KR20080037900A - Chlorometal compound catalyst used in oxychlorination of methane and method for producing chlorocompound using same - Google Patents

Chlorometal compound catalyst used in oxychlorination of methane and method for producing chlorocompound using same Download PDF

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KR20080037900A
KR20080037900A KR1020060105165A KR20060105165A KR20080037900A KR 20080037900 A KR20080037900 A KR 20080037900A KR 1020060105165 A KR1020060105165 A KR 1020060105165A KR 20060105165 A KR20060105165 A KR 20060105165A KR 20080037900 A KR20080037900 A KR 20080037900A
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chlorometal
reaction
methane
compound catalyst
metal
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KR101108801B1 (en
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배종욱
이용호
이금형
조동현
김성원
오상승
비제이 사미어
채호정
김예훈
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주식회사 엘지화학
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
    • C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
    • C07C17/154—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of saturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
    • C07C19/03—Chloromethanes

Abstract

A chlorometal compound catalyst used in oxychlorination of methane is provided to maximize conversion rate of methane, and a method for producing chloro compounds using oxychlorination of methane is provided to perform oxychlorination in a fixed bed reactor, a fluidized bed reactor, or a circulating fluidized bed reactor by using the chlorometal compound catalyst. In a chlorometal compound catalyst used in oxychlorination of methane, the chlorometal compound catalyst is characterized in that copper, a Group 1A metal, a Group 2A metal, zinc, and a lanthanide metal are supported on a support. The chlorometal compound catalyst comprises 1 to 20 wt.% of copper, 0.1 to 10 wt.% of a Group 1A metal, 0.1 to 10 wt.% of a Group 2A metal, 0.1 to 5 wt.% of zinc, and 1 to 10 wt.% of a lanthanide metal based on the total weight of the chlorometal compound catalyst comprising the support. The Group 1A metal is sodium, lithium, or potassium. The Group 2A metal is magnesium or calcium. The lanthanide metal is lanthanium or cerium. The chlorometal compound catalyst is supported on the support in an impregnated or ion-exchanged form. The support comprises zeolite, alumina, or silica. The zeolite is a ZSM5 type, X type, Y type, or SAPO type zeolite.

Description

메탄의 옥시클로리네이션 반응에 사용하는 클로로금속화합물 촉매 및 이를 이용한 클로로화합물 제조방법{Chlorometal compound catalyst used in Oxychlorination of methane and method for producing chlorocompound using same}Chlorometal compound catalyst used in Oxychlorination of methane and method for producing chlorocompound using same}

본 발명은 메탄의 옥시클로리네이션 반응에 사용하는 클로로금속화합물 촉매 및 상기 촉매를 이용한 클로로화합물의 제조방법에 관한 것으로서, 보다 상세하게는 메탄을 옥시클로리네이션 반응시킬 때 메탄 전환율을 높일 수 있는 클로로금속화합물 촉매 및 이를 이용한 클로로화합물 제조방법에 관한 것이다.The present invention relates to a chlorometal compound catalyst used in the oxcyclorelation reaction of methane and a method for producing a chloro compound using the catalyst, and more particularly, to increase the methane conversion rate when the methane is subjected to the oxcyclorelation reaction. It relates to a chlorometal compound catalyst and a method for producing a chloro compound using the same.

유가의 지속적인 상승으로 인하여 가격이 저렴하며 매장량이 풍부한 천연가스 활용 방안에 관한 연구는 그 중요성이 더욱 증대되고 있으며, 주로 천연가스 중의 메탄을 산소를 이용하는 열분해 반응 및 촉매를 이용하는 커플링 반응에 관한 선행 기술이 많이 보고 되어 있다. 이와 함께 메탄의 활성화를 위하여 클로린 화합물을 이용할 수 있는 종래의 방안으로서, 메탄과 클로린을 고온에서 열분해하는 방법이 미국 등록특허 제4199533호, 미국 등록특허 제4804797호, 미국 등록특허 제4714796호 및 미국 등록특허 제4983783호 등에 개시되어 있다. 그러나, 상기 메탄 의 클로린에 의한 고온 열분해 방법은 선택도 조절에 있어 단순히 제공되는 열공급량 및 반응시간에 의존하므로 메틸렌클로라이드나 코크와 같은 부산물의 발생이 부가적으로 많이 발생한다. Due to the continuous increase in oil prices, research on the utilization of low-cost and rich reserves of natural gas has become more important. The preceding studies on the thermal decomposition reaction of methane in natural gas using oxygen and the coupling reaction using catalyst are mainly performed. A lot of techniques have been reported. In addition, as a conventional method that can use a chlorine compound for the activation of methane, the method of pyrolyzing methane and chlorine at high temperature is US Patent No. 4199533, US Patent No. 4804797, US Patent No. 4714796 and US Patent No. 4983783 and the like. However, the high-temperature pyrolysis of methane by chlorine depends on the amount of heat supplied and the reaction time simply provided to control the selectivity, so that by-products such as methylene chloride and coke are additionally generated.

