KR20100052129A - Pb substituted chlorapatite catalyst for methane coupling reaction and method for preparing the same - Google Patents

Pb substituted chlorapatite catalyst for methane coupling reaction and method for preparing the same Download PDF

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KR20100052129A
KR20100052129A KR1020080111020A KR20080111020A KR20100052129A KR 20100052129 A KR20100052129 A KR 20100052129A KR 1020080111020 A KR1020080111020 A KR 1020080111020A KR 20080111020 A KR20080111020 A KR 20080111020A KR 20100052129 A KR20100052129 A KR 20100052129A
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catalyst
methane
substituted
chlorapatite
solution
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KR101054900B1 (en
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이관영
서동진
이대원
임성우
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고려대학교 산학협력단
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • 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

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Abstract

PURPOSE: A Pb-substituted chlorapatite catalyst for methane coupling reaction, which is stable at a high temperature, a manufacturing method thereof, and a manufacturing method of C2 compounds using the same are provided to improve activity and to offer high-temperature stability to the catalyst with high C2 yield. CONSTITUTION: A Pb substitution chlorine apatite catalyst for methane coupling reaction is marked as Ca_(10-x) Pb_x (PO4)6Cl2. A manufacturing method of the catalyst comprises following steps: mixing a calcium precursor Ca (NO3) 2·4H2O aqueous solution and a Pb precursor Pb (NO3) 2O aqueous solution; adjusting pH of a mixture to 9; mixing and refluxing the mixture with a 0.6M (NH4) 2HPO4 solution and a 0.2M NH4Cl solution; drying the mixture after aging; and plasticizing dried mixture.

Description

메탄 이량화용 Ｐｂ 치환 클로르아파타이트 촉매 및 이의 제조 방법{Pb substituted chlorapatite catalyst for Methane coupling reaction and method for preparing the same}Pb substituted chlorapatite catalyst for Methane coupling reaction and method for preparing the same}

본 발명은 고온에서도 변하지 않는 고온 안정성을 가지고 있으면서 Pb 치환 하이드록시아파타이트 촉매와 비교하였을 때 높은 C2 수율을 갖는 메탄 이량화용 Pb 치환 클로르아파타이트 촉매에 관한 것이다. 또한, 본 발명은 진공증착기(vacuum evaporator)를 이용, 공기 중의 기체 유입을 최소화하고, reflux를 수행해 촉매 제조시 일정한 조건을 유지할 수 있도록 하는 촉매 제법을 통해 Pb 치환 클로르아파타이트를 제조하여 고온에서의 안정성이 높고 활성이 높은 메탄 이량화용 Pb 치환 클로르아파타이트 촉매의 제조방법을 제공하는데 있다.The present invention relates to a Pb-substituted chlorapatite catalyst for methane dimerization having a high C 2 yield as compared with a Pb-substituted hydroxyapatite catalyst while having high temperature stability which does not change even at high temperatures. In addition, the present invention by using a vacuum evaporator (vacuum evaporator) to minimize the inflow of gas in the air, by performing a reflux process to prepare a Pb-substituted chlorapatite through a catalyst preparation to maintain a constant condition during the production of the stability at high temperatures To provide a high and high activity Pb-substituted chlorapatite catalyst for methane dimerization.

천연 가스의 주성분인 메탄은 저장 및 수송이 어렵고, 안정한 물질로서 지금까지의 기술로는 다른 물질로의 변환이 어려워 매장량이 석유의 매장량과 거의 비슷한 수준임에도 불구하고 천연 가스의 사용은 그 범위가 연료로써의 이용에 국한 되고 있다. Methane, the main component of natural gas, is difficult to store and transport, and it is a stable substance, and it is difficult to convert it to other materials with the technology so far. It is limited to use as.

최근 메탄 이량화 반응은 석유 에너지 수요 해결의 대안으로서 주목받고 있다. 메탄 이량화 반응은 메탄을 직접 에탄 또는 에틸렌(이하 C2 화합물)로 변환시킨다. 메탄을 곧바로 C2 화합물로 변환하기 때문에 메탄 가스의 개질 후에 다시 C2 화합물로 합성하는 등의 방식처럼 여러 과정을 거치지 않고 간단한 공정을 통해 C2 화합물을 얻을 수 있으므로 그 이용 가치가 높아 많은 연구가 진행되고 있다. Recently, methane dimerization has attracted attention as an alternative to petroleum energy demand. The methane dimerization reaction directly converts methane to ethane or ethylene (hereafter C 2 compounds). Since the conversion of methane directly to C 2 compounds that can be obtained with C 2 compound by a simple process without going through a number of processes as a method, such as for synthesizing a C 2 compound after reforming of the methane number increases its use value R It's going on.

