WO2016099046A1 - Butadiene production method - Google Patents
Butadiene production method Download PDFInfo
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- WO2016099046A1 WO2016099046A1 PCT/KR2015/012694 KR2015012694W WO2016099046A1 WO 2016099046 A1 WO2016099046 A1 WO 2016099046A1 KR 2015012694 W KR2015012694 W KR 2015012694W WO 2016099046 A1 WO2016099046 A1 WO 2016099046A1
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- butene
- butadiene
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/12—Alkadienes
- C07C11/16—Alkadienes with four carbon atoms
- C07C11/167—1, 3-Butadiene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/20—Use of additives, e.g. for stabilisation
Definitions
- the present invention relates to a method for producing butadiene, and more particularly, to a method for producing butadiene in which the strength of the catalyst is maintained even in the oxidative dehydrogenation reaction to ensure long-term operation stability, and the selectivity is not reduced due to less side reactions.
- 1,3-Butadiene is an intermediate of petrochemical products, and its demand and value are gradually increasing all over the world.
- Methods for producing 1,3-butadiene include naphtha cracking, direct dehydrogenation of butenes, and oxidative dehydrogenation of butenes.
- the oxidative dehydrogenation of butene is a reaction in which butene and oxygen react to generate 1,3-butadiene and water, which is very thermodynamically advantageous because stable water is produced.
- the oxidative dehydrogenation of the butenes has a problem of increasing the reactor differential pressure due to the decrease in strength of the catalyst after the reaction.
- an object of the present invention is to provide a butadiene production method in which the strength of the catalyst is maintained even in the oxidative dehydrogenation reaction to ensure long-term operating stability, and the side reaction is small so that the selectivity does not decrease. It is done.
- the present invention is a method for producing butadiene by oxidative dehydrogenation by adding butene and oxygen in a reactor containing a metal composite oxide catalyst, the molar ratio of butene and oxygen is 1.8 to 2.2 It provides a butadiene production method characterized in that.
- Butadiene production method of the present invention is a method for producing butadiene by injecting butene and oxygen in a reactor containing a metal composite oxide catalyst and oxidative dehydrogenation, characterized in that the molar ratio of butene and oxygen is 1.8 to 2.2. .
- the molar ratio of butene and oxygen is less than 1.8, lattice oxygen in the catalyst is consumed and structural stability is deteriorated, and thus catalyst strength is lowered.
- the molar ratio of butene and oxygen exceeds 2.2, by-products There is a problem that a lot of generated butadiene selectivity is lowered.
- the butene may be, for example, 1-butene.
- the butenes may be, for example, at least 95% pure, at least 98% pure, or at least 99% pure.
- the oxidizing dehydrogenation is butene reference gas space velocity, for example (GHSV; Gas Hourly Space Velocity) is from 30 to 80 h - 1 BE (Butene) , 40 to 200 h - 1 BE, or 50 to 150 h - 1 BE days It is possible to achieve high conversion and selectivity within this range.
- GHSV Gas Hourly Space Velocity
- the reaction may further include one or more selected from the group consisting of, for example, steam, carbon dioxide and nitrogen.
- butene: oxygen: steam: nitrogen is, for example, 1: 1.8 to 2.2: 1 to 12:10 to 30 and 1: 1.8 to 2.2: It may be 1 to 10:10 to 25 or 1: 1.8 to 2.2: 1 to 8:12 to 25, and within this range, there is an excellent operation stability and selectivity.
- the oxidative dehydrogenation reaction may be carried out, for example, at a reaction temperature of 250 to 450 ° C, 290 to 400 ° C, or 290 to 350 ° C.
- the reaction may further include, for example, recycling carbon dioxide discharged after the reaction when carbon dioxide is additionally added to the reactant.
- the metal composite oxide catalyst may be, for example, a compound represented by Chemical Formula 1, in which case, butene conversion and butadiene selectivity may be excellent.
- E is at least one selected from the group consisting of nickel, sodium, potassium, rubidium and cesium;
- A, b, c, d, and e are 0.1 to 10, 0.1 to 10, 1 to 20, and 0 to 5 when a is 12;
- Y is a value determined for fitting valences by other components.
- the E may be, for example, cesium, potassium or a mixture thereof, in which case the butene conversion and butadiene selectivity are excellent.
