relates to a multi-purpose catalyst molding method characterized in that the 10 to 50 wt%, 0.1 to 5 wt% residual catalyst support oxide powder sintering accelerator.
  • the first heat treatment relates to a multipurpose catalyst molding method characterized by maintaining at 250 to 500 ° C. for 1 to 3 hours.
  • the second heat treatment relates to a multipurpose catalyst molding method characterized by maintaining at 500 to 1000 ° C for 1 to 3 hours.
  • the binder relates to a multipurpose catalyst molding method characterized by being an aqueous binder.
  • the mixer relates to a multipurpose catalyst molding method characterized by being a ball mill using zirconia balls.
  • the present invention relates to a multipurpose catalyst prepared by the above molding method.
  • the multi-purpose catalyst molding method having a chocolate bar shape related to an embodiment of the present invention is a wide plate-shaped jelly type
  • the semi-solidified catalyst can be produced in a desired size or shape by punching or by cutting with a knife, as well as a quick and large-scale production of small ceramic moldings with simple shapes.
  • the heat treatment may be performed while adding a suitable binder material during the heat treatment, so that the pore amount of the finished catalyst may be appropriately adjusted.
  • Figure 2 is a photograph of the completed catalyst after the drying and heat treatment of the present invention.
  • FIG. 1 (a) ⁇ (d) is a view showing a multi-purpose catalyst manufacturing process in order according to an embodiment of the present invention, as shown in Figure 1, the support oxide and catalyst of HDX (Hydro De Sulfurization) catalyst After the oxide was mixed with deionized water to prepare a slurry, a slurry catalyst was uniformly mixed using a ball mill using zirconia balls. The amount of deionized water is adjusted while adjusting the PH in consideration of the type of binder system such as the metal oxide powder and the catalyst support oxide powder to be added, and the viscosity of the slurry is changed according to the change of the pH so that the deionized water can have the desired viscosity. Input while adjusting the amount of.
  • HDX Hydro De Sulfurization
  • the pH of the slurry is controlled by adjusting the amount of deionized water added to the additive during the preparation of the slurry.
  • the amount of each powder added to the slurry is 10 to 50 wt% of the metal oxide powder, 0.1 to 5 wt% of the sintering accelerator powder, and all of them are catalyst support oxides.
  • the slurry is prepared by mixing deionized water with the weighed powder. .
  • the metal oxide not only NiO used as a desulfurization catalyst but also metal oxides such as MoO 3 , CoO, and NiO may be mixed and added.
  • the amount of the metal oxide alone or mixed is added at 10 wt% or less, the function as a catalyst is remarkably reduced, and when it is added at 50 wt% or more, the strength of the catalyst is weakened and the brittleness is worsened.
  • Sintering accelerator is added 0.1 ⁇ 5 wt% of SiO 2 , when the sintering accelerator is added less than 0.1 wt% has little effect on the sintering promotion, if it exceeds 5 wt%, the strength is too high according to the sintering of the finished catalyst It is high, and the function as a catalyst falls.
  • the catalyst support oxide is to maintain the appropriate form and strength of the prepared catalyst is to be adjusted according to the addition amount of the metal oxide powder.
  • the pH was maintained at 7 during the preparation of the slurry, which can be controlled by adding deionized water. If the pH is less than 6, as the binder system is affected by the PH, the viscosity of the entire slurry is lowered, not only is it time consuming to form the catalyst before sintering, but also does not reach the desired final sintered body shape. On the other hand, when the pH of the slurry exceeds 8, the viscosity becomes high and it is difficult to maintain the jelly type plate shape. Therefore, the binder is additionally supplied depending on the PH, and thus the manufacturing order is changed, which is different from the binder added based on the PH value 7 and the manufacturing method thereof.
  • the semi-dried catalyst was re-dried at a temperature of 50-70 ° C. for 2-4 hours to remove deionized water as shown in the photograph of FIG.
  • deionized water can be removed in a short time, but cracks and voids are generated on the surface, which affects the shape of the final sintered body. Ionized water will not be removed in the desired amount within 2 to 4 hours.
  • the dried plate-shaped slurry can be used for punching and when a catalyst in the form of a rod is cut into a certain size and shape as shown in FIG. 1 (d) by using a tool having a sharp surface.
  • the catalyst specimen in the form of chocolate cut to a certain size is subjected to heat treatment in two steps.
  • the first heat treatment is maintained for 1 to 3 hours at 250 ⁇ 350 °C °C per minute By using the temperature rise condition of 5 degreeC Slowly heat treatment.
  • the reason for the heat treatment at the temperature of 250 ⁇ 350 °C is to remove the polymer aqueous binder constituting the binder system to maintain the semi-sintered state as a pretreatment process for sintering.
  • the catalyst specimen in a semi-sintered state is heated to perform a second heat treatment.
  • the second heat treatment is to maintain the oxide powder added by maintaining for 1 to 3 hours at 500 ⁇ 800 °C sintered to become a completed catalyst as shown in the photo of FIG.
  • the desulfurization catalyst capable of producing a large amount of ceramic shaped articles in a simple shape can easily separate sulfur compounds in carbon dioxide, which are difficult to separate, and thus include a liquid including a desulfurizer, which is a major component for completing a fuel cell system.
  • a liquid including a desulfurizer which is a major component for completing a fuel cell system.
  • ⁇ -Al 2 O 3 gamma alumina
  • Ni metal powder ⁇ -Al 2 O 3
  • SiO 2 ⁇ -Al 2 O 3
  • 50 wt% of ⁇ -Al 2 O 3 49 wt% of NiO powder, and 1 wt of SiO 2.
  • the pH is measured to be 6.58, so additional deionized water, ⁇ -Al 2 O 3 , and neutralizing agent are added to adjust the pH to 7. Mix them for several minutes and then add the binder.