[반응식 1]Scheme 1

2CH4 + ½O2 → C2H6 + H2O2CH 4 + ½O 2 → C 2 H 6 + H 2 O

메탄 이량화 반응은 약 700oC 이상의 고온에서 상기 반응과 같은 메탄의 부분 산화 반응을 통해 얻어진 에탄은 하기 과정과 같이 다시 탈수소화 반응을 거쳐 에틸렌으로 변환된다. In the methane dimerization reaction, the ethane obtained through the partial oxidation of methane as the above reaction at a high temperature of about 700 ° C. or more is converted to ethylene through dehydrogenation again as follows.

[반응식 2]Scheme 2

C2H6 → C2H4 + H2 C 2 H 6 → C 2 H 4 + H 2

에틸렌, 에탄에 비해 메탄이 더욱 안정하므로 에틸렌, 에탄이 더욱 산화되기 쉬우며 하기 과정과 같은 메탄의 완전 산화 반응이 상기 두 반응보다 열역학적으로 더욱 유리하여 메탄 이량화 반응에는 에탄, 에틸렌에 대한 선택성이 좋은 촉매의 개발이 가장 중요하다. Since methane is more stable than ethylene and ethane, ethylene and ethane are more easily oxidized, and the complete oxidation of methane is more thermodynamically advantageous than the two reactions. The development of a good catalyst is of utmost importance.

[반응식 3]Scheme 3

CH4 + 2O2 → CO2 + 2H2OCH 4 + 2O 2 → CO 2 + 2H 2 O

메탄 이량화 반응은 700oC 이상의 고온에서 진행되므로 높은 활성과 함께 고온에서의 안정성이 중요한 조건이다. 현재 메탄 이량화 반응용 촉매로는 희토류 금속이 주로 이용되고 있으나, 그 외에도 다양한 전위 금속 산화물을 이용한 촉매 제조 연구도 활발히 진행되고 있다.Since the methane dimerization proceeds at high temperatures of 700 ° C. or higher, stability at high temperatures with high activity is an important condition. Currently, rare earth metals are mainly used as methane dimerization catalysts, but researches on catalyst production using various potential metal oxides are also actively conducted.

대한민국등록특허 제10-197160호에서는 메탄 이량화용 Pb치환 하이드록시아파타이트 촉매를 제시하였다. 그러나, 촉매의 제조 시간이 길고 그 제법 하에서 촉매 합성 수율이 낮다는 문제점이 있다.Korean Patent Registration No. 10-197160 proposed a Pb-substituted hydroxyapatite catalyst for methane dimerization. However, there is a problem that the production time of the catalyst is long and the yield of catalyst synthesis is low under the preparation method.

본 발명의 목적은 고온에서도 변하지 않는 고온 안정성을 가지고 있으면서 Pb 치환 하이드록시아파타이트 촉매와 비교하였을 때 높은 C2 수율을 갖는 메탄 이량화용 Pb 치환 클로르아파타이트 촉매 및 이의 제조방법을 제공하는데 있다.An object of the present invention is to provide a Pb-substituted chlorapatite catalyst for methane dimerization having a high C 2 yield and a method for preparing the same, as compared with Pb-substituted hydroxyapatite catalysts having high temperature stability which does not change even at high temperatures.

본 발명의 다른 목적은 진공증착기(vacuum evaporator)를 이용, 공기 중의 기체 유입을 최소화하고, reflux를 수행해 촉매 제조시 일정한 조건을 유지할 수 있도록 하는 촉매 제법을 통해 Pb 치환 클로르아파타이트를 제조하여 고온에서의 안정성이 높고 활성이 높은 메탄 이량화용 Pb 치환 클로르아파타이트 촉매 및 이의 제조방법을 제공하는데 있다.Another object of the present invention is to prepare a Pb-substituted chlorapatite by using a vacuum evaporator to minimize the inflow of gas into the air, and to perform reflux to maintain a constant condition during the preparation of the catalyst, thereby producing a Pb-substituted chlorapatite at a high temperature. The present invention provides a Pb-substituted chlorapatite catalyst for methane dimerization having high stability and high activity, and a method for preparing the same.

본 발명의 또다른 목적은 제조한 상기 촉매를 사용하여 메탄으로부터 에탄 또는 에틸렌을 선택적으로 얻는 방법을 제공하는 데 있다.Another object of the present invention is to provide a method for selectively obtaining ethane or ethylene from methane using the prepared catalyst.

본 발명의 메탄 이량화용 Pb 치환 클로르아파타이트 촉매는 Ca10-xPbx(PO4)6Cl2(여기서, X의 범위가 0≤X≤10이다) 의 화화식을 갖는 것을 특징으로 한다.Pb-substituted chlorapatite catalyst for methane dimerization of the present invention is Ca 10-x Pb x (PO 4 ) 6 Cl 2 (wherein X ranges from 0 ≦ X ≦ 10) It is characterized by having a formula of.

