KR0176417B1 - Method for prolongating life of catalyst for vapor phase methanol carbonylation - Google Patents
Method for prolongating life of catalyst for vapor phase methanol carbonylation Download PDFInfo
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- KR0176417B1 KR0176417B1 KR1019960010346A KR19960010346A KR0176417B1 KR 0176417 B1 KR0176417 B1 KR 0176417B1 KR 1019960010346 A KR1019960010346 A KR 1019960010346A KR 19960010346 A KR19960010346 A KR 19960010346A KR 0176417 B1 KR0176417 B1 KR 0176417B1
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- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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Abstract
본 발명에서는 기상 메탄올 카르보닐화 반응용 촉매를 사용하여 초산을 생산하는 도중 촉매성분을 촉매층에 보충하여 촉매의 수명을 연장시킴으로써 공정을 중단시키지 않고서 연속적으로 초산을 제조한다.In the present invention, acetic acid is continuously produced by supplementing the catalyst component to the catalyst layer during the production of acetic acid using the catalyst for gaseous methanol carbonylation reaction to extend the life of the catalyst without interrupting the process.
Description
본 발명은 기상 메탄올 카르보닐화 반응용 촉매의 수명 연장 방법에 관한 것이다.The present invention relates to a method for extending the life of a catalyst for gas phase methanol carbonylation reaction.
초산은 공업적으로 매우 중요한 물질로서, 이것을 생산하는 기술로서는 메탄올을 액상에서 카르보닐화시켜서 얻는 방법이 상업화되어 있다. 그러나 액상 카르보닐화 반응은 반응물의 부식성이 커서 공장 건설비용이 높아지고, 또한 촉매로 사용되는 로듐 화합물이 안정하지 못하여 많은 양의 물을 투여하여 촉매를 안정화시켜야 하는 결과 투여된 물을 제거하기 위한 시설 투자 비용 및 그것의 유지 비용이 많이 드는 문제점이 있다.Acetic acid is an industrially important substance, and as a technique for producing this, a method obtained by carbonylating methanol in a liquid phase has been commercialized. However, the liquid carbonylation reaction has a high corrosiveness of the reactants, which increases the cost of plant construction. Also, the rhodium compound used as a catalyst is not stable, and a large amount of water must be administered to stabilize the catalyst. There is an investment cost and its maintenance costly issue.
이에 액상 공정의 문제점을 해결하기 위하여 기상 비균질 촉매 시스템이 개발되게 되었다. 기상메탄올 카르보닐화 반응이라 함은 반응물인 메틴올과 생성물인 초산과 초산메틸, 그리고 일부의 물 등이 액상이 아닌 기상을 유지할 수 있는 조건을 의미한다. 기상 비균질 촉매를 사용하는 예로서, 본 발명자들이 출원한 미합중국 특허출원 제8,183,334호와 대한민국 특허출원 제92-11524호, 제92-20188호, 제92-25281호, 제92-21568호 및 제93-14392호를 들 수 있는데 이들 문헌에는 로듐과 활성 탄소를 근간으로 하는 촉매계를 사용한 공정들이 소개되어 있다.In order to solve the problem of the liquid phase process, a gaseous heterogeneous catalyst system has been developed. Gas phase methanolylation refers to conditions under which a reactant methol and a product, acetic acid and methyl acetate, and some water can maintain a gaseous phase rather than a liquid phase. As an example of using a gaseous heterogeneous catalyst, U.S. Patent Application Nos. 8,183,334 and Korean Patent Application Nos. 92-11524, 92-20188, 92-25281, 92-21568, and 93 filed by the present inventors -14392, which describes processes using a catalyst system based on rhodium and activated carbon.
그러나 이러한 비균질 기상 메탄올 카르보닐화 반응에서도 문제점이 도출되고 있는 바 특히 활성금속이 반응중 생산물과 함께 반응기 밖으로 미량씩 계속 유출되고, 이러한 유출 현상이 오랫동안 지속되면서 촉매중의 활성금속의 상당량이 손실되어 촉매의 생산성 및 선택성이 저하되는 원인이 된다는 것이다.However, a problem has arisen in such a heterogeneous gaseous methanol carbonylation reaction. Particularly, active metals continue to flow out of the reactor along with the products during the reaction. This is the cause of deterioration of the productivity and selectivity of the catalyst.