또한, 메탄의 활성화 방법인 옥시클로리네이션 반응과 관련된 선행기술로는 국제공개출원번호 WO84/003277호, 미국 등록특허 제4769504호 및 미국 등록특허 제5087786호 에서 구리 및 철을 기본 성분으로 하는 담지 촉매 상에서 메탄과 산소 및 염화가스의 반응에 의한 메틸클로라이드(CH3Cl)의 생성에 관한 내용이 개시되어 있다. 이와 관련된 논문으로는 촉매의 안정성 향상 및 메틸클로라이드로(CH3Cl)의 선택도를 향상하기 위한 방법으로서 기본 촉매 성분인 구리에 제 2 금속의 첨가에 의한 효과 및 압력 등에 관한 연구가 보고되어 있다. (J. Am. Chem. Soc., 107(1985), 7097; Appl. Catal., 46(1989), 251 및 Chem. Eng. Sci., 49(1994)4627). 그러나, 상기 기술에 의할 경우, 촉매 활성의 한계로 인해 낮은 전환율을 나타내고 있고, 특히 산소의 존재로 인하여 메탄이 산화되어 수율이 저하되며, 고온 반응시 일부 구리 성분의 휘발에 따른 촉매활성 저하가 나타나는 문제가 있다.In addition, the prior art related to the oxcyclolination reaction, which is a method of activating methane, is supported by International Publication No. WO84 / 003277, US Patent No. 4769504, and US Patent No. 5087786 based on copper and iron. Disclosed is the production of methyl chloride (CH 3 Cl) by reaction of methane with oxygen and chloride gas over a catalyst. In this paper, studies on the effects and pressures of the addition of a second metal to the basic catalyst component copper have been reported as methods for improving the stability of the catalyst and improving the selectivity of methyl chloride furnace (CH 3 Cl). . (J. Am. Chem. Soc., 107 (1985), 7097; Appl. Catal., 46 (1989), 251 and Chem. Eng. Sci., 49 (1994) 4627). However, according to the above technique, the conversion rate is low due to the limitation of the catalytic activity, in particular, the presence of oxygen oxidizes methane due to the presence of oxygen, and lowers the catalytic activity due to volatilization of some copper components at high temperature. There is a problem.

본 발명이 이루고자 하는 기술적 과제는 메탄의 옥시클로리네이션 반응에 사용하는 클로로금속화합물 촉매에 있어서 메탄의 전환율을 극대화 할 수 있는 클로로금속화합물 촉매를 제공하는 데 있다.The technical problem to be achieved by the present invention is to provide a chlorometal compound catalyst that can maximize the conversion of methane in the chlorometal compound catalyst used in the octacyclolation reaction of methane.

본 발명이 이루고자 하는 또 다른 기술적 과제는 메탄의 옥시클로리네이션 반응을 이용한 클로로화합물의 제조방법에 있어서, 고정층 반응기, 유동층 반응기 또는 순환 유동층 반응기 내에서 상기 클로로금속화합물 촉매를 사용하여 옥시클로리네이션 반응을 진행시키는 것을 특징으로 하는 클로로화합물의 제조방법을 제공하는 데 있다.Another technical problem to be achieved by the present invention is a method for preparing a chloro compound using an oxcyclorelation reaction of methane, using a chlorometal compound catalyst in a fixed bed reactor, a fluidized bed reactor or a circulating fluidized bed reactor. It is to provide a method for producing a chloro compound, characterized in that to advance the reaction.

본 발명은 메탄의 옥시클로리네이션 반응에 사용되는 클로로금속화합물 촉매에 있어서,The present invention is a chlorometal compound catalyst used in the oxcyclorelation reaction of methane,

구리, 1A족 금속, 2A족 금속, 아연 및 란타나이드계 금속이 담체에 담지되는 것을 특징으로 하는 클로로금속화합물 촉매에 관한 것이다.The present invention relates to a chlorometal compound catalyst characterized in that copper, a Group 1A metal, a Group 2A metal, zinc and a lanthanide metal are supported on a carrier.

또한 본 발명은 메탄의 옥시클로리네이션 반응을 이용한 클로로화합물의 제조방법에 있어서, 상기 클로로금속화합물 촉매를 사용하여 옥시클로리네이션 반응을 진행시키는 것을 특징으로 하는 클로로화합물의 제조방법에 관한 것이다.The present invention also relates to a method for producing a chloro compound using the chlorocyclo compound reaction of methane, wherein the chlorocyclo compound reaction is carried out using the chlorometal compound catalyst.