본 발명의 메탄 이량화용 Pb 치환 클로르아파타이트 촉매 방법은 칼슘 전구체[Ca(NO3)2·4H2O] 수용액과 Pb 전구체[Pb(NO3)2O] 수용액을 진공증착기(vacuum evaporator)를 이용하여 혼합하고, pH를 9로 맞춘 후, 0.6M의 (NH4)2HPO4 용액과 0.2M의 NH4Cl 용액을 혼합하고, reflux를 수행하며 숙성시킨 후 건조 및 소성시킨 것을 특징으로 한다.The Pb-substituted chlorapatite catalyst method for methane dimerization of the present invention uses a vacuum evaporator to convert an aqueous calcium precursor [Ca (NO 3 ) 2 .4H 2 O] solution and an aqueous Pb precursor [Pb (NO 3 ) 2 O] solution into a vacuum evaporator. After mixing by adjusting the pH to 9, 0.6M (NH 4 ) 2 HPO 4 solution and 0.2M NH 4 Cl solution, characterized in that the reflux was carried out to age, dried and calcined.

바람직하게, 상기 칼슘 전구체 수용액과 Pb 전구체 수용액은 진공증착기(vacuum evaporator)로 탈가스시킨 것을 특징으로 한다.Preferably, the calcium precursor aqueous solution and the Pb precursor aqueous solution are characterized in that the degassed by a vacuum evaporator (vacuum evaporator).

바람직하게, Ca10-xPbx(PO4)6Cl2(여기서, X의 범위가 0≤X≤10) 촉매 존재하에서 메탄, 산소 및 He 기체를 함유하는 혼합 기체를 접촉시켜 메탄의 이량화 반응을 수행하는 것을 특징으로 한다.Preferably, dimerization of methane by contacting a mixed gas containing methane, oxygen and He gas in the presence of Ca 10-x Pb x (PO 4 ) 6 Cl 2 (where X ranges from 0 ≦ X ≦ 10) catalyst It is characterized by carrying out the reaction.

본 발명에 의하여 제조된 Pb 치환 클로르아파타이트 촉매는 메탄을 에틸렌, 에탄으로 직접 변환하는데 있어 높은 활성을 갖는다. The Pb substituted chlorapatite catalyst prepared according to the present invention has a high activity in converting methane directly into ethylene and ethane.

또한, Pb 치환 클로르아파타이트를 제조하는 방법에 있어 전구체 용액을 vacuum evaporator를 통해 산소나 이산화탄소 등의 기체를 제거하고, 촉매의 숙성 과정에서 reflux를 수행하는 등의 과정을 통해 촉매 합성의 고온에서 안정하고, 높은 활성을 갖도록 제조할 수 있다.In addition, in the method of preparing Pb-substituted chlorapatite, the precursor solution is removed at a high temperature in the synthesis of the catalyst by removing gases such as oxygen or carbon dioxide through a vacuum evaporator, and performing reflux during the aging of the catalyst. It can be prepared to have high activity.

또한, 본 발명의 Pb 치환 클로르아파타이트는 장시간의 반응에도 촉매의 상태가 변하지 않았고, 메탄 이량화 반응에 적용한 결과에서도 Pb 치환 클로르아파타이트는 Pb 치환 하이드록시아파타이트보다 C2 선택도가 우수한 효과를 갖는다. In addition, the Pb-substituted chlorapatite of the present invention did not change the state of the catalyst even after a long time reaction, and even when applied to the methane dimerization reaction, the Pb-substituted chlorapatite has an effect of superior C 2 selectivity than Pb-substituted hydroxyapatite.

이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다. Hereinafter, the present invention will be described in detail.

본 발명의 촉매는 클로르아파타이트를 기본으로 하여 활성물질인 Pb를 치환해 제조된다. 클로르아파타이트는 다음의 화학식 1과 같은 형태를 가지는 물질로서 백색이며 단단한 성질을 가지고 있어 인공 치아 및 인공 뼈의 재료로 사용되고 있는 물질이지만 촉매로써 이용된 사례는 보고된 바가 없다. The catalyst of the present invention is prepared by substituting Pb as an active substance based on chlorapatite. Chloropatite is a material having a form such as the following Chemical Formula 1, which is white and hard, and thus is used as a material for artificial teeth and bones, but there have been no reports of using it as a catalyst.

[화학식 1][Formula 1]

Ca10(PO4)6Cl2 Ca 10 (PO 4 ) 6 Cl 2

상기의 클로르아파타이트에 Ca 대신 Pb를 치환하면 다음의 화학식 2와 같은 형태의 물질을 합성할 수 있다. Chlorine은 CH4 활성화에 효과가 있는 것으로 알려져 있는 물질이므로 C2 화합물에 대한 선택성을 높여주는 Pb와 함께 이용한다면 하이드록시아파타이트의 경우에 비해 메탄의 활성화에 효과가 있고 C2 화합물에 대한 선택성 또한 우수해져 활성이 높은 촉매의 제조가 가능하다. Substituting Pb instead of Ca in the chlorapatite may synthesize a material of the form as shown in Formula 2 below. Chlorine is known to be effective in activating CH 4 , so when used in combination with Pb, which enhances the selectivity for C 2 compounds, it is more effective at activating methane and more selective for C 2 compounds than hydroxyapatite. It is possible to manufacture a catalyst having high activity.