- the molar ratio of molybdenum: bismuth: iron: cobalt: cesium: potassium in Chemical Formula 1 is 12: 0.1-10: 0.1-10: 1-20: 0-5: 0-3 days And, as another example 12: 0.5 ⁇ 2: 0.5 ⁇ 2: 5 ⁇ 15: 0 ⁇ 1: 0 ⁇ 0.5, preferably 12: 0.8 ⁇ 2: 0.8 ⁇ 2: 6 ⁇ 10: 0 ⁇ It may be 0.9: 0 to 0.5, or 12: 0.8 to 2: 0.8 to 2: 6 to 10: 0.01 to 0.9: 0.01 to 0.5, and the conversion, selectivity, and yield of the product are excellent within this range.
- the strength of the metal composite oxide catalyst is, for example, 3.0 or more kgf / cm 2 , 3.0 to 6.0 kgf / cm 2 , or 3.0 to 5.0 kgf / cm 2 , and the effect of excellent long-term operating safety and butadiene selectivity within this range is excellent. have.
- the bismuth molybdate-based composite oxide catalyst may be prepared by the following steps, for example:
- Each of the metal precursors used in step 1) is not particularly limited and may be conventionally used in the art.
- the precursors of nickel, sodium, potassium, rubidium and cesium are not particularly limited, but ammonium chloride, carbonate, nitrate, acetate chloride of each metal, Oxide, etc.
- the bismuth precursor may be bismuth nitrate, and the precursor of molybdenum may be ammonium molybdate.
- Step 1) is a step of preparing a first solution by mixing each metal precursor material in a solvent in order to mix the metal components constituting the bismuth molybdate-based composite oxide.
- the solvent may be distilled water, but is not particularly limited.
- a strong acid is additionally added to the solvent, or the bismuth precursor is separated and dissolved in a solvent containing a strong acid, and then added to the mixed solution of the other metal precursor to prepare a first solution. can do.
- the strong acid may be nitric acid, but is not limited thereto.
- step 2) in order to mix the molybdenum precursor in the first solution, a molybdenum precursor is dissolved in a solvent to prepare a second solution, and then the first solution is added to mix and react.
- the reaction may be performed while stirring, the stirring may be performed at a stirring speed of 100 to 800 rpm in the temperature range of 25 to 80 °C.
- Step 3) is a step of obtaining a bismuth molybdate-based composite oxide by drying, molding and calcining the reactant produced after the reaction.
- the firing may be performed for 1 to 24 hours at a temperature of 400 to 600 °C, for example, preferably may be performed for 2 to 10 hours at a temperature of 450 to 500 °C.
- the reactor used for the oxidative dehydrogenation reaction is not particularly limited as long as it is typically a reactor that can be used in the art, and may be, for example, a tubular reactor, a tank reactor, a fluidized bed reactor, or a fixed bed reactor.
- the stationary phase reactor may be, for example, a multi-tube reactor or a plate reactor.
- the reactor may be, for example, a reactor which is installed in an electric furnace to maintain a constant reaction temperature of the catalyst layer, and the oxidative dehydrogenation reaction proceeds while the reactant continuously passes through the catalyst layer.
- Bismuth nitrate pentahydrate (Bi (NO 3 ) 3 .5 (H 2 O)), iron nitrate hexahydrate (Fe (NO 3 ) 3 .9 (H 2 O)), cobalt nitrate hexahydrate (Co ( NO 3 ) 2 .6 (H 2 O)), potassium nitrate (KNO 3 ), and cesium nitrate (CsNO 3 ) were dissolved in distilled water to prepare a first solution. At this time, bismuth nitrate pentahydrate was dissolved separately in aqueous nitric acid solution and then added.
- a second solution was prepared by dissolving ammonium molybdate tetrahydrate ((NH 4 ) 6 (Mo 7 O 24 ) .4 (H 2 O)) in distilled water.
- the first solution was added to the second solution, followed by stirring at 40 ° C. for 1 hour to form a precipitate.
- the precipitate was dried in an oven at 120 ° C. for 24 hours, and then calcined at 450 ° C. for 5 hours to form Mo 12.
- ⁇ .8 2 Fe 0 .8 0 Bi 2 ⁇ 6 ⁇ Co 10 Cs 0.9 K 0.01 0 .01 ⁇ 0.5 ⁇ Oy (where y is a mole of oxygen atoms that satisfies the valence of the constituent elements other than oxygen)
- a component bismuth molybdate catalyst was prepared.