이하, 본 발명에 대하여 구체적으로 설명하도록 한다.Hereinafter, the present invention will be described in detail.

본 발명은 메탄의 옥시클로리네이션 반응을 통하여 클로로화합물을 제조함에 있어서, 구리 및 1A족 금속을 기본으로 하는 촉매상에, 주기율표상의 2A족 금속 및 아연과 란타나이드 계열의 금속 성분을 추가로 첨가한 클로로금속화합물 촉매를 사용하여 고정층, 유동층 또는 순환 유동층 반응기에서 수행할 수 있다.In the present invention, in the preparation of chloro compounds through the oxcyclorelation reaction of methane, on the catalyst based on copper and Group 1A metal, additional metal components of Group 2A and zinc and lanthanide series on the periodic table are added. One chlorometal compound catalyst can be used in a fixed bed, fluidized bed or circulating fluidized bed reactor.

주기율표상에서 상기 1A족 계열의 대표적인 금속으로는 나트륨(Na), 칼륨(K), 리튬(Li) 등이 있으며, 이들은 단독 또는 함께 사용할 수 있으며, 이들을 함께 사용하게 되면 보다 높은 활성을 보인다.Representative metals of the Group 1A series on the periodic table include sodium (Na), potassium (K), lithium (Li) and the like, these can be used alone or together, and when used together shows a higher activity.

상기 2A족 계열의 대표적인 금속성분은 마그네슘(Mg), 칼슘(Ca) 등을 들 수 있으며, 상기 성분을 2 이상 함께 첨가하여 촉매를 제조할 수 있다. Representative metal components of the Group 2A series may include magnesium (Mg), calcium (Ca), and the like, and two or more of the above components may be added together to prepare a catalyst.

촉매 구성 성분 중의 기본 금속인 구리 성분은 담체를 포함한 전체 촉매 중량 대비 1 내지 20 중량% 사용하며, 바람직하게는 5 내지 15 중량%를 사용할 수 있다.The copper component, which is the basic metal in the catalyst component, is used in an amount of 1 to 20% by weight based on the total weight of the catalyst including the carrier, and preferably 5 to 15% by weight.

상기 1A족 금속 성분은 담체를 포함한 전체 촉매 중량에 대하여 0.1 내지 10 중량%로 사용이 가능하며 바람직하게는 0.5 내지 5 중량%를 사용할 수 있다.The Group 1A metal component may be used in an amount of 0.1 to 10% by weight, and preferably 0.5 to 5% by weight, based on the total weight of the catalyst including the carrier.

상기 2A족 금속 성분은 담체를 포함한 전체 촉매 중량에 대하여 0.1 내지 10 중량%로 사용이 가능하며 바람직하게는 1 내지 5 중량%를 사용할 수 있다.The Group 2A metal component may be used in an amount of 0.1 to 10% by weight, and preferably 1 to 5% by weight, based on the total weight of the catalyst including the carrier.

본 발명에서는 이상의 3원 금속 외에 란타나이드 계열 금속 및 아연이 포함된다.In the present invention, in addition to the above ternary metal, a lanthanide series metal and zinc are included.

상기 란타나이드 계열 금속성분은 대표적으로 란탄(La)과 세륨(Ce)이며, 담체를 포함한 전체 촉매 중량에 대하여 1 내지 10 중량%, 보다 바람직하게는 2 내지 8 중량%를 사용할 수 있다.The lanthanide-based metal components are typically lanthanum (La) and cerium (Ce), and may be used in an amount of 1 to 10 wt%, more preferably 2 to 8 wt%, based on the total catalyst weight including the carrier.

상기 아연은 담체를 포함한 전체 촉매 중량에 대하여 0.1 내지 5 중량%로 사용이 가능하며 바람직하게는 0.5 내지 3 중량%를 사용할 수 있다. 아연의 함량이 0.1 중량% 이하인 경우는 반응활성이 낮으며, 5 중량% 이상인 경우는 촉매 비활성화가 빨라지는 문제점이 발생할 수 있다.The zinc may be used in an amount of 0.1 to 5% by weight, and preferably 0.5 to 3% by weight, based on the total weight of the catalyst including the carrier. If the zinc content is less than 0.1% by weight, the reaction activity is low, and when the content of 5% by weight or more may cause a problem of faster catalyst deactivation.

또한, 본 발명은 촉매의 반응 활성점의 증가를 위하여 상기 촉매성분이 제 올라이트 등의 담체에 함침, 또는 이온 교환되어 사용된다.  In addition, the present invention is used by impregnating or ion-exchanging the catalyst component in a carrier such as zeolite in order to increase the reaction active point of the catalyst.