[화학식 2][Formula 2]

Ca10-xPbx(PO4)6Cl2, 단 X는 0≤X≤10Ca 10-x Pb x (PO 4 ) 6 Cl 2 , where X is 0≤X≤10

Pb 치환 클로르아파타이트 촉매 제조는 다음과 같다. 칼슘 전구체는 시그마 알드리치 제품의 Ca(NO3)2·4H2O를 1M 수용액으로 제조하여 사용하였다. Pb 전구체는 시그마 알드리치 제품의 Pb(NO3)2O를 1M 수용액으로 제조하여 사용하였다. 진공증착기(vacuum evaporator)를 이용하여 탈가스(de-gasing)한 Ca 전구체 용액과 Pb 전구체 용액을 혼합하고 NH4OH를 이용해 pH를 9로 맞춘 후, 0.6M의 (NH4)2HPO4 용액과 0.2M의 NH4Cl 용액을 혼합한다. de-gasing이 충분히 이루어지지 않으면 용액 속에 녹아 있는 이산화탄소나 산소가 촉매 생성 반응에 관여하여 부산물이 생성될 수 있으므로 적당하지 않고, 약 1시간 정도의 de-gasing 과정 후 용액을 혼합하는 것이 적절하다. 또한 혼합 후 reflux를 수행하며 90oC에서 2시간 숙성시킨 후 50oC 진공에서 3시간 건조한다. Reflux 과정을 통해 촉매 제조 시 온도, 압력 등의 조건이 일정하게 유지되도록 하는 것이 바람직하다. 건조가 끝난 결과물을 산소 분위기 하에서 300oC에서 한 시간, 800oC에서 두 시간 동안 소성한다.Preparation of Pb substituted chlorapatite catalyst is as follows. The calcium precursor was used by preparing Ca (NO 3 ) 2 .4H 2 O from Sigma Aldrich in 1M aqueous solution. The Pb precursor was used by preparing Pb (NO 3 ) 2 O from Sigma Aldrich in 1M aqueous solution. After degassing the Ca precursor solution and the Pb precursor solution using a vacuum evaporator, and adjusting the pH to 9 using NH 4 OH, a 0.6M (NH 4 ) 2 HPO 4 solution was used. And 0.2M NH 4 Cl solution. If degassing is not sufficiently done, carbon dioxide or oxygen dissolved in the solution may be involved in the catalyst formation reaction, and by-products may be generated. It is not appropriate to mix the solution after about 1 hour of degassing. In addition, the mixture is refluxed and aged at 90 ° C. for 2 hours, followed by drying at 50 ° C. for 3 hours. Through the Reflux process, it is desirable to keep the conditions such as temperature and pressure constant during the preparation of the catalyst. Fired for two hours and the resultant is dried over from one hour, 800 o C at 300 o C under an oxygen atmosphere.

한편, 상기 물질을 활용하여 제조된 Pb 치환 클로르아파타이트 촉매를 반응기에 충전하여 725 내지 800oC의 다양한 온도에서 메탄의 이량화 반응을 수행할 수 있다. 반응 온도가 725oC 미만이면 메탄의 전환율이 낮아 바람직하지 못하고, 800℃를 초과하는 경우 에너지의 효율 측면과 촉매의 비활성화 및 안정성 측면에서 바람직하지 못하다. 본 발명의 촉매의 경우 775oC와 800oC에서 반응을 수행하는 것이 촉매 활성 및 안정성 면에서 가장 바람직하다. Meanwhile, the Pb-substituted chlorapatite catalyst prepared by using the material may be charged to a reactor to perform dimerization of methane at various temperatures of 725 to 800 ° C. If the reaction temperature is less than 725 o C is not preferable because the conversion of methane is low, and if it is higher than 800 ℃ in terms of energy efficiency and deactivation and stability of the catalyst is not preferable. In the case of the catalyst of the present invention, it is most preferable to perform the reaction at 775 ° C. and 800 ° C. in terms of catalyst activity and stability.

처리되는 메탄과 산소의 부피비는 2:1인 것이 적절하며, 운반 기체로는 헬륨을 처리되는 기체의 68%를 혼합하는 것이 바람직하다. 본 발명에 따른 촉매를 사용하여 메탄 이량화 반응을 수행하면, 촉매 표면에서 메탄과 산소가 선택적으로 반응하여 직접 에탄과 에틸렌이 생성된다.It is appropriate that the volume ratio of methane and oxygen to be treated is 2: 1, and as the carrier gas, it is preferable to mix helium with 68% of the treated gas. When methane dimerization is carried out using the catalyst according to the invention, methane and oxygen are selectively reacted on the surface of the catalyst to produce ethane and ethylene directly.