따라서 기상 비균질 메탄올 카르보닐화 반응용 촉매는 일정시간이 지난 뒤 새로이 재생시키거나 새 것으로 교환해 주어야 한다. 촉매를 재생하는 경우에는 일반적으로 일단 반응을 중단시키고 반응기 안의 반응물질과 생성물질을 제거하여야 하며 좋은 재생효과를 얻기 위해서는 장시간에 걸쳐 여러 번의 재생 작업이 필요하다. 완전히 새 것으로 교환하는 경우에도 반응을 일단 중단하여야 하며 반응관에 충진되어 있는 촉매를 제거하여야 하는 번거로움이 있다. 또, 촉매의 수명이 짧으면 이 공정의 실용화에 큰 장애가 된다.Therefore, the catalyst for gaseous heterogeneous methanol carbonylation reaction must be regenerated or exchanged for a new one after a certain time. In the case of regenerating the catalyst, it is generally required to stop the reaction and remove the reactants and products in the reactor, and several regeneration operations are required for a long time in order to obtain a good regeneration effect. Even when the exchange is completely new, the reaction must be stopped once and the catalyst charged in the reaction tube has to be removed. In addition, the short lifetime of the catalyst is a major obstacle to the practical use of this process.
이에 본 발명의 목적은 로듐촉매를 사용하여 메탄올을 카르보닐화시키는 반응 공정에서 장시간 사용으로 인하여 활성과 선택성이 저하된 촉매층에 새로운 활성금속을 추가 공급하여 줌으로써, 촉매를 재생 또는 교환하기위해 반응 공정을 장시간 중단시킴이 없이 연속적으로 초산을 생산할 수 있는 방법을 제공함에 있다.Accordingly, an object of the present invention is to supply a new active metal to the catalyst layer deteriorated in activity and selectivity due to prolonged use in the reaction process of carbonylating methanol using a rhodium catalyst, thereby regenerating or exchanging the catalyst. The present invention provides a method for producing acetic acid continuously without stopping for a long time.
상기 목적을 달성하기 위하여 본 발명에서는 로듐이 불활성 담체에 담지되어 이루어진 촉매층에 기상 메탄올 카르보닐화 반응중 추가적으로 로듐금속 또는 로듐화합물과, 알칼리 금속, 알칼리 토금속 또는 전이금속을 포함하는 활성 금속염 혼합물을 공급하여, 로듐 화합물의 양을 불활성 담체의 양을 기준으로 0.1 내지 20중량%(로듐 환산)로 유지시킨다.In order to achieve the above object, in the present invention, an active metal salt mixture including a rhodium metal or a rhodium compound and an alkali metal, an alkaline earth metal or a transition metal is additionally supplied to a catalyst layer in which rhodium is supported on an inert carrier during a gas phase methanol carbonylation reaction. Thus, the amount of the rhodium compound is maintained at 0.1 to 20% by weight (in terms of rhodium) based on the amount of the inert carrier.
반응공정중 추가적으로 공급되는 활성 금속염 혼합물은 로듐 화합물과 로듐의 양을 기준으로 1 내지 1,000몰%의 알칼리 금속, 알칼리 토금속 또는 전이금속 화합물을 분말 형태 또는 이들을 물 또는 유기 용매에 용해시킨 형태일 수 있다.The active metal salt mixture additionally supplied during the reaction process may be in the form of powder of 1 to 1,000 mol% of alkali metal, alkaline earth metal or transition metal compound based on the amount of rhodium compound and rhodium or dissolved in water or an organic solvent. .
또한 반응공정중 추가로 공급되는 활성 금속염 혼합물은 반응초기에 미리 촉매층위에 적층시켜 둠으로써 불활성 담체에 담지되어 있는 활성 금속이 반응중 촉매층으로부터 유출될 때 적층되어 있던 활성 금속 성분이 촉매층에 분산되도록 하여 손실된 활성금속을 보충하게 할 수도 있다.In addition, the active metal salt mixture which is additionally supplied during the reaction process is deposited on the catalyst layer in advance at the beginning of the reaction so that the active metal components deposited on the inert carrier are dispersed in the catalyst layer when the active metal is discharged from the catalyst layer during the reaction. It can also make up for lost active metals.