상기 담체는 제올라이트, 알루미나 또는 실리카 등이 있으며, 이 중 2 이상의 성분을 혼합하여 사용할 수 있다. 상기 제올라이트는 ZSM5형, Y형, X형, SAPO형 등이 사용될 수 있으며, 더욱 바람직한 담체로는 Y형 제올라이트 또는 ZSM5 이다.The carrier may be zeolite, alumina or silica, and two or more components thereof may be mixed and used. The zeolite may be ZSM5 type, Y type, X type, SAPO type and the like, and more preferred carrier is Y type zeolite or ZSM5.

또한, 촉매의 담지방법으로 상기 다원금소 성분을 담체에 동시에 담지하거나 또는 순차적으로 담지하여 촉매로 사용할 수 있다. In addition, the method of supporting the catalyst may be used as a catalyst by supporting the multi-element component at the same time or sequentially supported on the carrier.

촉매 구성 성분 중의 담체의 함량은 담체를 포함한 전체 촉매 함량에 대하여 45 내지 95 중량% 일 수 있으며, 바람직하게는 65 내지 90 중량%일 수 있다.The content of the carrier in the catalyst component may be 45 to 95% by weight, preferably 65 to 90% by weight relative to the total catalyst content, including the carrier.

다음으로, 메탄의 옥시클로리네이션 반응을 이용한 클로로화합물의 제조방법에 있어서 상기 클로로금속화합물 촉매를 사용하여 옥시클로리네이션 반응을 진행시키는 것을 특징으로 하는 클로로화합물의 제조방법에 대하여 설명한다. Next, a method for producing a chloro compound, characterized in that the chlorocyclo compound reaction is carried out using the chlorometal compound catalyst in the method for producing a chloro compound using an oxcyclorelation reaction of methane.

본 발명의 상기 옥시클로리네이션 반응 조건은 반응 온도 100 내지 600oC 및 반응 압력 1 내지 20기압 하에서 진행되며, 더욱 바람직하게는 반응 온도 200 내지 500oC 및 반응 압력 1 내지 10기압 하에서 진행될 수 있다. 또한, 반응물의 공간 속도(WHSV; liter/kgcat/hr)는 200 내지 10000의 영역에서 수행이 가능하며 더욱 바람직하게는 1000에서 7000의 영역에서 수행이 가능하다. 이와 함께 반응물인 메탄과 염화가스의 몰 비는 0.1 내지 5 범위안에서 사용 가능하며 반응기 크기 및 분리 공정 비용을 고려하여 1 내지 3에서 반응을 수행하는 것이 더욱 바람직하다. 반응물인 산소는 폭발 범위를 벗어나는 영역에서 당량비로 주입할 수 있다.The oxcyclolation reaction conditions of the present invention is carried out under a reaction temperature of 100 to 600 o C and a reaction pressure of 1 to 20 atm, more preferably may be carried out under a reaction temperature of 200 to 500 o C and a reaction pressure of 1 to 10 atm. have. In addition, the space velocity (WHSV; liter / kgcat / hr) of the reactant may be performed in the range of 200 to 10000, and more preferably in the range of 1000 to 7000. In addition, the molar ratio of reactant methane and chloride gas can be used in the range of 0.1 to 5, and more preferably to carry out the reaction at 1 to 3 in consideration of the reactor size and the separation process cost. The reactant oxygen can be injected in equivalence ratios in areas outside the explosive range.

촉매의 클로리네이션 반응과 메탄의 클로리네이션 반응이 분리되어 진행되는 듀얼 베드 형태의 순환 유동층 반응기(circulatinfg fluidized-bed)를 사용하여 클로로화합물을 제조하는 경우, 상기 촉매의 클로리네이션 반응은 200oC ~ 400oC에서 수행하는 것이 바람직하고 메탄의 클로리네이션 반응은 300oC ~ 500oC의 영역에서 수행하면서 공간속도(WHSV; liter/kgcat/hr)는 200~5000의 영역에서 수행하는 것이 가능하다.In the case of preparing a chloro compound using a dual bed type circulatinfg fluidized-bed in which the cloning reaction of the catalyst and the cloning reaction of methane are performed, the cloning reaction of the catalyst is 200 o It is preferable to carry out at C ~ 400 o C, the cloning reaction of methane is carried out in the range of 300 o C ~ 500 o C, while the space velocity (WHSV; liter / kgcat / hr) is carried out in the range of 200 ~ 5000 It is possible to do

이하 하기의 실시예를 통하여 본 발명을 더욱 상세하게 설명하지만, 본 발명의 범위가 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.