이하, 실시 예를 통하여 본 발명의 촉매 제조 및 분석, 반응 결과를 더욱 상세히 설명하기로 한다. 이들 실시 예는 단지 본 발명을 예시하기 위한 것이며, 본 발명의 보호 범위가 이들 실시 예에 의해 국한되는 것은 아니다.Hereinafter, the catalyst production and analysis of the present invention through the examples, the reaction results will be described in more detail. These examples are only for illustrating the present invention, and the protection scope of the present invention is not limited to these examples.

<실시예 1> &Lt; Example 1 >

Pb 치환 클로르아파타이트 촉매 제조Preparation of Pb substituted chlorapatite catalyst

Ca(NO3)2·4H2O 11.332g을 증류수에 녹여 1M, 48ml의 수용액을 준비하였다(용액 A). Pb(NO3)2 3.975g 을 증류수에 녹여 1M, 12Ml의 수용액을 준비하고(용액 B), NH4Cl 0.642g 을 증류수에 녹여 0.2M, 60Ml의 수용액을 준비하였고(용액 C), (NH4)2HPO4 4.754g 을 증류수에 녹여 0.6M, 60Ml의 수용액을 준비하였다(용액 D). 각각 vacuum evaporator를 이용해 1시간 동안 de-gasing하여 용액 안에 녹아 있는 기체를 제거하고, 용액 A와 B의 혼합물을 NH4OH를 이용, pH를 9로 맞춘다. 용액 A와 B의 혼합 용액에 용액 D를 2Ml/min 속도로 적하시키고, 용액 C를 적하시킨 후 90oC에서 2시간 동안 교반하며 숙성시킨 후 결과물을 24시간 동안 상온에서 유지시킨 후, 여과 및 세척을 거쳐 50oC에서 진공 건조한다. 산소 분위기 하에서 300oC에서 1시간, 800oC에서 2시간 동안 소성하여 다음의 화학식 3과 같은 Pb 치환 클로르아파타이트 촉매를 제조하였다.11.332 g of Ca (NO 3 ) 2 .4H 2 O was dissolved in distilled water to prepare an aqueous solution of 1 M and 48 ml (solution A). 3.975 g of Pb (NO 3 ) 2 was dissolved in distilled water to prepare an aqueous solution of 1 M, 12 Ml (solution B), and 0.642 g of NH 4 Cl was dissolved in distilled water to prepare an aqueous solution of 0.2 M, 60 Ml (solution C), (NH 4 ) 4.754 g of 2 HPO 4 was dissolved in distilled water to prepare an aqueous solution of 0.6 M and 60 Ml (solution D). Each degassed for 1 hour using a vacuum evaporator to remove the dissolved gas in the solution. The mixture of solution A and B was adjusted to pH 9 using NH 4 OH. To the mixed solution of solution A and B, solution D was added dropwise at a rate of 2Ml / min, solution C was added dropwise, aged at 90 ° C. for 2 hours, and the resultant was kept at room temperature for 24 hours, followed by filtration and Wash and vacuum dry at 50 ° C. The Pb-substituted chlorapatite catalyst was prepared by calcining at 300 ° C. for 1 hour and 800 ° C. for 2 hours in an oxygen atmosphere.

[화학식 3](3)

Ca8.0Pb2.0(PO4)6Cl2 Ca 8.0 Pb 2.0 (PO 4 ) 6 Cl 2

촉매 활성 측정시험Catalytic Activity Test

촉매의 활성 측정시험은 제조된 Pb 치환 클로르아파타이트 촉매를 반응기에 충전하여 725 내지 800oC의 다양한 온도에서 메탄, 산소 및 He 기체를 함유하는 혼합 기체를 접촉시켜 메탄의 이량화 반응을 수행하여 에탄과 에틸렌이 생성하였다. 반응을 거친 기체가 얼음물 트랩을 거치도록 하여 수분을 제거하였고, 직접 기체 크로마토그래피에 주입하여 분석하였다. 반응을 거친 기체서 반응물인 메탄, 산소와 그 외에 일산화탄소, 이산화탄소, 에탄, 에틸렌 등이 검출되었으며, 미반응 메탄과 C1을 기준으로 한 생성물의 반응기 출구에서의 양의 합을 100으로 하여 메탄의 전환율을 결정하였다. 또한 C1을 기준으로 한 생성물의 총량을 100으로 하여 각 생성물의 선택도를 결정하였다. The activity measurement test of the catalyst was carried out by charging the prepared Pb-substituted chlorapatite catalyst to the reactor and contacting a mixed gas containing methane, oxygen, and He gas at various temperatures of 725 to 800 ° C. to perform dimerization reaction of methane. And ethylene were produced. The reaction gas was passed through an ice water trap to remove moisture and analyzed by direct injection into gas chromatography. The reactant gas, methane, oxygen and other carbon monoxide, carbon dioxide, ethane, ethylene, etc., was detected, and the sum of the amounts of unreacted methane and the product at the outlet of the reactor based on C 1 was 100. The conversion rate was determined. In addition, the selectivity of each product was determined based on the total amount of products based on C 1 .