이하 본 발명에 대하여 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명에 사용되는 로듐 화합물의 예로서는 일반식 RhX3, RhX3·3H2O, Rh2(CO)4X4, [Rh(CO)X4]Y, Rh2(CO)8, Rh(NO3)3, [Rh(CO)2X2]Y, Rh2O3, [Rh(C2H4)2X]2, Rh[(C6H5)3P2](CO)X, 금속 Rh, RhX[(C6H5)3P]2(CH3Y)2, Rh(SnCl3)[(C6H5)P]3, RhX(CO)[(C6H5)3Z]2, [R4Y][Rh(CO)2Z']2, [R4Y]2[Rh(CO)Z'4], RhX[(C6H5)3P]3, RhX[(C6H5)3P]H2, [(C6H5)3P]3Rh(CO)H, Y4Rh2X2(SnX3)4등의 화합물을 들 수 있다. 상기 식들에서 X는 Cl, Br 또는 I이고, Y는 Li, Na 또는 K이고, Z는 As, P 또는 Sb이고, Z는 As, P 또는 Sb이고, Z'는 As, P 또는 N이고, R은 C1-C12알킬이다.Examples of the rhodium compound used in the present invention include the general formula RhX 3 , RhX 3 · 3H 2 O, Rh 2 (CO) 4 X 4 , [Rh (CO) X 4 ] Y, Rh 2 (CO) 8 , Rh (NO 3 ) 3 , [Rh (CO) 2 X 2 ] Y, Rh 2 O 3 , [Rh (C 2 H 4 ) 2 X] 2 , Rh [(C 6 H 5 ) 3 P 2 ] (CO) X, Metal Rh, RhX [(C 6 H 5 ) 3 P] 2 (CH 3 Y) 2 , Rh (SnCl 3 ) [(C 6 H 5 ) P] 3 , RhX (CO) [(C 6 H 5 ) 3 Z] 2 , [R 4 Y] [Rh (CO) 2 Z '] 2 , [R 4 Y] 2 [Rh (CO) Z' 4 ], RhX [(C 6 H 5 ) 3 P] 3 , RhX And compounds such as [(C 6 H 5 ) 3 P] H 2 , [(C 6 H 5 ) 3 P] 3 Rh (CO) H, Y 4 Rh 2 X 2 (SnX 3 ) 4 . Wherein X is Cl, Br or I, Y is Li, Na or K, Z is As, P or Sb, Z is As, P or Sb, Z 'is As, P or N, and R is Is C 1 -C 12 alkyl.
로듐 화합물의 첨가량은 Rh양이 불활성 담체를 기준으로 0.1 내지 20중량%로 유지되도록 하는 양이 적당하고, 바람직하게는 0.6 내지 5중량%로 유지되게 하는 양이다.The amount of the rhodium compound to be added is an amount such that the amount of Rh is maintained at 0.1 to 20% by weight based on the inert carrier, and is preferably an amount to be maintained at 0.6 to 5% by weight.
활성 금속이 담지되는 불활성 담체로는 예를 들면 활성탄, 점토, 알루미나, 실리카 또는 실리카-알루미나를 들 수 있다.Examples of the inert carrier on which the active metal is supported include activated carbon, clay, alumina, silica or silica-alumina.
알칼리 금속과 알칼리 토금속은 예컨대 염소, 브롬, 요오드, 니트로 등과의 염의 형태이고, 알칼리 금속 또는 알칼리 토금 속의 첨가량은 로듐의 양을 기준으로 하여 1내지 1,000몰%이며, 바람직하기로는 200내지 800몰%이고, 200내지 400몰%의 양이 가장 바람직하다.Alkali metals and alkaline earth metals are, for example, in the form of salts with chlorine, bromine, iodine, nitro, etc., and the amount of the alkali metal or alkaline earth metal added is 1 to 1,000 mol% based on the amount of rhodium, preferably 200 to 800 mol%. And an amount of 200 to 400 mol% is most preferred.