[실시예 1 내지 3] [Examples 1-3]

실시예 1은 메탄의 옥시클로리네이션 반응을 60cm 길이의 외경 1인치인 INCOLLOY 고정층 반응기 상에서 수행하였으며, 반응 조건은 반응온도 400oC, 반응물의 공간속도(WHSV; L/kgcat/hr)는 5000 및 반응물인 메탄/염화수소/산소의 몰 비는 1.5:1:0.5로 고정하고 질소로 희석하여 실험하였다. 사용한 촉매는 (10wt%Cu+1wt%K+5wt%La+3.5wt%Mg +1.25wt%Zn+1.5wt%Li) 조성의 클로로금속화합물이며, 이를 Y-zeolite 상에 담지한 후 100oC에서 건조하여 사용하였다.Example 1 was carried out an octacyclolation reaction of methane on a 60-cm outer diameter 1 inch INCOLLOY fixed bed reactor, the reaction conditions of the reaction temperature of 400 ° C, the reactant space velocity (WHSV; L / kgcat / hr) of 5000 And the molar ratio of the reactant methane / hydrogen chloride / oxygen was fixed at 1.5: 1: 0.5 and diluted with nitrogen. The catalyst used is a chlorometal compound of (10wt% Cu + 1wt% K + 5wt% La + 3.5wt% Mg + 1.25wt% Zn + 1.5wt% Li) composition, which is supported on Y-zeolite and then 100 o C Dried over and used.

실시예 2와 3은 (10wt%Cu+1wt%K+7wt%La+2wt%Mg+2wt%Zn) 조성의 클로로금속화합물을 Y-zeolite, 알루미나 상에 각각 담지한 것 외에는 상기 실시예 1과 동일한 조건으로 수행하였다.Examples 2 and 3 are the same as those of Example 1 except that chlorometal compounds having a composition of (10wt% Cu + 1wt% K + 7wt% La + 2wt% Mg + 2wt% Zn) are supported on Y-zeolite and alumina, respectively. It was performed under the same conditions.

[실시예 4]Example 4

실시예 4는 메탄의 옥시클로리네이션 반응을 30cm 길이의 외경 1/2인치인 INCOLLOY 고정층 반응기 상에서 수행하였으며, 반응 조건은 반응온도 400oC, 반응물의 공간속도(WHSV; L/kgcat/hr)는 5000 및 반응물인 메탄/염화수소/산소의 몰 비는 1.5:1:0.5로 고정하고 질소로 희석하여 실험하였다. 사용한 촉매는 (10wt%Cu+1wt%K+7.5wt%La+4wt%Mg +0.5wt%Zn+1wt%Li) 조성의 클로로금속화합물이며, 이를 알루미나 상에 담지한 후 100oC에서 건조하여 사용하였다.Example 4 was carried out an octacyclolation reaction of methane on an INCOLLOY fixed bed reactor having an outer diameter of 1/2 inch of 30 cm length, the reaction conditions of the reaction temperature 400 ° C, the space velocity of the reactants (WHSV; L / kgcat / hr) The molar ratio of 5000 and the reactant methane / hydrogen chloride / oxygen was fixed at 1.5: 1: 0.5 and diluted with nitrogen. The catalyst used is a chlorometal compound of (10wt% Cu + 1wt% K + 7.5wt% La + 4wt% Mg + 0.5wt% Zn + 1wt% Li) composition, which is supported on alumina and dried at 100 ° C. Used.

[비교예 1]Comparative Example 1

비교예1은 상기 실시예4에서 클로로금속화합물의 조성물 중 Zn가 제거된 (10wt%Cu+1wt%K+7.5wt%La+4wt%Mg +1wt%Li) 클로로금속화합물을 사용한 것 외에는 실시예4와 동일한 조건에서 수행하였다. Comparative Example 1 is an example except for using the chlorometal compound (10wt% Cu + 1wt% K + 7.5wt% La + 4wt% Mg + 1wt% Li) in the composition of the chlorometal compound in Example 4 It was carried out under the same conditions as 4.

상기 실시예 1 내지 4 및 비교예 1의 촉매 반응 실험결과는 다음 표 1와 같다.The catalytic reaction test results of Examples 1 to 4 and Comparative Example 1 are as shown in Table 1 below.