  • the binder and the neutralizing agent are mixed with deionized water, mixed for several minutes, and then weighed powders are added. Thereafter, the mixed slurry was injected into a mold, and then a catalyst in the form of a rod was prepared by using a tool having a sharp surface in accordance with a desired shape and size. After the molding process was completed, the sample was dried at 60 ° C. for 3 hours, and then heat treated. In order to remove the added aqueous binder system, the first heat treatment was performed at 300 ° C. for 2 hours, and then the second heat treatment was performed at 800 ° C. for 1 hour.
  • a catalyst was prepared in substantially the same manner as in Example 1 except that the metal oxide powder was changed to 24 wt% of MoO 3 powder, 7 wt% of CoO powder, and 69 wt% of gamma alumina.
  • a catalyst was prepared in substantially the same manner as in Example 1, except that the metal oxide powder was changed to 24 wt% of MoO 3 powder, 8 wt% of NiO powder, and 68 wt% of gamma alumina.
  • Example 1 Except for changing the metal oxide powder to 87 wt% Fe 2 O 3 powder, 8 wt% Cr 2 O 3 powder, 2 wt% CuO powder 3 wt% other powder in order to prepare a general reforming catalyst in Example 1 was prepared in substantially the same manner as in Example 1.
  • the catalyst was prepared in substantially the same manner as in Example 1, except that the catalyst was dried at 100 ° C. for 1 hour to prepare a semi-dried catalyst.
  • the catalyst was prepared using the same method until the deionized water removal and the first heat treatment of the slurry prepared in Example 1, and the catalyst was prepared without performing the second heat treatment.
  • the brittleness was measured by simply pressurizing the catalyst prepared by hand, and expressed as 1 to 5 depending on the degree of the brittleness.
  • the method of preparing a catalyst having a chocolate bar form as described above is not limited to the configuration and operation of the embodiments described above.
  • the above embodiments may be configured such that various modifications may be made by selectively combining all or part of the embodiments.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The present invention relates to a method for molding a catalyst having various shapes such as a bar and, more specifically, to a method for preparing a catalyst, capable of rapidly mass molding a catalyst into a desired size and shape by making a ceramic thick film, such as a jelly, into a plate, cutting a catalyst into various shapes and sizes, and then carrying out sintering treatment. Provided is the method for preparing a catalyst, comprising the steps of: preparing a slurry by adding a metal oxide powder, a binder and deionized water, and then mixing the same; adjusting the pH and the viscosity of the slurry by controlling the amount of the powder to be added to the slurry; forming a semi-dried state by mixing the slurry in a mixer, and then removing deionized water; drying the slurry in a semi-dried state by maintaining the same in a drier at 50-70°C for 2-5 hours; and sintering the dried catalyst through a first and a second heat treatment.

Description

막대 형상을 갖는 다목적용 촉매 성형방법 및 이의 방법으로 제조된 촉매. Multi-purpose catalyst molding method having a rod shape and a catalyst prepared by the method.
본 발명은 막대 등 다양한 형상을 갖는 촉매를 성형하는 방법에 관한 것으로서, 더욱 상세하게는 조형틀을 이용하여 젤리와 같은 세라믹 후막을 판상으로 제조한 후 다양한 형태와 크기로 촉매를 절단한 다음, 두 단계의 소결처리를 거쳐 원하는 크기 및 형상으로 신속하고 대량으로 성형할 수 있는 다목적용 촉매 제조방법에 관한 것이다.The present invention relates to a method for forming a catalyst having a variety of shapes, such as a rod, more specifically using a mold Versatile for making ceramic thick films such as jelly into plates, cutting catalysts into various shapes and sizes, and then molding them quickly and in large quantities to desired sizes and shapes through two stages of sintering. It relates to a method for producing a catalyst.
연료전지(Fuel Cell)는 메탄올, 에탄올, 천연가스와 같은 탄화수소 계열의 물질 내에 함유되어 있는 탄소수소의 연료와 산소나 공기의 산화제를 이용하여 화학에너지를 직접 전기 에너지로 변환시키는 발전 시스템이다. 이러한 연료전지는 기본적으로 시스템을 구성하기 위하여 스택(STACK), 연료처리장치(FUEL PROCESSOR), 연료탱크, 연료펌프 등을 구비한다. 연료탱크 내의 연료를 연료펌프로 연료처리장치에 공급하고 연료처리장치는 공급된 연료를 개질 및 전환하여 수소를 발생시키고 그 수소를 스택으로 공급한다. 스택에서는 상기 수소를 공급받아 산소와 전기 화학적으로 반응시켜 전기에너지를 발생시킨다.A fuel cell is a power generation system that converts chemical energy directly into electrical energy by using a fuel of carbon hydrogen contained in a hydrocarbon-based material such as methanol, ethanol, and natural gas, and an oxidant of oxygen or air. Such a fuel cell basically includes a stack, a fuel processor, a fuel tank, a fuel pump, and the like to form a system. The fuel in the fuel tank is supplied to the fuel processing device with a fuel pump, and the fuel processing device reforms and converts the supplied fuel to generate hydrogen and supply the hydrogen to the stack. The stack receives the hydrogen and reacts with oxygen electrochemically to generate electrical energy.
이러한 연료전지에 공급연료로 탄화수소가 포함된 도시가스가 이용될 경우, 일반적으로 탄소수소 내에는 미량의 황이 포함되어 있는 것은 물론 사용되는 도시가스에는 부취제로 작용하는 황 화합물인 TBM(Tertiary Butyl Mercaptan)과 THT(Tetrahydrothiophene)가 3:7의 비율로 약 15ppm 함유되어 있기 때문에, 연료전지의 연료극 뿐만 아니라 연료 개질 촉매의 황피독이 필연적으로 발생하게 되어 연료전지의 성능감소 뿐만 아니라 연료개질기를 포함한 연료전지 시스템의 성능하락의 주요인이 된다. 따라서 황이 포함된 연료를 연료전지로 사용하기 위해서는 상기 황화물의 제거가 필수적이다. When a city gas containing hydrocarbons is used as a feed fuel in such a fuel cell, tertiary butyl meraptan (TBM), which is a sulfur compound that acts as a deodorant in addition to containing trace amounts of sulfur in carbon dioxide, is generally used. And about 15 ppm of THT (Tetrahydrothiophene) in a ratio of 3: 7, not only the fuel cell anode but also the sulfur poisoning of the fuel reforming catalyst inevitably occurs, thereby reducing the performance of the fuel cell as well as the fuel cell system including the fuel reformer. It is a major cause of the performance degradation. Therefore, in order to use a fuel containing sulfur as a fuel cell, the removal of the sulfide is essential.