전이금속의 첨가량은 로듐의 양을 기준으로 하여 1내지 1000몰%, 바람직하기로는 30내지 300몰%이다.The amount of the transition metal added is 1 to 1000 mol%, preferably 30 to 300 mol%, based on the amount of rhodium.
활성 금속염 혼합물을 용해시키기 위한 용매로는 로듐 화합물과 알칼리 금속, 알칼리 토금속 또는 전이금속 화합물이 용해되는 모든 종류의 유기용매를 사용할 수 있고, 메탄올 또는 초산이 바람직하다.As a solvent for dissolving the active metal salt mixture, all kinds of organic solvents in which a rhodium compound and an alkali metal, alkaline earth metal or transition metal compound are dissolved can be used, and methanol or acetic acid is preferable.
이하 실시예를 통하여 본 발명을 더욱 상세히 설명한다.The present invention will be described in more detail with reference to the following examples.
[실시예 1]Example 1
활성탄의 양을 기준으로 3중량%의 Rh와 Rh의 양을 기준으로 하여 100몰%의 Co가 담지되도록 (RhCl3·3H2O)과 Co(NO3)2·6H2O를 녹인 수용액으로 담체인 활성탄을 함침시켜 Rh 및 Co를 담지시킨 후 300℃에서 소결시켜 촉매를 제조하였다. 위의 방법으로 제조된 촉매 6cc(3.4g)를 외경 1/2인치인 티탄 반응관에 충진하였다. 그런 다음 온도를 서서히 반응온도까지 올리고 반응관에 메탄올과 일산화탄소를 1:2의 비로 유입하고 조촉매인 요오드화메틸을 메탄올 양을 기준으로 10몰% 주입하였다. 반응 압력은 160psi, 반응 온도는 250℃로 하여 반응을 수행하였다.An aqueous solution of (RhCl 3 · 3H 2 O) and Co (NO 3 ) 2 · 6H 2 O dissolved in 3% by weight of Rh and 100 mol% of Co, based on the amount of activated carbon. The catalyst was prepared by impregnating activated carbon as a carrier to support Rh and Co and sintering at 300 ° C. 6cc (3.4g) of the catalyst prepared by the above method was filled in a titanium reaction tube having an outer diameter of 1/2 inch. Then, the temperature was gradually increased to the reaction temperature, and methanol and carbon monoxide were introduced into the reaction tube at a ratio of 1: 2, and 10 mol% of methyl iodide as a promoter was injected based on the amount of methanol. The reaction was carried out at a reaction pressure of 160 psi and a reaction temperature of 250 ° C.
위와 같은 반응 조건하에서 초기에 얻어진 메탄올 전환율 및 초산과 초산메틸의 수율을 다음 표 1에 나타내었다.The methanol conversion and the yields of acetic acid and methyl acetate initially obtained under the above reaction conditions are shown in Table 1 below.
반응시간 경과에 따른 촉매의 초산에 대한 선택성 변화를 알아보기 위해 위 반응조건(250℃, 160psi)에서 6개월 동안 반응시킨 후 메탄올 전환율 및 초산 수율을 측정한 결과는 표 1과 같이 나타나 초산 수율이 매우 저하되어 있었다.In order to determine the change in the selectivity of acetic acid of the catalyst with the reaction time, the reaction rate for 6 months in the above reaction conditions (250 ℃, 160psi) after measuring the methanol conversion and acetic acid yield is shown in Table 1 as shown in Table 1 It was very low.
6개월동안 사용된 위 촉매의 활성을 회복시키기 위해 반응기에 충진된 활성탄의 양을 기준으로 3중량%의 Rh와 Rh의 양을 기준으로 하여 100몰%의 Co가 되도록 (RhCl3·3H2O)과 Co(NO3)2·6H2O를 물에 녹인 수용액을 촉매층에 주입하였다. 활성금속 성분이 보충된 후의 측정된 메탄올 전환율 및 초산 수율을 표 1에 나타내었다. 활성금속 성분의 보충에 의해 촉매의 초산에 대한 선택성이 회복되었음을 알 수 있다.To restore the activity of the above catalyst used for 6 months, 3% by weight of Rh based on the amount of activated carbon charged in the reactor and 100 mol% of Co based on the amount of Rh (RhCl 3 .3H 2 O ) And Co (NO 3 ) 2 .6H 2 O in water was injected into the catalyst layer. The measured methanol conversion and acetic acid yield after supplementing the active metal components are shown in Table 1. It can be seen that replenishment of the active metal component restored the selectivity of the catalyst to acetic acid.