- 1-butene and oxygen were used as reactants, and additionally nitrogen and steam were introduced together.
- a metal tubular reactor was used, and the metal composite oxide catalyst prepared above was charged so that the volume of the catalyst layer in contact with the reactant was fixed at 50 cc, and the steam was injected into the vaporizer in the form of water, and then at 340 ° C.
- the reactor was designed to vaporize with steam and mix with other reactants 1-butene and oxygen to enter the reactor.
- the amount of butene was controlled using a mass flow controller for liquids, oxygen and nitrogen were controlled using a mass flow controller for gases, and the amount of steam was controlled using a liquid pump.
- the proportion of reactants and gas hourly space velocity (GHSV) were set based on 1-butene.
- Example 1 The metal composite oxide catalyst used in Example 1 and Comparative Examples 1 to 6 and its reaction characteristics were measured by the following method, and the results are shown in Table 1 below.
- Catalyst strength (kgf) The strength was measured in the horizontal direction by the tensile strength measuring device.
- Oxygen reduction rate (%) in the catalyst It was measured using Energy-dispersive X-ray spectroscopy (EDX).
- Example 1 the butadiene production method according to the present invention (Example 1) was hardly observed a decrease in the oxygen content and the catalyst strength in the catalyst, on the contrary, OBR as in the prior art, but Comparative Examples 1 to 3 When less than 1.8, it was confirmed that oxygen in the catalyst lattice was released during the reaction, thereby decreasing the strength of the catalyst.
Abstract
The present invention relates to a butadiene production method and, more specifically, to a method for producing butadiene by introducing butene and oxygen into a reactor having a metal composite oxide catalyst therein and subjecting same to oxidative dehydrogenation, the butadiene production method being characterized in that the molar ratio of butene to oxygen is 1.8 to 2.2. The present invention has the effect of providing a butadiene production method which secures long-term operational stability by maintaining the strength of a catalyst even if subjected to oxidative dehydrogenation and does not diminish selectivity by reducing a side reaction.
Description
〔출원(들)과의 상호 인용〕[Reciprocal citation with application (s)]
본 출원은 2014년 12월 16일자 한국 특허 출원 제10-2014-0181338호 및 2015년 11월 24일자 한국 특허 출원 제10-2015-0164750호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application claims the benefit of priority based on Korean Patent Application No. 10-2014-0181338 filed December 16, 2014 and Korean Patent Application No. 10-2015-0164750 filed November 24, 2015. All content disclosed in the literature is included as part of this specification.
본 발명은 부타디엔 제조방법에 관한 것으로, 보다 상세하게는 산화 탈수소화 반응에도 촉매의 강도가 유지되어 장시간 운전 안정성이 확보되고, 또한 부반응이 적어 선택도가 저하되지 않는 부타디엔 제조방법에 관한 것이다. The present invention relates to a method for producing butadiene, and more particularly, to a method for producing butadiene in which the strength of the catalyst is maintained even in the oxidative dehydrogenation reaction to ensure long-term operation stability, and the selectivity is not reduced due to less side reactions.
1,3-부타디엔은 석유화학 제품의 중간체로서 전세계적으로 그 수요와 가치가 점차 증가하고 있다. 1,3-Butadiene is an intermediate of petrochemical products, and its demand and value are gradually increasing all over the world.
1,3-부타디엔을 제조하는 방법으로는 납사 크래킹, 부텐의 직접 탈수소화 반응, 부텐의 산화적 탈수소화 반응 등이 있다.Methods for producing 1,3-butadiene include naphtha cracking, direct dehydrogenation of butenes, and oxidative dehydrogenation of butenes.
이 중에서도 부텐의 산화적 탈수소화 반응은 부텐과 산소가 반응하여 1,3-부타디엔과 물을 생성하는 반응으로, 안정한 물이 생성되므로 열역학적으로 매우 유리하다.Among them, the oxidative dehydrogenation of butene is a reaction in which butene and oxygen react to generate 1,3-butadiene and water, which is very thermodynamically advantageous because stable water is produced.
또한, 부텐의 직접 탈수소화 반응과 달리 발열 반응이므로, 직접 탈수소화 반응에 비하여 낮은 반응온도에서도 높은 수율의 1,3-부타디엔을 얻을 수 있으며, 추가적인 열공급이 필요하지 않아 상용화 공정으로 매우 적합하다.In addition, unlike the direct dehydrogenation of butenes, it is exothermic, so that a high yield of 1,3-butadiene can be obtained even at low reaction temperatures compared to the direct dehydrogenation, and it is very suitable as a commercialization process because no additional heat supply is required.