Figure 112006078387339-PAT00001
Figure 112006078387339-PAT00001

[실시예 5]Example 5

실시예 5는 순환유동층 반응기에서 실시한 것으로서, 1개의 반응기를 이용하여 각각의 반응 즉, 옥시데이션 (촉매의 클로리네이션) 과 메탄 클로리네이션 반응을 스위칭 운전하여 수행하였다. 먼저 염화수소와 산소를 이용하여 촉매를 클로리네이션 시킨 후에 메탄의 클로리네이션 반응을 100cm 길이의 외경 1인치인 INCOLLOY 유동층 반응기 상에서 수행하였다. 사용된 촉매는 (10wt%Cu+1wt%K+5wt%La+1wt%Mg+0.5wt%Zn+3wt%Li) 조성의 클로로금속화합물이며, 이를 Y-zeolite 상에 담지한 후에 100oC에서 건조하여 사용하였다. 상기 촉매 클로리네이션 반응은 반응온도 250oC, 공간속도(WHSV; L/kgcat/hr)는 900 및 반응물인 염화수소/산소의 몰 비는 1:0.5에서 질소로 희석하여 수행하였으며, 메탄의 클로리네이션 반응은 반응온도 350oC, 공간속도(WHSV; L/kgcat/hr)는 900 및 반응물인 메탄을 질소로 4배 희석하여 1.5분간 수행하였다. 최종적으로 메탄 전환율 65%를 나타내었으며, 생성물로는 메틸클로라이드(41%), 메틸렌클로라이드(41%) 및 클로로포름(18%)의 선택도를 나타내었으며, 산화물인 CO2는 생성되지 않았다. Example 5 was carried out in a circulating fluidized bed reactor, and each reaction was carried out using one reactor, that is, oxidation (chlorination of the catalyst) and methane chloride reaction. First, the catalyst was cloned using hydrogen chloride and oxygen, and then the reaction of methane was carried out on an INCOLLOY fluidized bed reactor having an outer diameter of 1 inch having a length of 100 cm. The catalyst used is a chlorometal compound of (10wt% Cu + 1wt% K + 5wt% La + 1wt% Mg + 0.5wt% Zn + 3wt% Li) composition, which is supported on Y-zeolite and then at 100 o C. It was dried and used. The catalytic cloning reaction was carried out by dilution with nitrogen at a reaction temperature of 250 ° C., a space velocity (WHSV; L / kgcat / hr) of 900 and a molar ratio of hydrogen chloride / oxygen as a reactant of 1: 0.5, and chlorine methane. The reaction was carried out for 1.5 minutes by diluting the reaction temperature of 350 ° C., the space velocity (WHSV; L / kgcat / hr) of 900 and the reactant methane four times with nitrogen. Finally, the methane conversion was 65%, and the product showed selectivity of methyl chloride (41%), methylene chloride (41%) and chloroform (18%), and no oxide CO2 was produced.

[비교예 2] Comparative Example 2

비교예 2는 순환유동층 반응기에서 수행한 것으로서, 1개의 반응기를 이용하여 각각의 반응 즉, 옥시데이션 (촉매의 클로리네이션) 과 메탄 클로리네이션 반응을 스위칭 운전하여 수행하였다. 먼저 염화수소와 산소를 이용하여 촉매를 클로리네이션시킨 후에 메탄의 클로리네이션 반응을 100cm 길이의 외경 1인치인 INCOLLOY 유동층 반응기 상에서 수행하였다. 사용한 촉매는 상업용 에틸렌 옥시클로리네이션 반응에 사용되고 있는 촉매를 이용하였으며 알루미나 담체에 (10wt%Cu+1wt%K)의 조성으로 활성 성분이 담지어 있다. 상기 촉매는 100oC에서 건조한 후에 촉매 반응을 수행하였다. 촉매의 클로리네이션 반응은 반응온도 250oC, 공간속도(WHSV; L/kgcat/hr)는 900 및 반응물인 염화수소/산소의 몰 비는 1:0.5에서 질소로 희석하여 수행하였으며, 메탄의 클로리네이션 반응은 반응온도 350oC, 공간속도(WHSV; L/kgcat/hr)는 350 및 반응물인 메탄을 과량의 질소로 희석하여 몰 비 1:4에서 1.5분간 수행하였다. 최종적으로 메탄 전환율 31%를 나타내었으며, 생성물로는 메틸클로라이드(40%), 메틸렌클로라이드(35%) 및 클로로포름(25%)의 선택도를 나타내었다.Comparative Example 2 was performed in a circulating fluidized bed reactor, and each reaction was carried out using a single reactor, that is, oxidation (chlorination of catalyst) and methane chloride reaction. First, the catalyst was cloned using hydrogen chloride and oxygen, and then the reaction of methane was carried out on an INCOLLOY fluidized bed reactor having an outer diameter of 1 inch having a length of 100 cm. The catalyst used was a catalyst used in a commercial ethylene oxcyclolation reaction, and the active ingredient is contained in the composition of (10 wt% Cu + 1 wt% K) on an alumina carrier. The catalyst was dried at 100 ° C. and then subjected to a catalytic reaction. The reaction of the catalyst was carried out by dilution with nitrogen at a reaction temperature of 250 ° C., a space velocity (WHSV; L / kgcat / hr) of 900, and a molar ratio of hydrogen chloride / oxygen as a reactant of 1: 0.5. The reaction was carried out at a reaction temperature of 350 ° C., space velocity (WHSV; L / kgcat / hr) at 350, and the reactant methane was diluted with excess nitrogen for 1.5 minutes at a molar ratio of 1: 4. Finally, the methane conversion was 31%, and the product showed selectivity of methyl chloride (40%), methylene chloride (35%) and chloroform (25%).