이와 같이, 탄화수소 내에 소량으로 존재하는 황을 제거하기 위하여 연료전지에는 탈황촉매가 제공되어야 하며, 종래에는 국내 공개특허공보 10-2013-0072520호(2013.07.02)와 같이 여러 재질의 담체를 성형과정에서 이용하여 고온에서 사용 가능한 다공질 금속필터를 제조하거나, 국내 공개특허공보 특1999-014412호(1999.02.25)와 같이 플라이 애쉬 및 규조토를 포함하는 다공성 미생물 세라믹 담체를 제조하여 악취를 제거하였으며, 일본 공개특허공보 평9-164334호(1997.06.24)는 무기산화물의 담체 상에 몰리브덴을 산화물로 함유시켜 건조, 소성한 후에 니켈 등 기타물질을 첨가하여 다시 소성하여 탈황용 촉매로 사용하였으나, 이러한 촉매들은 성형 시, 프레스 방법을 이용하여 제작하기 때문에 형태 및 그 크기에 제한이 있게 된다. As such, in order to remove sulfur present in a small amount in a hydrocarbon, a fuel cell must be provided with a desulfurization catalyst. In the prior art, a carrier of various materials, such as Korean Patent Publication No. 10-2013-0072520 (2013.07.02), was formed. In order to manufacture a porous metal filter that can be used at high temperatures, or to manufacture a porous microbial ceramic carrier including fly ash and diatomaceous earth as in Korea Patent Publication No. 1999-014412 (1999.02.25) to remove odors, Japan Patent Publication No. 9-164334 (1997.06.24) contained molybdenum as an oxide on a carrier of an inorganic oxide, dried, calcined, and then calcined again by adding other materials such as nickel, but used as a catalyst for desulfurization. Since they are manufactured using a press method during molding, there is a limit in shape and size thereof.
종래에는 탈황이나 탈취를 목적으로 하는 촉매를 제작하기 위해서는 일반적으로 프레스 방법을 이용하여 촉매 형상 및 크기를 용도에 맞게 제작하고 있으나, 이 경우에 제조되는 촉매의 크기를 조절하기도 용이하지 않다. 또한, 프레스 가공의 경우 소형이거나 복잡한 형상을 갖는 촉매를 제조하기에 어려운 문제점이 있었던 것이다.Conventionally, in order to manufacture a catalyst for the purpose of desulfurization or deodorization, the shape and size of the catalyst are generally manufactured by using a press method, but in this case, it is not easy to control the size of the prepared catalyst. In addition, in the case of press working, there is a problem in that it is difficult to produce a catalyst having a small or complicated shape.
상기와 같은 종래기술의 문제점을 해결하고자, 본 발명은 막대와 같은 초콜릿 바 형상을 갖는 판상의 모습으로 젤리와 같이 부드럽고 휘어지기 쉬운 세라믹 후막을 제작하여 다양한 형태와 크기로 절단한 다음, 소결과 같은 가열처리를 통해서 일정한 경도를 갖는 촉매를 제공하기 위한 것이다.In order to solve the problems of the prior art as described above, the present invention is to produce a ceramic thick film that is soft and flexible, such as jelly in the shape of a plate having a bar shape chocolate bar It is intended to provide a catalyst having a certain hardness through the heat treatment such as sintering after cutting into various shapes and sizes.
위에서 설명된 본 발명이 이루고자 하는 기술적 과제들은 예시의 목적을 위하여 개시된 것이고, 본 발명이 속한 기술 분야에서 통상의 지식을 가진 자라면 본 발명의 사상과 범위 안에서 다양한 수정, 변경, 부가가 가능한 것으로 이상에서 언급한 기술적 과제들로 제한되지 않는다.Technical problems to be achieved by the present invention described above are disclosed for the purpose of illustration, and those skilled in the art to which the present invention pertains various modifications, changes, and additions within the spirit and scope of the present invention. It is not limited to the technical challenges mentioned in.
상기 과제를 실현하기 위한 본 발명의 일실시예와 관련되는 초콜릿 바 형태를 갖는 다목적용 촉매를 성형하는 방법에 있어서, 금속산화물 분말과, 촉매 지지체 산화물 분말, 소결촉진제 및 탈이온수를 첨가한 후, 혼합하여 슬러리를 제조하는 단계; 상기 슬러리에 첨가되는 탈이온수 및 분말의 첨가량을 조절하여 PH 및 슬러리 점성을 조절하는 단계, 슬러리를 혼합기에서 혼합한 후, 탈이온수를 제거하여 젤리 형태의 반건조 상태를 형성하는 단계, 상기 반건조 상태의 슬러리를 50~70℃에서 2~5시간 건조기에 유지시켜 건조하는 단계, 상기 건조된 촉매를 제1, 2차 열처리를 통하여 소결하는 단계로 이루어진 다목적용 촉매 성형방법에 특징이 있는 것이다.In the method for forming a multi-purpose catalyst having a chocolate bar form according to an embodiment of the present invention for realizing the above object, after adding a metal oxide powder, a catalyst support oxide powder, a sintering accelerator and deionized water, Mixing to prepare a slurry; Adjusting the amount of deionized water and powder added to the slurry to adjust the pH and slurry viscosity, after mixing the slurry in a mixer, to remove the deionized water to form a semi-dry state of jelly form, the semi-dry Maintaining the slurry in a state in a dryer for 2 to 5 hours at 50 ~ 70 ℃ drying, characterized in that the multi-purpose catalyst molding method consisting of the step of sintering the dried catalyst through the first, second heat treatment.