그러나, 상기 부텐의 산화적 탈수소화 반응은 반응 후 촉매의 강도 저하로 인하여 반응기 차압이 상승하는 문제가 있다.However, the oxidative dehydrogenation of the butenes has a problem of increasing the reactor differential pressure due to the decrease in strength of the catalyst after the reaction.
〔선행기술문헌〕[Prior art document]
〔특허문헌〕[Patent Documents]
일본 공개특허공보 제2011-006395호(2011.01.13)Japanese Laid-Open Patent Publication No. 2011-006395 (2011.01.13)
상기와 같은 종래기술의 문제점을 해결하고자, 본 발명은 산화 탈수소화 반응에도 촉매의 강도가 유지되어 장시간 운전 안정성이 확보되고, 또한 부반응이 적어 선택도가 저하되지 않는 부타디엔 제조방법을 제공하는 것을 목적으로 한다. In order to solve the problems of the prior art as described above, an object of the present invention is to provide a butadiene production method in which the strength of the catalyst is maintained even in the oxidative dehydrogenation reaction to ensure long-term operating stability, and the side reaction is small so that the selectivity does not decrease. It is done.
본 발명의 상기 목적 및 기타 목적들은 하기 설명된 본 발명에 의하여 모두 달성될 수 있다.The above and other objects of the present invention can be achieved by the present invention described below.
상기의 목적을 달성하기 위하여, 본 발명은 부텐과 산소를 금속 복합산화물 촉매가 내장된 반응기에 투입하여 산화 탈수소화 반응시켜 부타디엔을 제조하는 방법에 있어서, 상기 부텐과 산소의 몰비가 1.8 내지 2.2인 것을 특징으로 하는 부타디엔 제조방법을 제공한다. In order to achieve the above object, the present invention is a method for producing butadiene by oxidative dehydrogenation by adding butene and oxygen in a reactor containing a metal composite oxide catalyst, the molar ratio of butene and oxygen is 1.8 to 2.2 It provides a butadiene production method characterized in that.
본 발명에 따르면 산화 탈수소화 반응에도 촉매의 강도가 유지되고 반응기 차압 상승이 억제되어 장시간 운전 안정성이 확보되고, 또한 부반응이 적어 선택도가 저하되지 않는 부타디엔 제조방법을 제공하는 효과가 있다. According to the present invention, there is an effect of providing a butadiene production method in which the strength of the catalyst is maintained even in the oxidative dehydrogenation reaction, the rise in the reactor differential pressure is suppressed, and the long-term operation stability is secured, and the side reactions are small and the selectivity is not reduced.
이하 본 발명을 상세하게 설명한다. Hereinafter, the present invention will be described in detail.
본 발명자들은 반응기에 부텐과 산소(O2)가 소정 비(ratio)로 투입되는 경우 반응기 내에 충전된 촉매의 강도가 유지되어 장시간 운전 안정성(long run stability)이 확보되고, 또한 부타디엔 선택도가 저하되지 않는 것을 확인하고, 이를 토대로 본 발명을 완성하게 되었다. When the butene and oxygen (O 2 ) are introduced into the reactor at a predetermined ratio, the inventors maintain the strength of the catalyst charged in the reactor to ensure long run stability, and also lower butadiene selectivity. The present invention was completed based on this finding.
본 발명의 부타디엔 제조방법은 부텐과 산소를 금속 복합산화물 촉매가 내장된 반응기에 투입하고 산화 탈수소화 반응시켜 부타디엔을 제조하는 방법에 있어서, 상기 부텐과 산소의 몰비가 1.8 내지 2.2인 것을 특징으로 한다. 상기 부텐과 산소의 몰비가 1.8 미만인 경우 촉매 내의 격자 산소(lattice oxygen)가 소모되어 구조적인 안정성이 붕괴되고, 따라서 촉매 강도가 저하되며, 반대로 상기 부텐과 산소의 몰비가 2.2를 초과하는 경우 부산물이 많이 생성되어 부타디엔 선택도가 저하되는 문제가 있다.Butadiene production method of the present invention is a method for producing butadiene by injecting butene and oxygen in a reactor containing a metal composite oxide catalyst and oxidative dehydrogenation, characterized in that the molar ratio of butene and oxygen is 1.8 to 2.2. . When the molar ratio of butene and oxygen is less than 1.8, lattice oxygen in the catalyst is consumed and structural stability is deteriorated, and thus catalyst strength is lowered. On the contrary, when the molar ratio of butene and oxygen exceeds 2.2, by-products There is a problem that a lot of generated butadiene selectivity is lowered.