**촉매의 안정성 측정**** Measurement of catalyst stability **

실시예1 내지 4(고정층 반응기 사용)의 반응 종료 후 Cu 원소분석을 실시한 결과, 반응전과 비교하여 반응 후에는 Cu 성분이 80%만 담체에 존재하는 것으로 확인되었다.As a result of performing elemental analysis of Cu after completion of the reaction of Examples 1 to 4 (using a fixed bed reactor), it was confirmed that only 80% of the Cu component was present in the carrier after the reaction compared with before the reaction.

실시예 5 (순환 유동층 반응기 사용)의 반응 종료 후 Cu 원소분석을 실시한 결과, 반응전과 비교하여 반응 후에는 Cu 성분의 손실은 거의 없는 것으로 확인되었다.As a result of performing elemental analysis of Cu after the completion of the reaction of Example 5 (using a circulating fluidized bed reactor), it was confirmed that there was almost no loss of Cu component after the reaction as compared with before the reaction.

이상, 실시예 및 비교예에서 확인된 바와 같이, 메탄의 옥시클로리네이션반응을 수행함에 있어서 본 발명에 따른 조성을 포함하는 클로로금속화합물이 그렇지 않은 경우보다 더 높은 메탄의 전환율을 보였고 Y-zeolite가 알루미나에 비해 높은 메탄 전환률을 보였다. 특별히 실시예 4와 비교예 1을 통해 Zn가 포함된 클로로금속화합물이 Zn가 포함되지 않은 것보다 메탄 전환률이 높은 것을 확인할 수 있었다. 또한, 순환 유동층 반응기의 스위칭 운전 개념을 도입할 경우(실시예 5) 상기 메탄올의 전환율은 더욱 크게 높아지고, Cu촉매의 열에 대한 안정성 및 메탄의 완전 산화물인 CO2의 생성의 억제도 크게 향상됨을 확인할 수 있었다.As can be seen from the examples and the comparative examples, the chlorometal compound comprising the composition according to the present invention exhibited higher conversion of methane than the other case in performing the oxcyclorelation reaction of methane and the Y-zeolite was It showed higher methane conversion compared to alumina. In particular, through Example 4 and Comparative Example 1, it was confirmed that the chlorometal compound containing Zn has a higher methane conversion rate than that containing no Zn. In addition, when the switching operation concept of the circulating fluidized bed reactor was introduced (Example 5), the conversion rate of methanol was further increased, and the stability to the heat of the Cu catalyst and the suppression of the generation of CO 2, which is a complete oxide of methane, were also greatly improved. there was.

본 발명에 따르면, 종래 메탄의 옥시클로리네이션 반응에 사용하는 클로로금속화합물 촉매에 비해 메탄의 전환율이 높을 뿐만 아니라, 순환 유동층 반응기에서 본 발명에 따른 촉매를 사용하여 반응시킬 경우 메탄의 전환율은 50%이상으로 크게 향상함과 동시에 메탄 산화물의 생성을 억제할 수 있는 효과가 있다. According to the present invention, not only the conversion of methane is higher than that of the chlorometal compound catalyst used in the oxcyclorelation of conventional methane, but also the conversion of methane is 50 when the reaction is performed using the catalyst according to the present invention in a circulating fluidized bed reactor. It is greatly improved to more than% and at the same time has the effect of suppressing the production of methane oxide.

Claims (11)