또한 구체적으로는, 상기 건조하는 단계 전에 펀칭이나 나이프로 절단하는 단계를 더 포함하는 것에 특징이 있는 다목적용 촉매 성형방법에 관한 것이다.Also specifically, the present invention relates to a multipurpose catalyst molding method characterized by further comprising the step of cutting with punching or knife before the drying step.
또한 구체적으로는, 상기 점성을 조절하는 단계에서 PH는 6 내지 8 범위 내인 것에 특징이 있는 다목적용 촉매 성형방법에 관한 것이다.Also specifically, the step of adjusting the viscosity relates to a multi-purpose catalyst molding method characterized in that the pH is in the range of 6 to 8.
또한 구체적으로는, 상기 금속산화물 분말은 10~50 wt%, 소결촉진제 0.1~5 wt% 잔부 촉매 지지체 산화물 분말인 것에 특징이 있는 다목적용 촉매 성형방법에 관한 것이다.Further specifically, the metal oxide powder relates to a multi-purpose catalyst molding method characterized in that the 10 to 50 wt%, 0.1 to 5 wt% residual catalyst support oxide powder sintering accelerator.
또한 구체적으로는, 상기 제1차 열처리는 250~500℃에서 1~3시간 유지하는 것에 특징이 있는 다목적용 촉매 성형방법에 관한 것이다.More specifically, the first heat treatment relates to a multipurpose catalyst molding method characterized by maintaining at 250 to 500 ° C. for 1 to 3 hours.
또한 구체적으로는, 상기 제2차 열처리는 500~1000℃에서 1~3시간 유지하는 것에 특징이 있는 다목적용 촉매 성형방법에 관한 것이다.More specifically, the second heat treatment relates to a multipurpose catalyst molding method characterized by maintaining at 500 to 1000 ° C for 1 to 3 hours.
또한 구체적으로는, 상기 바인더는 수계 결합제인 것에 특징이 있는 다목적용 촉매 성형방법에 관한 것이다.More specifically, the binder relates to a multipurpose catalyst molding method characterized by being an aqueous binder.
또한 구체적으로는, 상기 혼합기는 지르코니아 볼을 사용하는 볼밀인 것에 특징이 있는 다목적용 촉매 성형방법에 관한 것이다.More specifically, the mixer relates to a multipurpose catalyst molding method characterized by being a ball mill using zirconia balls.
이와 더불어, 위의 성형방법으로 제조된 다목적용 촉매에 관한 것이다.In addition, the present invention relates to a multipurpose catalyst prepared by the above molding method.
위에서 제시하고 있는 촉매를 제작하기 위해서, 본 발명의 일실시예와 관련된 초콜릿 바 형상을 갖는 다목적용 촉매 성형방법은 넓은 판상의 젤리 타입의 반 응고된 촉매를 펀칭을 이용하거나 나이프로 절단하여 원하는 크기나 형상으로 제조할 수 있는 것은 물론, 간단한 형상의 작은 세라믹 성형체를 신속하게 대량으로 제조할 수 있는 것이다. 게다가, 열처리 시 적당한 바인더 물질을 첨가하면서 열처리를 실시할 수 있어 완성된 촉매의 기공량을 적절하게 조절할 수도 있다.In order to manufacture the catalyst presented above, the multi-purpose catalyst molding method having a chocolate bar shape related to an embodiment of the present invention is a wide plate-shaped jelly type The semi-solidified catalyst can be produced in a desired size or shape by punching or by cutting with a knife, as well as a quick and large-scale production of small ceramic moldings with simple shapes. In addition, the heat treatment may be performed while adding a suitable binder material during the heat treatment, so that the pore amount of the finished catalyst may be appropriately adjusted.
본 발명의 도1의 (a)~(d)는 다목적용 촉매 제조과정을 순서대로 나타낸 순서도이다.1 (a) to (d) of the present invention are flowcharts sequentially showing a multipurpose catalyst manufacturing process.
도 2는 본 발명의 건조 및 열처리 이후의 완성된 촉매를 촬영한 사진이다.Figure 2 is a photograph of the completed catalyst after the drying and heat treatment of the present invention.
이하, 첨부된 도면을 참조하여 본 발명의 바람직한 실시예를 상세하게 설명하도록 한다. 도면들 중 동일한 구성요소들은 가능한 어느 곳에서든지 동일한 부호로 표시한다. 또한 본 발명의 요지를 불필요하게 할 수 있는 공지의 기능 및 구성에 대한 상세한 설명은 생략한다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. Like elements in the figures are denoted by the same reference numerals wherever possible. In addition, detailed description of well-known functions and structures which may make the gist of the present invention unnecessary are omitted.
도 1의 (a)~(d)는 본 발명의 실시예에 따른 다목적용 촉매 제조과정을 순서대로 나타낸 도면으로서, 도 1에 도시한 바와 같이, HDX(Hydro De Sulfurization) 촉매의 지지체 산화물과 촉매 산화물을 탈이온수와 혼합하여 슬러리 형태로 제작한 후, 지르코니아 볼을 사용하는 볼밀을 이용하여 균일하게 혼합한 슬러리 상태의 촉매를 제조하였다. 탈이온수의 양은 투입되는 금속산화물 분말, 촉매 지지체 산화물 분말 등 바인더 시스템의 종류를 고려하여 PH를 조절하면서 투입하며, PH의 변화에 따라 슬러리의 점성에 변화가 발생되므로 원하는 점성을 가질 수 있도록 탈이온수의 양을 조절하면서 투입한다. 또한, 슬러리의 점성에 따라 촉매 소결 시 형상에 변화를 야기할 수 있으므로 슬러리의 제조과정에서 첨가물에 대한 탈이온수의 첨가량을 조절하여 슬러리의 PH를 조절한다. 1 (a) ~ (d) is a view showing a multi-purpose catalyst manufacturing process in order according to an embodiment of the present invention, as shown in Figure 1, the support oxide and catalyst of HDX (Hydro De Sulfurization) catalyst After the oxide was mixed with deionized water to prepare a slurry, a slurry catalyst was uniformly mixed using a ball mill using zirconia balls. The amount of deionized water is adjusted while adjusting the PH in consideration of the type of binder system such as the metal oxide powder and the catalyst support oxide powder to be added, and the viscosity of the slurry is changed according to the change of the pH so that the deionized water can have the desired viscosity. Input while adjusting the amount of. In addition, since the viscosity of the slurry may cause a change in the shape of the catalyst during sintering, the pH of the slurry is controlled by adjusting the amount of deionized water added to the additive during the preparation of the slurry.