상기 부텐은 일례로 1-부텐일 수 있다.The butene may be, for example, 1-butene.
상기 부텐은 일례로 순도가 95% 이상, 98 % 이상, 또는 99 % 이상일 수 있다.The butenes may be, for example, at least 95% pure, at least 98% pure, or at least 99% pure.
상기 산화 탈수소화 반응은 일례로 부텐 기준 기체공간속도(GHSV; Gas Hourly Space Velocity)가 30 내지 80 h-
1BE(Butene), 40 내지 200 h-
1BE, 또는 50 내지 150 h-
1BE일 수 있고, 이 범위 내에서 높은 전환율과 선택도를 나타내는 효과가 있다. The oxidizing dehydrogenation is butene reference gas space velocity, for example (GHSV; Gas Hourly Space Velocity) is from 30 to 80 h - 1 BE (Butene) , 40 to 200 h - 1 BE, or 50 to 150 h - 1 BE days It is possible to achieve high conversion and selectivity within this range.
상기 반응은 일례로 스팀, 이산화탄소 및 질소로 이루어진 군으로부터 선택된 1종 이상을 더 포함할 수 있다.The reaction may further include one or more selected from the group consisting of, for example, steam, carbon dioxide and nitrogen.
상기 반응이 부텐, 산소, 스팀 및 질소를 모두 포함하는 경우 이들의 몰비(부텐:산소:스팀:질소)는 일례로 1:1.8~2.2:1~12:10~30, 1:1.8~2.2:1~10:10~25 혹은 1:1.8~2.2:1~8:12~25일 수 있고, 이 범위 내에서 운전 안정성 및 선택도가 우수한 효과가 있다.When the reaction includes all butene, oxygen, steam and nitrogen, their molar ratio (butene: oxygen: steam: nitrogen) is, for example, 1: 1.8 to 2.2: 1 to 12:10 to 30 and 1: 1.8 to 2.2: It may be 1 to 10:10 to 25 or 1: 1.8 to 2.2: 1 to 8:12 to 25, and within this range, there is an excellent operation stability and selectivity.
상기 산화 탈수소화 반응은 일례로 반응온도 250 내지 450℃, 290 내지 400℃, 또는 290 내지 350℃에서 실시될 수 있다.The oxidative dehydrogenation reaction may be carried out, for example, at a reaction temperature of 250 to 450 ° C, 290 to 400 ° C, or 290 to 350 ° C.
상기 반응은 일례로 반응물에 이산화탄소가 부가적으로 투입되는 경우 반응 후 배출되는 이산화탄소를 재순환시키는 단계를 더 포함할 수 있다.The reaction may further include, for example, recycling carbon dioxide discharged after the reaction when carbon dioxide is additionally added to the reactant.
상기 금속 복합산화물 촉매는 일례로 하기 화학식 1로 표시되는 화합물일 수 있고, 이 경우 부텐 전환율 및 부타디엔 선택도가 우수한 효과가 있다.The metal composite oxide catalyst may be, for example, a compound represented by Chemical Formula 1, in which case, butene conversion and butadiene selectivity may be excellent.
[화학식 1][Formula 1]
MoaBibFecCodEeOyMoaBibFecCodEeOy
상기 식에서, E는 니켈, 나트륨, 칼륨, 루비듐 및 세슘으로 이루어진 군으로부터 선택되는 1종 이상인 것이며; 상기 a, b, c, d, e는 a가 12인 경우 b, c, d, e는 각각 0.1 내지 10, 0.1 내지 10, 1 내지 20, 0 내지 5이고; 상기 y는 다른 성분에 의해 원자가를 맞추기 위해 정해지는 값이다.Wherein E is at least one selected from the group consisting of nickel, sodium, potassium, rubidium and cesium; A, b, c, d, and e are 0.1 to 10, 0.1 to 10, 1 to 20, and 0 to 5 when a is 12; Y is a value determined for fitting valences by other components.