촉매의 활성 측정 시험에 대한 결과인 CH4 전환율은 도 1에 나타내었고, C2 선택도는 도 2에 나타내었으며, C2 수율은 도 3에 각각 나타내었다. 반응조건은 촉매량 0.36g, 총 유량 37Ml/min, CH4:O2:He=8:4:25, W/F=1.6×10-4gcat·hr/ml이다.CH 4 conversion, which is a result of the activity measurement test of the catalyst, is shown in FIG. 1, C 2 selectivity is shown in FIG. 2, and C 2 yield is shown in FIG. 3, respectively. The reaction conditions were 0.36 g of catalyst, 37 Ml / min of total flow rate, CH 4 : O 2 : He = 8: 4: 25, and W / F = 1.6 × 10 -4 g cat · hr / ml.

도 1 내지 도 3에 도시된 바와 같아, 800oC에서 CH4 전환율 34.7%, C2 선택도 60.9%, C2 수율 21.1%를 갖는 것을 확인할 수 있으며, 이러한 결과는 기존 특허[메탄 이량화용 Pb 치환 하이드록시아파타이트 촉매의 제조 방법,10-0197160]의 결과(Ca9.5Pb0.50(PO4)6(OH)2, C2 수율 20.5% at 750℃)보다 우수한 결과임을 알 수 있다.As shown in Figures 1 to 3, it can be seen that having a CH 4 conversion of 34.7%, C 2 selectivity 60.9%, C 2 yield 21.1% at 800 o C, these results are the existing patent [Pb for methane dimerization It can be seen that the result of the production method of substituted hydroxyapatite catalyst, 10-0197160 (Ca 9.5 Pb 0.50 (PO 4 ) 6 (OH) 2 , C 2 yield 20.5% at 750 ℃).

<비교실시예 1>Comparative Example 1

Ca(NO3)2·4H2O 14.165g 을 증류수에 녹여 1M, 60Ml의 수용액을 준비하였다(용액 A). NH4Cl 0.642g을 증류수에 녹여 0.2M, 60Ml의 수용액을 준비하였고(용액 B), (NH4)2HPO4 4.754g 을 증류수에 녹여 0.6M, 60Ml의 수용액을 준비하였다(용액 C). 각각 vacuum evaporator를 이용해 1시간 동안 de-gasing하여 용액 안에 녹아 있는 기체를 제거하고, 용액 A를 NH4OH를 이용, pH를 9로 맞춘다. 용액 A에 용액 C를 2Ml/min 속도로 적하시키고, 용액 B를 적하시킨 후 90℃에서 2시간 동안 교반하며 숙성시킨 후 결과물을 24시간 동안 상온에서 유지시킨 후, 여과 및 세척을 거쳐 50℃에서 진공 건조하였다. 그후, 산소 분위기 하에서 300℃에서 1시간, 800℃에서 2시간 동안 소성하여 다음의 화학식 4와 같은 촉매를 제조하였다.14.165 g of Ca (NO 3 ) 2 .4H 2 O was dissolved in distilled water to prepare an aqueous solution of 1 M and 60 Ml (solution A). 0.642 g of NH 4 Cl was dissolved in distilled water to prepare an aqueous solution of 0.2 M, 60 Ml (solution B), and 4.754 g of (NH 4 ) 2 HPO 4 was dissolved in distilled water to prepare an aqueous solution of 0.6 M, 60 Ml (solution C). Each was degassed for 1 hour using a vacuum evaporator to remove the dissolved gas in the solution, and solution A was adjusted to 9 using NH 4 OH. To solution A, solution C was added dropwise at a rate of 2 Ml / min, solution B was added dropwise, aged at 90 ° C. for 2 hours, and the resultant was kept at room temperature for 24 hours, followed by filtration and washing at 50 ° C. Dried in vacuo. Thereafter, the mixture was calcined at 300 ° C. for 1 hour and at 800 ° C. for 2 hours to prepare a catalyst as shown in Formula 4 below.