슬러리에 첨가되는 각 분말들의 첨가량은 금속산화물 분말 10~50 wt%, 소결촉진제 분말 0.1~5 wt%, 전부가 촉매 지지체 산화물로 이루어진 것으로, 칭량된 분말에 탈이온수를 혼합하여 슬러리를 제조하는 것이다. 금속산화물로는 탈황촉매로 이용되는 NiO 뿐만 아니라 MoO3, CoO, NiO 등의 금속산화물이 혼합되어 첨가될 수 있다. 단독 또는 혼합된 금속산화물이 10 wt% 이하로 첨가되면 촉매로서의 기능이 현저하게 감소하며, 50 wt% 이상 첨가되면 촉매의 강도가 약화되어 부스러짐성이 나빠지게 된다. 소결촉진제는 SiO2가 0.1~5 wt% 첨가되며, 소결촉진제가 0.1 wt% 미만으로 첨가되면 소결 촉진에 대한 효과가 거의 없으며, 5 wt%를 초과하면 완성된 촉매의 소결 촉진에 따라 강도가 너무 높아 촉매로서의 기능이 떨어지게 된다. 촉매 지지체 산화물은 제조된 촉매가 적절한 형태와 강도를 유지하기 위한 것으로 금속산화물 분말의 첨가량에 따라 조절되는 것이다.The amount of each powder added to the slurry is 10 to 50 wt% of the metal oxide powder, 0.1 to 5 wt% of the sintering accelerator powder, and all of them are catalyst support oxides. The slurry is prepared by mixing deionized water with the weighed powder. . As the metal oxide, not only NiO used as a desulfurization catalyst but also metal oxides such as MoO 3 , CoO, and NiO may be mixed and added. When the amount of the metal oxide alone or mixed is added at 10 wt% or less, the function as a catalyst is remarkably reduced, and when it is added at 50 wt% or more, the strength of the catalyst is weakened and the brittleness is worsened. Sintering accelerator is added 0.1 ~ 5 wt% of SiO 2 , when the sintering accelerator is added less than 0.1 wt% has little effect on the sintering promotion, if it exceeds 5 wt%, the strength is too high according to the sintering of the finished catalyst It is high, and the function as a catalyst falls. The catalyst support oxide is to maintain the appropriate form and strength of the prepared catalyst is to be adjusted according to the addition amount of the metal oxide powder.
본 발명에서는 최종 소결 촉매의 형상에 영향을 주지 않기 위해서 슬러리의 준비단계시 PH를 7로 유지하였으며, 이는 탈이온수 첨가를 통해서 조절이 가능하다. PH가 6 미만인 경우에는 바인더 시스템이 PH에 영향을 받음에 따라 전체 슬러리의 점도가 낮아지고, 소결이전의 촉매 형성에 시간이 많이 소비될 뿐만 아니라 목적하는 최종 소결체의 형상에 도달하지 못하게 된다. 반면 슬러리의 PH가 8을 초과하는 경우에는 점성이 높아지게 되어 젤리타입의 판 형태를 유지하는데 어려움이 발생한다. 따라서 PH에 따라 추가로 공급되는 바인더가 존재하며, 이로 인해서 제조하는 순서가 달라지며, 이는 PH 값 7을 기준으로 첨가되는 바인더와 그 제조방법이 달라진다. In the present invention, in order to not affect the shape of the final sintering catalyst, the pH was maintained at 7 during the preparation of the slurry, which can be controlled by adding deionized water. If the pH is less than 6, as the binder system is affected by the PH, the viscosity of the entire slurry is lowered, not only is it time consuming to form the catalyst before sintering, but also does not reach the desired final sintered body shape. On the other hand, when the pH of the slurry exceeds 8, the viscosity becomes high and it is difficult to maintain the jelly type plate shape. Therefore, the binder is additionally supplied depending on the PH, and thus the manufacturing order is changed, which is different from the binder added based on the PH value 7 and the manufacturing method thereof.
PH를 조절하여 적절한 점성을 갖는 슬러리 촉매를 조형틀로 이동한 후, 이를 도1의 (b)와 같이 조형틀 내에 투입하고 탈이온수를 제거하여 젤리와 같은 반 건조 상태의 촉매를 형성하였다. 반 건조된 상태의 촉매를 50~70℃의 온도에서 2~4시간 재건조하여 도1의 (c)의 사진에서 보듯이 탈이온수를 제거하였다. 반 건조된 촉매를 70℃ 이상에서 건조하는 경우에는 탈이온수를 빠른 시간 내에 제거할 수 있으나, 표면에 크랙 및 기공(Void)이 발생하여 최종 소결체의 형상에 영향을 미치게 되며, 50℃ 이하에서는 탈이온수가 2~4시간 내에 원하는 양 만큼 제거되지 않게 된다. 건조된 판상의 슬러리를 펀칭을 이용할 수 있으며 막대 형태의 촉매를 제작할 경우 날카로운 표면을 갖는 도구를 이용하여 도1의 (d)와 같이 일정한 크기 및 형태로 절단한다.After adjusting the pH to move the slurry catalyst having an appropriate viscosity to the mold, it was introduced into the mold as shown in Figure 1 (b) and deionized water was removed to form a catalyst in a semi-dry state, such as jelly. The semi-dried catalyst was re-dried at a temperature of 50-70 ° C. for 2-4 hours to remove deionized water as shown in the photograph of FIG. When the semi-dried catalyst is dried at 70 ° C. or higher, deionized water can be removed in a short time, but cracks and voids are generated on the surface, which affects the shape of the final sintered body. Ionized water will not be removed in the desired amount within 2 to 4 hours. The dried plate-shaped slurry can be used for punching and when a catalyst in the form of a rod is cut into a certain size and shape as shown in FIG. 1 (d) by using a tool having a sharp surface.