상기 E는 일례로 세슘, 칼륨 또는 이들의 혼합일 수 있고, 이 경우 부텐 전환율 및 부타디엔 선택도가 우수한 효과가 있다.The E may be, for example, cesium, potassium or a mixture thereof, in which case the butene conversion and butadiene selectivity are excellent.
상기 E가 세슘 및 칼륨인 경우 상기 화학식 1에서 몰리브덴 : 비스무스 : 철 : 코발트 : 세슘 : 칼륨의 몰비는 일례로 12 : 0.1~10 : 0.1~10 : 1~20 : 0~5 : 0~3일 수 있고, 또 다른 예로 12 : 0.5~2 : 0.5~2 : 5~15 : 0~1 : 0~0.5일 수 있으며, 바람직하게는 12 : 0.8~2 : 0.8~2 : 6~10 : 0~0.9 : 0~0.5, 또는 12 : 0.8~2 : 0.8~2 : 6~10 : 0.01~0.9 : 0.01~0.5일 수 있고, 이 범위 내에서 생성물의 전환율, 선택율 및 수율이 뛰어난 효과가 있다.When E is cesium and potassium, the molar ratio of molybdenum: bismuth: iron: cobalt: cesium: potassium in Chemical Formula 1 is 12: 0.1-10: 0.1-10: 1-20: 0-5: 0-3 days And, as another example 12: 0.5 ~ 2: 0.5 ~ 2: 5 ~ 15: 0 ~ 1: 0 ~ 0.5, preferably 12: 0.8 ~ 2: 0.8 ~ 2: 6 ~ 10: 0 ~ It may be 0.9: 0 to 0.5, or 12: 0.8 to 2: 0.8 to 2: 6 to 10: 0.01 to 0.9: 0.01 to 0.5, and the conversion, selectivity, and yield of the product are excellent within this range.
상기 금속 복합산화물 촉매의 강도는 일례로 3.0 이상 kgf/cm2, 3.0 내지 6.0 kgf/cm2, 또는 3.0 내지 5.0 kgf/cm2이고, 이 범위 내에서 장시간 운전 안전성 및 부타디엔 선택도가 우수한 효과가 있다.The strength of the metal composite oxide catalyst is, for example, 3.0 or more kgf / cm 2 , 3.0 to 6.0 kgf / cm 2 , or 3.0 to 5.0 kgf / cm 2 , and the effect of excellent long-term operating safety and butadiene selectivity within this range is excellent. have.
상기 비스무스 몰리브데이트계 복합산화물 촉매는 일례로 하기의 단계에 의하여 제조될 수 있다:The bismuth molybdate-based composite oxide catalyst may be prepared by the following steps, for example:
1) 비스무스 전구체; 철 전구체; 코발트 전구체; 및 니켈, 나트륨, 칼륨, 루비듐 및 세슘 중 1종 이상의 금속 전구체;를 포함하는 제1 용액을 제조하는 단계; 2) 몰리브덴 전구체가 용해되어 있는 제2 용액에 상기 제1 용액을 첨가하여 혼합하고 반응시키는 단계; 및 3) 상기 반응 후 건조하고 성형 및 소성시키는 단계.1) bismuth precursors; Iron precursors; Cobalt precursors; And one or more metal precursors of nickel, sodium, potassium, rubidium, and cesium; 2) adding, mixing and reacting the first solution to a second solution in which molybdenum precursor is dissolved; And 3) drying, molding and firing after the reaction.
상기 단계 1)에서 사용된 각 금속 전구체는 특별히 한정되지 않고 당분야에서 통상적으로 사용되는 것을 사용할 수 있다.Each of the metal precursors used in step 1) is not particularly limited and may be conventionally used in the art.
구체적인 예로, 상기 니켈, 나트륨, 칼륨, 루비듐 및 세슘의 전구체는 특별히 한정되는 것은 아니나, 상기 각 금속의 암모늄염화물(ammonium), 탄산염화물(carbonate), 질산염화물(nitrate), 아세트산염화물(acetate), 산화물(oxide) 등일 수 있으며, 또 다른 예로 상기 비스무스 전구체는 비스무스 나이트레이트일 수 있고, 상기 몰리브덴의 전구체는 암모늄 몰리브데이트일 수 있다.As a specific example, the precursors of nickel, sodium, potassium, rubidium and cesium are not particularly limited, but ammonium chloride, carbonate, nitrate, acetate chloride of each metal, Oxide, etc. The bismuth precursor may be bismuth nitrate, and the precursor of molybdenum may be ammonium molybdate.