메탄의 옥시클로리네이션 반응에 사용되는 클로로금속화합물 촉매에 있어서,In the chlorometal compound catalyst used for the oxcyclorelation reaction of methane, 구리, 1A족 금속, 2A족 금속, 아연 및 란타나이드계 금속이 담체에 담지되는 것을 특징으로 하는 클로로금속화합물 촉매.A chlorometal compound catalyst, wherein copper, a Group 1A metal, a Group 2A metal, zinc, and a lanthanide metal are supported on a carrier. 제1항에 있어서, 담체를 포함한 상기 클로로금속화합물 촉매의 전체 중량에 대하여 상기 구리 성분은 1 내지 20중량%, 상기 1A족 금속 성분은 0.1 내지 10중량%, 상기 2A족 금속 성분은 0.1 내지 10중량%, 상기 아연 성분은 0.1 내지 5중량% 및 상기 란타나이드계 금속 성분은 1 내지 10중량%으로 이루어지는 것을 특징으로 하는 클로로금속화합물 촉매.The method according to claim 1, wherein the copper component is 1 to 20% by weight, the Group 1A metal component is 0.1 to 10% by weight, and the Group 2A metal component is 0.1 to 10 based on the total weight of the chlorometal compound catalyst including a carrier. Wt%, the zinc component is 0.1 to 5% by weight and the lanthanide metal component is chlorometal compound catalyst, characterized in that consisting of 1 to 10% by weight. 제1항에 있어서, 상기 1A족 금속은 나트륨, 리튬 또는 칼륨인 것을 특징으로 하는 클로로금속화합물 촉매.The chlorometal compound catalyst according to claim 1, wherein the Group 1A metal is sodium, lithium or potassium. 제1항에 있어서, 상기 2A족 금속은 마그네슘 또는 칼슘인 것을 특징으로 하는 클로로금속화합물 촉매.The chlorometal compound catalyst of claim 1, wherein the Group 2A metal is magnesium or calcium. 제1항에 있어서, 란타나이드계 금속은 란타늄 또는 세륨인 것을 특징으로 하는 클로로금속화합물 촉매.The chlorometal compound catalyst according to claim 1, wherein the lanthanide metal is lanthanum or cerium. 제 1항 내지 제5항 중 어느 한 항에 있어서, 상기 클로로금속화합물 촉매는 담체에 함침 또는 이온교환된 형태로 담지되는 것을 특징으로 하는 클로로금속화합물 촉매.The chlorometal compound catalyst according to any one of claims 1 to 5, wherein the chlorometal compound catalyst is supported in an impregnated or ion exchanged form on a carrier. 제6항에 있어서, 상기 담체는 제올라이트, 알루미나 또는 실리카를 포함하는 것을 특징으로 하는 클로로금속화합물 촉매.The chlorometal compound catalyst according to claim 6, wherein the carrier comprises zeolite, alumina or silica. 제7항에 있어서, 상기 제올라이트는 ZSM5형, X형, Y형 또는 SAPO형 인 것을 특징으로 하는 클로로금속화합물 촉매.8. The chlorometal compound catalyst according to claim 7, wherein the zeolite is ZSM5 type, X type, Y type or SAPO type. 메탄의 옥시클로리네이션 반응을 이용한 클로로화합물의 제조방법에 있어서, 고정층 반응기, 유동층 반응기 또는 순환 유동층 반응기 내에서 제1항 기재의 클로로금속화합물 촉매를 사용하여 옥시클로리네이션 반응시켜 제조하는 것을 특징으로 하는 클로로화합물의 제조방법.A method for producing a chloro compound using an oxcyclorelation reaction of methane, characterized in that the chlorocyclo compound reaction according to claim 1 in the fixed bed reactor, fluidized bed reactor or circulating fluidized bed reactor to produce A method for producing a chloro compound. 제9항에 있어서, 상기 고정층 반응기 또는 유동층 반응기 내의 옥시클로리네이션 반응은 100 내지 600oC 반응온도, 1 내지 20기압의 반응압력 및 200 내지 10000 liter/kgcat/hr의 반응물 공간 속도 하에서 진행시키는 것을 특징으로 하는 클로로화합물의 제조방법.10. The process according to claim 9, wherein the oxcyclorelation reaction in the fixed bed or fluidized bed reactor is carried out under a reaction temperature of 100 to 600 ° C., a reaction pressure of 1 to 20 atmospheres and a reactant space velocity of 200 to 10000 liter / kgcat / hr. Method for producing a chloro compound, characterized in that. 제9항에 있어서, 상기 순환 유동층 반응기 내의 옥시클로리네이션 반응은 촉매의 클로리네이션 반응과 메탄의 클로리네이션 반응을 분리하여 반응시키되, 상기 촉매의 클로리네이션 반응은 200 내지 400oC 반응온도 하에서 진행시키고, 상기 메탄의 클로리네이션 반응은 300 내지 500oC 반응온도 및 200 내지 5000 liter/kgcat/hr의 반응물 공간속도 하에서 진행시키는 것을 특징으로 하는 클로로화합물의 제조방법.10. The method according to claim 9, wherein the oxcyclorelation reaction in the circulating fluidized bed reactor is carried out by separating the chlorination reaction of the catalyst from the chlorination reaction of methane, and the reaction of the catalyst is carried out at 200 to 400 ° C. The process for producing a chloro compound, characterized in that the reaction proceeds under temperature, the reaction of the methane is carried out at 300 to 500 ° C reaction temperature and the reactant space velocity of 200 to 5000 liter / kgcat / hr.
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