[화학식 4][Formula 4]

Ca10(PO4)6Cl2 Ca 10 (PO 4 ) 6 Cl 2

그리고, 제조된 촉매의 활성 측정 시험을 수행하여 도 1 내지 도 3에 각각 CH4 전환율, C2 선택도, C2 수율을 함께 나타내었다. 800℃에서 CH4 전환율 28.2%, C2 선택도 16.2%, C2 수율 4.6%를 보였다. In addition, the activity measurement test of the prepared catalyst was performed to show CH 4 conversion, C 2 selectivity, and C 2 yield, respectively, in FIGS. 1 to 3. At 800 ° C., CH 4 conversion was 28.2%, C 2 selectivity was 16.2%, and C 2 yield was 4.6%.

<실시예 2∼4><Examples 2-4>

상기 실시예 1의 Ca(NO3)2·4H2O 수용액의 양과 Pb(NO3)2 수용액의 양을 조절하여, Ca10-xPbx(PO4)6Cl2에서 X= 1, 3, 4인 Pb 치환 클로르아파타이트를 제조하였다.The amount of Ca (NO 3 ) 2 .4H 2 O aqueous solution and the amount of Pb (NO 3 ) 2 aqueous solution of Example 1 were adjusted, and X = 1, 3 in Ca 10-x Pb x (PO 4 ) 6 Cl 2 . , Pb-substituted chlorapatite having 4 was prepared.

그리고, 실시예 1과 동일한 조건으로 각각의 제조된 촉매의 활성 측정 시험을 수행하여 도 1 내지 도 3에 각각 CH4 전환율, C2 선택도, C2 수율을 함께 나타내었다. In addition, the activity measurement test of each prepared catalyst was carried out under the same conditions as in Example 1 to show CH 4 conversion, C 2 selectivity, and C 2 yield, respectively in FIGS. 1 to 3.

도시된 바와 같이, 가장 높은 C2 수율을 보이는 800℃에서는 모두가 Pb를 치환하지 않은 촉매보다 높은 C2 수율을 보였다. Showed the highest C 2 C 2 higher yield than the catalyst are not all substituted for Pb in 800 ℃ exhibit yield as shown.

<비교 실시예 2>Comparative Example 2

제조된 Pb 치환 클로르아파타이트 촉매의 열적 안정성을 검토하기 위해 PbO/Al2O3를 제조하여 비교하였다. PbO/Al2O3는 Pb(NO3)2 16.56g 을 증류수에 녹여 1M, 50Ml의 수용액을 준비하였다. Al(NO3)3·9H2O 18.757g 을 증류수에 녹여 1M, 50Ml의 수용액을 준비하여 혼합하고 Na2CO3를 이용, pH를 9로 맞추고 2시간동안 교반한 뒤 여과 및 세척을 거쳐 건조하고 세척하여 제조한 후 800℃/air 조건에서 10시간, 20시간, 30시간 동안 노출시켜서 각각 ICP-AES 분석을 수행하였다. In order to examine the thermal stability of the prepared Pb substituted chlorapatite catalyst, PbO / Al 2 O 3 was prepared and compared. PbO / Al 2 O 3 dissolve 16.56 g of Pb (NO 3 ) 2 in distilled water to prepare an aqueous solution of 1M, 50Ml. 18.757 g of Al (NO 3 ) 3 · 9H 2 O was dissolved in distilled water to prepare an aqueous solution of 1M and 50Ml, mixed, adjusted to pH 9 with Na 2 CO 3 , stirred for 2 hours, filtered and washed and dried. ICP-AES analysis was performed by exposing for 10 hours, 20 hours, and 30 hours at 800 ° C./air conditions.

제조한 Ca7.5Pb2.5(PO4)6Cl2 촉매에 대해서 마찬가지로 800℃/air 조건에서 10시간, 20시간, 30시간, 40시간 후에 ICP-AES 분석을 수행하였다. 하기의 표1에서와 같이, 결과를 정리해 보면 Ca7.5Pb2.5(PO4)6Cl2 샘플의 경우 고온에서 40시간이 지난 후에도 큰 변화가 없었으나 PbO/Al2O3 는 시간이 지날수록 Pb 농도의 비율이 감소하여 Pb 치환 클로르아파타이트가 열적 안정성이 우수함을 알 수 있다. The prepared Ca 7.5 Pb 2.5 (PO 4 ) 6 Cl 2 catalyst was also subjected to ICP-AES analysis after 10 hours, 20 hours, 30 hours, and 40 hours at 800 ° C / air conditions. As shown in Table 1 below, the results of Ca 7.5 Pb 2.5 (PO 4 ) 6 Cl 2 samples did not change much after 40 hours at high temperature, but PbO / Al 2 O 3 did not change as time passes. It can be seen that the Pb-substituted chlorapatite has excellent thermal stability due to the decrease in the ratio of the concentration.