상기 단계 1)은 비스무스 몰리브데이트계 복합산화물을 구성하는 금속 성분들을 혼합하기 위하여, 각 금속 전구체 물질을 용매에 넣고 혼합하여 제1 용액을 제조하는 단계이다. 상기 용매는 증류수일 수 있으나, 특별히 한정되는 것은 아니다. 이때, 비스무스 전구체의 용해도를 높이기 위하여, 상기 용매에 강산을 추가로 첨가하거나 또는 비스무스 전구체를 강산이 포함된 용매에 분리하여 용해시킨 후 상기 다른 금속 전구체가 혼합된 용액에 첨가하여 제1 용액을 제조할 수 있다. 상기 강산은 질산일 수 있으나, 이에 제한되는 것은 아니다.Step 1) is a step of preparing a first solution by mixing each metal precursor material in a solvent in order to mix the metal components constituting the bismuth molybdate-based composite oxide. The solvent may be distilled water, but is not particularly limited. In this case, in order to increase the solubility of the bismuth precursor, a strong acid is additionally added to the solvent, or the bismuth precursor is separated and dissolved in a solvent containing a strong acid, and then added to the mixed solution of the other metal precursor to prepare a first solution. can do. The strong acid may be nitric acid, but is not limited thereto.
상기 단계 2)는 제1 용액에 몰리브덴 전구체를 혼합하기 위하여, 몰리브덴 전구체를 용매에 용해시켜 제2 용액을 제조한 후, 상기 제1 용액을 첨가하여 혼합하고 반응시키는 단계이다. 이때, 상기 반응은 교반하면서 수행하는 것일 수 있으며, 상기 교반은 25 내지 80℃의 온도범위에서 100 내지 800 rpm의 교반속도로 수행하는 것일 수 있다.In step 2), in order to mix the molybdenum precursor in the first solution, a molybdenum precursor is dissolved in a solvent to prepare a second solution, and then the first solution is added to mix and react. At this time, the reaction may be performed while stirring, the stirring may be performed at a stirring speed of 100 to 800 rpm in the temperature range of 25 to 80 ℃.
상기 단계 3)은 상기 반응 후 생성된 반응물을 건조하고 성형 및 소성하여 비스무스 몰리브데이트계 복합산화물을 수득하는 단계이다. 상기 소성은 일례로 400 내지 600 ℃의 온도에서 1 내지 24 시간 동안 수행할 수 있으며, 바람직하게는 450 내지 500 ℃의 온도에서 2 내지 10 시간 동안 수행하는 것일 수 있다.Step 3) is a step of obtaining a bismuth molybdate-based composite oxide by drying, molding and calcining the reactant produced after the reaction. The firing may be performed for 1 to 24 hours at a temperature of 400 to 600 ℃, for example, preferably may be performed for 2 to 10 hours at a temperature of 450 to 500 ℃.
상기 산화 탈수소화 반응에 사용되는 반응기는 통상적으로 이 기술분야에서 사용될 수 있는 반응기인 경우 특별히 제한되지 않고, 일례로 관형 반응기, 조형 반응기, 유동상 반응기 또는 고정상 반응기일 수 있다.The reactor used for the oxidative dehydrogenation reaction is not particularly limited as long as it is typically a reactor that can be used in the art, and may be, for example, a tubular reactor, a tank reactor, a fluidized bed reactor, or a fixed bed reactor.
상기 고정상 반응기는 일례로 다관식 반응기 또는 플레이트식 반응기일 수 있다.The stationary phase reactor may be, for example, a multi-tube reactor or a plate reactor.
상기 반응기는 일례로 전기로 안에 설치되어 촉매층의 반응온도가 일정하게 유지되고, 반응물이 촉매층을 연속적으로 통과하면서 산화 탈수소화 반응이 진행되는 반응기일 수 있다.The reactor may be, for example, a reactor which is installed in an electric furnace to maintain a constant reaction temperature of the catalyst layer, and the oxidative dehydrogenation reaction proceeds while the reactant continuously passes through the catalyst layer.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.