[실시예 2]Example 2
외경 1/2인치인 티탄 반응관의 중간에 활성탄 6cc(3.4g)을 충진하고, 충진된 활성탄의 양을 기준으로 3중량%의 Rh와 Rh의 양을 기준으로 하여 100몰%의 Co에 해당하는(RhCl3·3H2O)과 Co(NO3)2·6H2O의 분말을 혼합하여 충진된 활성탄층의 상부에 충진하였다. 그런다음 반응관에 메탄올과 일산화탄소를 1:2의 비로 유입하고 조촉매인 요오드화메틸을 메탄올 양을 기준으로 10몰%주입하였다. 반응 압력은 160psi, 반응 온도는 250℃로 하여 반응을 수행하였다.Filled with 6cc (3.4g) of activated carbon in the middle of a titanium reaction tube with an outer diameter of 1/2 inch, and corresponds to 100 mol% of Co based on the amount of Rh and Rh of 3% by weight based on the amount of activated carbon The (RhCl 3 · 3H 2 O) and Co (NO 3 ) 2 · 6H 2 O powder was mixed to fill the top of the filled activated carbon layer. Then, methanol and carbon monoxide were introduced into the reaction tube at a ratio of 1: 2, and 10 mol% of methyl iodide as a promoter was injected based on the amount of methanol. The reaction was carried out at a reaction pressure of 160 psi and a reaction temperature of 250 ° C.
위와 같은 반응조건하에서 1개월간 반응을 수행하고 난 후 얻어진 메탄올 전환율 및 초산과 초산메틸의 수율을 표 2에 나타내었다.The methanol conversion and the yield of acetic acid and methyl acetate obtained after performing the reaction for one month under the above reaction conditions are shown in Table 2.
반응시간 경과에 따른 촉매의 초산에 대한 선택성 변화를 알아보기 위해 위 반응조건 (250℃,1600psi)에서 6개월 동안 반응시킨 후 메탄올 전환율 및 초산 수율을 측정한 결과 표 2와 같이 나타나 초산 수율이 매우 저하되었음을 알 수 있었다.In order to determine the change in the selectivity of the catalyst for acetic acid over the reaction time, the reaction was carried out for 6 months at the reaction conditions (250 ℃, 1600 psi) after measuring the methanol conversion and acetic acid yield as shown in Table 2, the acetic acid yield is very high It was found that the degradation.
6개월동안 사용된 위 촉매의 활성을 회복시키기 위해 반응기에 충진된 활성탄의 양을 기준으로 3중량%의 Rh와 Rh의 양을 기준으로 하여 100몰%의 Co가 되도록 (RhCl3·3H2O)과 Co(NO3)2·6H2O를 물에 녹인 수용액을 촉매층에 주입하였다.To restore the activity of the above catalyst used for 6 months, 3% by weight of Rh based on the amount of activated carbon charged in the reactor and 100 mol% of Co based on the amount of Rh (RhCl 3 .3H 2 O ) And Co (NO 3 ) 2 .6H 2 O in water was injected into the catalyst layer.
활성 금속 성분이 보충된 후의 측정된 메탄올 전환율 및 초산 수율을 표 2에 나타내었다. 활성 금속 성분의 보충에 의해 촉매의 초산에 대한 선택성이 회복되었음을 알 수 있다.The measured methanol conversion and acetic acid yield after supplementing the active metal component is shown in Table 2. It can be seen that the replenishment of the active metal component restored the selectivity of the catalyst to acetic acid.