일정한 크기로 절단된 초콜릿 형태의 촉매시편은 2차에 걸쳐 열처리를 실시한다. 제1차 열처리는 250~350℃℃에서 1~3시간 동안 유지하며 이때 분당 5℃의 승온 조건을 이용하여 천천히 열처리를 실시한다. 이와 같이 250~350℃의 온도에서 가열처리 하는 이유는 바인더 시스템을 구성하고 있는 고분자 수계 결합제를 제거하고자 하는 것으로 소결을 위한 전처리 과정으로 반 소결 상태를 유지하기 위한 것이다. 제1차 열처리를 거친 후 반 소결 상태의 촉매시편을 가열하여 제2차 열처리를 실시한다. 제2차 열처리는 500~800℃에서 1~3 시간 동안 유지하는 것으로 첨가되는 산화물 파우더가 소결되어 도2의 사진과 같이 완성된 촉매가 되는 것이다.The catalyst specimen in the form of chocolate cut to a certain size is subjected to heat treatment in two steps. The first heat treatment is maintained for 1 to 3 hours at 250 ~ 350 ℃ ℃ per minute By using the temperature rise condition of 5 degreeC Slowly heat treatment. The reason for the heat treatment at the temperature of 250 ~ 350 ℃ is to remove the polymer aqueous binder constituting the binder system to maintain the semi-sintered state as a pretreatment process for sintering. After the first heat treatment, the catalyst specimen in a semi-sintered state is heated to perform a second heat treatment. The second heat treatment is to maintain the oxide powder added by maintaining for 1 to 3 hours at 500 ~ 800 ℃ sintered to become a completed catalyst as shown in the photo of FIG.
이와 같은 방법으로 간단한 형상의 세라믹 성형체를 대량으로 제조할 수 있는 탈황촉매는 분리가 어려운 탄소수소 내의 황 화합물을 용이하게 분리할 수 있어 연료전지 시스템을 완성할 수 있는 주요 부품인 탈황기를 포함한 액체 및 기체연료 개질기의 촉매로 적용될 경우 효율 향상에 기여할 수 있다. 동시에 이러한 탈황촉매를 포함한 액체연료 개질기를 상용화할 경우, 이를 활용한 디젤류 연료전지 시스템을 개발할 수 있어 수송 및 이동용 발전시장에 진입 또한 가능하게 된다.In this way, the desulfurization catalyst capable of producing a large amount of ceramic shaped articles in a simple shape can easily separate sulfur compounds in carbon dioxide, which are difficult to separate, and thus include a liquid including a desulfurizer, which is a major component for completing a fuel cell system. When applied as a catalyst for gaseous fuel reformers It can contribute to efficiency improvement. At the same time When commercializing a liquid fuel reformer including such a desulfurization catalyst, a diesel fuel cell system using the desulfurization catalyst can be developed, and thus it is also possible to enter a transportation and mobile power generation market.
이하 실시예 및 비교예를 통하여 본 발명에 대하여 더욱 상세하게 설명토록 하겠다. Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
(실시예 1)(Example 1)
탈황촉매를 제조하기 위하여 γ-Al2O3(감마 알루미나), Ni 금속 파우더 및 SiO2를 준비한 다음, 이들 촉매를 γ-Al2O3 50 wt%, NiO 파우더 49 wt%, SiO2 1 wt%로 각각 칭량하여 혼합하였으며, 이때의 첨가된 SiO2는 소결촉진제로 사용한다. 이후 슬러리를 제작하였으며, 슬러리 제작 시 투입되는 파우더에 따라서 PH의 변화가 발생하나 PH 값을 7이 되도록 한다. γ-Al2O3를 탈이온수에 혼합할 경우, PH가 6.58로 측정되기 때문에 PH를 7로 조절하기 위해서 추가적인 탈이온수와 γ-Al2O3, 그리고 중화제(neutralizing agent)를 첨가한다. 이들을 수 분간 혼합한 다음 바인더를 첨가한다. 반면 PH가 7이상인 경우에는 탈이온수에 바인더와 중화제를 혼합한 후 수 분간 혼합한 후에 칭량된 분말들을 첨가한다. 이후 혼합된 슬러리를 조형틀에 주입한 후 원하는 모양과 사이즈에 맞게 날카로운 표면을 갖는 도구를 이용하여 막대 형태의 촉매를 제조하였다. 성형 공정이 종료된 시편을 이용하여 60℃에서 3시간 동안 건조를 시킨 후 열처리를 실시하였다. 1차 열처리는 첨가된 수계 바인더 시스템을 제거하기 위해서 300℃에서 2시간동안 열처리를 하였으며, 이후 800℃에서 1시간동안 2차 열처리를 실시하였다. To prepare a desulfurization catalyst, γ-Al 2 O 3 (gamma alumina), Ni metal powder, and SiO 2 were prepared, and these catalysts were then prepared using 50 wt% of γ-Al 2 O 3 , 49 wt% of NiO powder, and 1 wt of SiO 2. Each was weighed and mixed in%, and the added SiO 2 was used as a sintering accelerator. After the slurry was produced, the pH changes depending on the powder injected during slurry production, but the PH value is set to 7. When γ-Al 2 O 3 is mixed with deionized water, the pH is measured to be 6.58, so additional deionized water, γ-Al 2 O 3 , and neutralizing agent are added to adjust the pH to 7. Mix them for several minutes and then add the binder. On the other hand, when the pH is 7 or more, the binder and the neutralizing agent are mixed with deionized water, mixed for several minutes, and then weighed powders are added. Thereafter, the mixed slurry was injected into a mold, and then a catalyst in the form of a rod was prepared by using a tool having a sharp surface in accordance with a desired shape and size. After the molding process was completed, the sample was dried at 60 ° C. for 3 hours, and then heat treated. In order to remove the added aqueous binder system, the first heat treatment was performed at 300 ° C. for 2 hours, and then the second heat treatment was performed at 800 ° C. for 1 hour.