[표 1]TABLE 1

열적 안정성 테스트 이후의 Ca7.5Pb2.5(PO4)6Cl2와 PbO/Al2O3의 ICP-AES 결과ICP-AES results of Ca 7.5 Pb 2.5 (PO 4 ) 6 Cl 2 and PbO / Al 2 O 3 after thermal stability test

(Concentration)(Concentration) 구분division 성분비Ingredient ratio IntendedIntended FreshFresh 10 hr10 hr 20 hr20 hr 30 hr30 hr 40 hr40 hr
Ca7.5Pb2.5(PO4)6Cl2

Ca 7.5 Pb 2.5 (PO 4 ) 6 Cl 2
Ca/PbCa / Pb 3.0 3.0 2.7 2.7 2.7 2.7 2.8 2.8 2.6 2.6 2.7 2.7 Ca/PCa / P 1.31.3 1.2 1.2 1.3 1.3 1.2 1.2 1.2 1.2 1.2 1.2 (Ca+Pb)/P(Ca + Pb) / P 1.7 1.7 1.71.7 1.7 1.7 1.6 1.6 1.6 1.6 1.6 1.6 Pb/PPb / P 0.4 0.4 0.5 0.5 0.5 0.5 0.4 0.4 0.5 0.5 0.4 0.4 PbO/Al2O3 PbO / Al 2 O 3 Al2/PbAl 2 / Pb 1.0 1.0 1.0 1.0 1.2 1.2 3.3 3.3

도 1은 Pb 치환 클로르아파타이트 촉매들에 대한 CH4 전환율을 도시한 그래프.1 is a graph depicting CH 4 conversion for Pb substituted chlorapatite catalysts.

도 2는 Pb 치환 클로르아파타이트 촉매들에 대한 C2 선택도를 도시한 그래프.FIG. 2 is a graph depicting C 2 selectivity for Pb substituted chlorapatite catalysts. FIG.

도 3은 Pb 치환 클로르아파타이트 촉매들에 대한 메탄 이량화 반응 수율을 도시한 그래프.FIG. 3 is a graph depicting methane dimerization yield for Pb substituted chlorapatite catalysts. FIG.

Claims (5)

Ca10-xPbx(PO4)6Cl2 (여기서, X의 범위는 0≤X≤10이다.)의 화학식인 메탄 이량화용 Pb 치환 클로르아파타이트 촉매.A Pb-substituted chlorapatite catalyst for methane dimerization of the formula Ca 10-x Pb x (PO 4 ) 6 Cl 2 , where X ranges from 0 ≦ X ≦ 10. 칼슘 전구체[Ca(NO3)2·4H2O] 수용액과 Pb 전구체[Pb(NO3)2O] 수용액을 혼합하고, pH를 9로 맞춘 후, 0.6M의 (NH4)2HPO4 용액과 0.2M의 NH4Cl 용액을 혼합하고, reflux를 수행하며 숙성시킨 후 건조 및 소성하여 다음 화화식의 메탄 이량화용 Pb 치환 클로르아파타이트 촉매 방법.After mixing the calcium precursor [Ca (NO 3 ) 2 .4H 2 O] aqueous solution and the Pb precursor [Pb (NO 3 ) 2 O] aqueous solution, adjusting the pH to 9, a 0.6M (NH 4 ) 2 HPO 4 solution And 0.2 M NH 4 Cl solution, followed by reflux, aged, dried, and calcined to form a Pb-substituted chlorapatite catalyst for methane dimerization. Ca10-xPbx(PO4)6Cl2 (여기서, X의 범위는 0≤X≤10이다.)Ca 10-x Pb x (PO 4 ) 6 Cl 2 , where X ranges from 0 ≦ X ≦ 10. 제2항에 있어서, 상기 칼슘 전구체 수용액과 Pb 전구체 수용액은 진공증착기(vacuum evaporator)로 탈가스시킨 것을 특징으로 하는 메탄 이량화용 Pb 치환 클로르아파타이트 촉매 방법.The method of claim 2, wherein the aqueous solution of calcium precursor and the aqueous solution of Pb precursor are degassed with a vacuum evaporator. 제1항 내지 제3 중 어느 하나의 Ca10-xPbx(PO4)6Cl2(여기서, X의 범위는 0≤X≤10이다) 촉매 존재하에서 메탄, 산소 및 He 기체를 함유하는 혼합 기체를 접촉시켜 메탄의 이량화 반응을 수행하는 것을 특징으로 하는 C2 화합물 제조 방법.Mixture containing methane, oxygen and He gas in the presence of a Ca 10-x Pb x (PO 4 ) 6 Cl 2 , wherein X ranges from 0 ≦ X ≦ 10 Method for producing a C 2 compound characterized in that to carry out the dimerization reaction of methane by contacting the gas. 제4항에 있어서, 상기 메탄, 산소 및 He 기체는 W/F 1.6×10-4gcat·hr/ml 이하의 조건에서 반응시키는 것을 특징으로 하는 C2 화합물 제조 방법.The method of claim 4, wherein the methane, oxygen and He gas The method for producing C 2 compounds, comprising a step of reacting under the condition of W / F 1.6 × 10 -4 gcat · hr / ml or less.
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