[실시예 3]Example 3
실시예 1에서와 같이 소결시켜 제조한 촉매 6cc(3.4g)를 외경 1/2인치인 반응관에 충진하였다. 충진된 촉매의 양을 기준으로 3중량%의 Rh와 Rh의 양을 기준으로 하여 100몰%의 Co에 해당하는(RhCl·3HO)과 Co(NO)·6HO의 분말을 혼합하여 충진된 촉매층의 상부에 적층하였다. 그런 다음 반응기를 서서히 가열하면서 반응물을 주입하여 실시예 1에서와 동일한 반응조건에서 6개월 동안 반응시킨 후 얻어진 메탄올 전환율 및 초산과 초산메틸의 수율을 다음 표 3에 나타내었다.6 cc (3.4 g) of the catalyst prepared by sintering as in Example 1 was charged into a reaction tube having an outer diameter of 1/2 inch. 3% by weight of Rh based on the amount of catalyst charged and 100% by mole of Co (RhCl 3HO) and Co (NO) · 6HO powders corresponding to 100 mol% of Co Laminated on top. Then, the reactants were injected while the reactor was slowly heated to react for 6 months under the same reaction conditions as in Example 1, and the methanol conversion obtained and the yields of acetic acid and methyl acetate are shown in Table 3 below.
표 3은 촉매층위에 분말형태로 추가로 적층된 활성 금속 성분이 계속적으로 촉매층으로 분산되어 반응과정중 손실되는 활성 금속 성분을 보충하여 줌으로써 촉매의 수명이 연장되었음을 보여준다.Table 3 shows that the life of the catalyst was extended by supplementing the active metal components lost during the reaction by continuously dispersing the active metal components further deposited in powder form on the catalyst layer.
이상에서 설명한 바와 같이 본 발명에 따르면 반응중 촉매의 교환 또는 재생을 위해 반응 공정을 중단시킴이 없이 반응기에 활성금속염 혼합물을 추가하여 줌으로써 초산을 효율적으로 제조할 수 있다.As described above, according to the present invention, acetic acid may be efficiently prepared by adding an active metal salt mixture to the reactor without stopping the reaction process for the exchange or regeneration of the catalyst during the reaction.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016108389A1 (en) * | 2014-12-29 | 2016-07-07 | 한국화학연구원 | Rh-c3n4 heterogeneous catalyst for preparing acetic acid by carbonylation reaction |
| WO2016108390A1 (en) * | 2014-12-29 | 2016-07-07 | 한국화학연구원 | Rh/wxc heterogeneous catalyst for preparing acetic acid through carbonylation reaction |
| WO2017018802A1 (en) * | 2015-07-27 | 2017-02-02 | 한국화학연구원 | Carbon nitride heterogeneous catalyst containing rhodium, process for producing same, and process for producing acetic acid using same |
| WO2018030655A1 (en) * | 2016-08-09 | 2018-02-15 | 한국화학연구원 | Carbon nitride heterogeneous catalyst containing rhodium and palladium, preparation method therefor, acetic acid preparation method using same, and acetic acid prepared thereby |
-
1996
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016108389A1 (en) * | 2014-12-29 | 2016-07-07 | 한국화학연구원 | Rh-c3n4 heterogeneous catalyst for preparing acetic acid by carbonylation reaction |
| WO2016108390A1 (en) * | 2014-12-29 | 2016-07-07 | 한국화학연구원 | Rh/wxc heterogeneous catalyst for preparing acetic acid through carbonylation reaction |
| US10196339B2 (en) | 2014-12-29 | 2019-02-05 | Korea Research Institute Of Chemical Technology | Rh/WxC heterogeneous catalyst for preparing acetic acid by carbonylation reaction |
| US10293335B2 (en) | 2014-12-29 | 2019-05-21 | Korea Research Institute Of Chemical Technology | Rh-C3N4 heterogeneous catalyst for preparing acetic acid by carbonylation reaction |
| WO2017018802A1 (en) * | 2015-07-27 | 2017-02-02 | 한국화학연구원 | Carbon nitride heterogeneous catalyst containing rhodium, process for producing same, and process for producing acetic acid using same |
| US10124321B2 (en) | 2015-07-27 | 2018-11-13 | Korea Research Institute Of Chemical Technology | Carbon nitride heterogeneous catalyst containing rhodium, method for preparing the same, and method for preparing acetic acid using the same |
| WO2018030655A1 (en) * | 2016-08-09 | 2018-02-15 | 한국화학연구원 | Carbon nitride heterogeneous catalyst containing rhodium and palladium, preparation method therefor, acetic acid preparation method using same, and acetic acid prepared thereby |
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