(실시예 2)(Example 2)
상기 실시예 1에서 금속산화물 파우더를 MoO3 분말 24 wt%와 CoO 분말 7 wt%, 감마알루미나 69 wt%로 변경한 것을 제외하고는, 실시예 1과 실질적으로 동일하게 촉매를 제조하였다.A catalyst was prepared in substantially the same manner as in Example 1 except that the metal oxide powder was changed to 24 wt% of MoO 3 powder, 7 wt% of CoO powder, and 69 wt% of gamma alumina.
(실시예 3)(Example 3)
상기 실시예 1에서 금속산화물 파우더를 MoO3 분말 24 wt%와 NiO 분말 8 wt%, 감마알루미나 68 wt%로 변경한 것을 제외하고는, 실시예 1과 실질적으로 동일하게 촉매를 제조하였다. A catalyst was prepared in substantially the same manner as in Example 1, except that the metal oxide powder was changed to 24 wt% of MoO 3 powder, 8 wt% of NiO powder, and 68 wt% of gamma alumina.
(실시예 4)(Example 4)
상기 실시예 1에서 일반 개질촉매를 제조하기 위하여 Fe2O3 분말 87 wt%와 Cr2O3 분말 8 wt%, CuO 분말 2 wt% 기타 분말 3 wt%로 금속산화물 파우더를 변경한 것을 제외하고는, 실시예 1과 실질적으로 동일하게 촉매를 제조하였다.Except for changing the metal oxide powder to 87 wt% Fe 2 O 3 powder, 8 wt% Cr 2 O 3 powder, 2 wt% CuO powder 3 wt% other powder in order to prepare a general reforming catalyst in Example 1 Was prepared in substantially the same manner as in Example 1.
(비교예 1)(Comparative Example 1)
상기 실시예 1에서 제조된 슬러리의 탈이온수를 제거하기 위하여, 100℃로 1시간 건조시켜 반건조 상태의 촉매를 제조한 것을 제외하고는, 실시예 1과 실질적으로 동일하게 촉매를 제조하였다.In order to remove the deionized water of the slurry prepared in Example 1, the catalyst was prepared in substantially the same manner as in Example 1, except that the catalyst was dried at 100 ° C. for 1 hour to prepare a semi-dried catalyst.
(비교예 2)(Comparative Example 2)
상기 실시예 1에서 제조된 슬러리의 탈이온수 제거 및 1차 열처리까지 동일한 방법을 이용하여 촉매를 제조하였으며, 2차 열처리를 실시하지 않고 촉매를 제조하였다. The catalyst was prepared using the same method until the deionized water removal and the first heat treatment of the slurry prepared in Example 1, and the catalyst was prepared without performing the second heat treatment.
상기 실시예 및 비교예에 따라 각각 제조된 촉매의 외관 및 특성을 비교해 보기 위하여, 실시예 1~4 및 비교예 1, 2의 촉매의 외관과 강도를 측정하였으며, 그 값을 표 1에 나타내었다.In order to compare the appearance and characteristics of the catalyst prepared according to the Examples and Comparative Examples, the appearance and strength of the catalysts of Examples 1 to 4 and Comparative Examples 1 and 2 were measured, and the values are shown in Table 1. .
외관 상 발견되는 갈라짐이나 크랙이 없으면 ○로 표시하였으며, 크랙이 발생되면 그 정도에 따라 △나 × 로 표기하였다. 강도를 측정하기 위하여 단순히 손으로 제조된 촉매를 가압하는 방법으로 부스러짐성을 측정하였으며, 부스러지는 정도에 따라 1 내지 5로 표시하였다.If no cracks or cracks were found in appearance, they were marked with ○, and if cracks occurred, they were marked with △ or × depending on the extent. In order to measure the strength, the brittleness was measured by simply pressurizing the catalyst prepared by hand, and expressed as 1 to 5 depending on the degree of the brittleness.
표 1
촉매 외관 부스러짐성
실시예 1 ○ 3
2 ○ 5
3 ○ 4
4 ○ 4
비교예 1 × 4
2 ○ 1
Table 1
catalyst Exterior Crumbness
Example One ○ 3
2 ○ 5
3 ○ 4
4 ○ 4
Comparative example One × 4
2 ○ One
구체적으로 표1에 나타나는 바와 같이 실시예 1~4인 NiO, CoMo, NiMo 각각의 산화물 및 개질 촉매 분말을 조성에 맞게 혼합, 성형 및 열처리를 실시하였을 경우, 최종 소결된 촉매의 부스러짐성을 실시예 1을 기준으로 수치화할 경우 부스러짐성은 2차 열처리를 실시하지 않은 비교예 2가 가장 낮은 값을 나타내었으나, 다른 촉매들은 부스러짐성이 상대적으로 우수한 결과를 나타내고 있음을 알 수 있다. 실시예 1~4 및 비교예 2는 외관상으로도 큰 문제는 없어 보이나 100℃의 높은 온도로 건조시킨 비교예 1의 촉매는 그 표면에 크랙이 발생하였다. 더욱 매끄러운 표면을 제조하기 위하여 폴리싱이나 연마와 같은 기계적인 방법을 이용하여 표면을 성형하여도 문제가 없으나, 표면적의 증가를 위해서 거친 표면이 촉매 활성을 보다 증가시킬 수 있을 것으로 판단한다. Specifically, as shown in Table 1, when the oxides and the reforming catalyst powders of NiO, CoMo, and NiMo, which are Examples 1 to 4, were mixed, molded, and heat treated according to their compositions, the final sintered catalyst was friable. When quantified based on Example 1, the brittleness of Comparative Example 2 without the secondary heat treatment showed the lowest value, but it can be seen that other catalysts show relatively excellent brittleness. In Examples 1 to 4 and Comparative Example 2, there is no problem in appearance, but the catalyst of Comparative Example 1 dried at a high temperature of 100 ° C. has cracked on its surface. Although it is not a problem to form the surface by using a mechanical method such as polishing or polishing to produce a smoother surface, it is determined that the rough surface may increase the catalytic activity in order to increase the surface area.
상기와 같은 초콜릿 바 형태를 갖는 촉매 제조방법은 위에서 설명된 실시예들의 구성과 작동 방식에 한정되는 것이 아니다. 상기 실시예들은 각 실시예들의 전부 또는 일부가 선택적으로 조합되어 다양한 변형이 이루어질 수 있도록 구성될 수도 있다. The method of preparing a catalyst having a chocolate bar form as described above is not limited to the configuration and operation of the embodiments described above. The above embodiments may be configured such that various modifications may be made by selectively combining all or part of the embodiments.

Claims (9)

  1. 초콜릿 바 형태를 갖는 다목적용 촉매를 성형하는 방법에 있어서, In the method of molding a multipurpose catalyst having a chocolate bar form,
    금속산화물 분말과, 촉매 지지체 산화물 분말, 소결촉진제 및 탈이온수를 첨가한 후, 혼합하여 슬러리를 제조하는 단계;Preparing a slurry by adding a metal oxide powder, a catalyst support oxide powder, a sintering accelerator, and deionized water, followed by mixing;
    상기 슬러리에 첨가되는 탈이온수 및 분말 첨가량을 조절하여 PH 및 슬러리 점성을 조절하는 단계;Adjusting pH and slurry viscosity by adjusting the amount of deionized water and powder added to the slurry;
    슬러리를 혼합기에서 혼합한 후, 탈이온수를 제거하여 젤리 형태의 반건조 상태를 형성하는 단계;Mixing the slurry in a mixer, followed by removing deionized water to form a semi-dry state of jelly form;
    상기 반건조 상태의 슬러리를 50~70℃에서 2~5시간 건조기에 유지시켜 건조하는 단계;Maintaining the semi-dry slurry in a drier for 2 to 5 hours at 50 to 70 ° C. and drying the slurry;
    상기 건조된 촉매를 제1, 2차 열처리를 통하여 소결하는 단계;로 이루어진 다목적용 촉매 성형방법.And sintering the dried catalyst through first and second heat treatments.
  2. 청구항 1에 있어서, The method according to claim 1,
    상기 건조하는 단계 전에 펀칭이나 나이프로 절단하는 단계;를 더 포함하는 것에 특징이 있는 다목적용 촉매 성형방법.Multi-purpose catalyst molding method characterized in that it further comprises; cutting with a punching or knife before the drying step.
  3. 청구항 1에 있어서,The method according to claim 1,
    상기 점성을 조절하는 단계에서 PH는 6 내지 8 범위 내인 것에 특징이 있는 다목적용 촉매 성형방법.In the step of adjusting the viscosity PH is a multi-purpose catalyst molding method characterized in that in the range of 6 to 8.
  4. 청구항 1에 있어서,The method according to claim 1,
    상기 금속산화물 분말은 10~50 wt%, 소결촉진제 0.1~5 wt% 잔부 촉매 지지체 산화물 분말인 것에 특징이 있는 다목적용 촉매 성형방법.Wherein the metal oxide powder is 10 to 50 wt%, 0.1 to 5 wt% sintering accelerator catalyst catalyst method for multi-purpose characterized in that the residual catalyst support oxide powder.
  5. 청구항 1에 있어서,The method according to claim 1,
    상기 제1차 열처리는 250~500℃에서 1~3시간 유지하는 것에 특징이 있는 다목적용 촉매 성형방법.The first heat treatment is a multi-purpose catalyst molding method characterized in that to maintain for 1 to 3 hours at 250 ~ 500 ℃.
  6. 청구항 1에 있어서,The method according to claim 1,
    상기 제2차 열처리는 500~1000℃에서 1~3시간 유지하는 것에 특징이 있는 다목적용 촉매 성형방법.The second heat treatment is a multi-purpose catalyst molding method characterized in that to maintain for 1 to 3 hours at 500 ~ 1000 ℃.
  7. 청구항 1에 있어서,The method according to claim 1,
    상기 바인더는 수계 결합제인 것에 특징이 있는 다목적용 촉매 성형방법.Multi-purpose catalyst molding method characterized in that the binder is an aqueous binder.
  8. 청구항 1에 있어서,The method according to claim 1,
    상기 혼합기는 지르코니아 볼을 사용하는 볼밀인 것에 특징이 있는 다목적용 촉매 성형방법.The mixer is a multi-purpose catalyst molding method characterized in that the ball mill using a zirconia ball.
  9. 청구항 1 내지 8 중 어느 한 항의 성형방법으로 제조된 다목적용 촉매.A multipurpose catalyst prepared by the molding method of any one of claims 1 to 8.
PCT/KR2015/004710 2014-06-19 2015-05-12 Method for molding multipurpose catalyst having bar shape, and catalyst prepared by method WO2015194758A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR970005386A (en) * 1995-07-29 1997-02-19 Composition and preparation method of tungsten-containing molybdenum-based alumina supported catalyst for hydrodesulfurization of petroleum products
JP2001261463A (en) * 2000-03-15 2001-09-26 Narita Seitoushiyo:Kk Ceramic porous body and its production process
KR20090082912A (en) * 2006-12-13 2009-07-31 와커 헤미 아게 Method for producing catalysts and their use for the gas phase oxidation of olefins
KR20110032624A (en) * 2009-09-23 2011-03-30 두산중공업 주식회사 Extrusion method of internal reforming catalyst for molten carbonate fuel cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR970005386A (en) * 1995-07-29 1997-02-19 Composition and preparation method of tungsten-containing molybdenum-based alumina supported catalyst for hydrodesulfurization of petroleum products
JP2001261463A (en) * 2000-03-15 2001-09-26 Narita Seitoushiyo:Kk Ceramic porous body and its production process
KR20090082912A (en) * 2006-12-13 2009-07-31 와커 헤미 아게 Method for producing catalysts and their use for the gas phase oxidation of olefins
KR20110032624A (en) * 2009-09-23 2011-03-30 두산중공업 주식회사 Extrusion method of internal reforming catalyst for molten carbonate fuel cell

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