[실시예]EXAMPLE
제조예: 비스무스 몰리브데이트계 복합산화물 촉매의 제조Preparation Example: Preparation of Bismuth Molybdate Composite Oxide Catalyst
비스무스 나이트레이트 5수화물(Bi(NO3)3·5(H2O)), 철 나이트레이트 9수화물(Fe(NO3)3·9(H2O)), 코발트 나이트레이트 6수화물(Co(NO3)2·6(H2O)), 칼륨 나이트레이트(KNO3), 및 세슘 나이트레이트(CsNO3)를 증류수에 용해시켜 제1 용액을 제조하였다. 이때 비스무스 나이트레이트 5수화물은 질산 수용액으로 따로 용해시킨 다음 첨가하였다. Bismuth nitrate pentahydrate (Bi (NO 3 ) 3 .5 (H 2 O)), iron nitrate hexahydrate (Fe (NO 3 ) 3 .9 (H 2 O)), cobalt nitrate hexahydrate (Co ( NO 3 ) 2 .6 (H 2 O)), potassium nitrate (KNO 3 ), and cesium nitrate (CsNO 3 ) were dissolved in distilled water to prepare a first solution. At this time, bismuth nitrate pentahydrate was dissolved separately in aqueous nitric acid solution and then added.
또한, 암모늄 몰리브데이트 4수화물((NH4)6(Mo7O24)·4(H2O))을 증류수에 용해시켜 제2 용액을 제조하였다.Further, a second solution was prepared by dissolving ammonium molybdate tetrahydrate ((NH 4 ) 6 (Mo 7 O 24 ) .4 (H 2 O)) in distilled water.
상기 제2 용액에 상기 제1 용액을 첨가한 다음 40 ℃에서 1 시간 동안 교반하여 침전물을 생성시켰고, 이 침전물을 24 시간 동안 120 ℃의 오븐에서 건조한 다음, 450 ℃에서 5시간 동안 소성하여 Mo12Bi0
.8~
2Fe0
.8~
2Co6
~
10Cs0
.01~0.9K0.01~
0.5Oy(여기에서 y는 산소 이외의 구성 원소의 원자가를 만족하는 산소 원자의 몰이다)의 다성분계 비스무스 몰리브데이트 촉매를 제조하였다.The first solution was added to the second solution, followed by stirring at 40 ° C. for 1 hour to form a precipitate. The precipitate was dried in an oven at 120 ° C. for 24 hours, and then calcined at 450 ° C. for 5 hours to form Mo 12. of the ~ .8 2 Fe 0 .8 0 Bi 2 ~ 6 ~ Co 10 Cs 0.9 K 0.01 0 .01 ~ 0.5 ~ Oy (where y is a mole of oxygen atoms that satisfies the valence of the constituent elements other than oxygen) A component bismuth molybdate catalyst was prepared.
실시예 1 및 비교예 1 내지 6Example # 1 and Comparative Examples 1 to 6
반응물로는 1-부텐과 산소를 사용하였으며, 부가적으로 질소와 스팀이 함께 유입되도록 하였다. 반응기로는 금속 관형 반응기를 사용하였고, 앞서 제조된 금속 복합산화물 촉매를, 반응물이 접촉하는 촉매층의 부피가 50 cc로 고정되도록 충전하였고, 스팀은 기화기(vaporizer)로 물의 형태로 주입되어 340℃에서 스팀으로 기화되어 다른 반응물인 1-부텐 및 산소와 함께 혼합되어 반응기에 유입되도록 반응 장치를 설계하였다. 부텐의 양은 액체용 질량유속조절기를 사용하여 제어하였으며, 산소 및 질소는 기체용 질량유속조절기를 사용하여 제어하였고, 스팀의 양은 액체 펌프를 이용해서 주입속도를 조절하였다. 또한, 반응물의 비율 및 GHSV(gas hourly space velocity)는 1-부텐을 기준으로 설정하였다.1-butene and oxygen were used as reactants, and additionally nitrogen and steam were introduced together. As a reactor, a metal tubular reactor was used, and the metal composite oxide catalyst prepared above was charged so that the volume of the catalyst layer in contact with the reactant was fixed at 50 cc, and the steam was injected into the vaporizer in the form of water, and then at 340 ° C. The reactor was designed to vaporize with steam and mix with other reactants 1-butene and oxygen to enter the reactor. The amount of butene was controlled using a mass flow controller for liquids, oxygen and nitrogen were controlled using a mass flow controller for gases, and the amount of steam was controlled using a liquid pump. In addition, the proportion of reactants and gas hourly space velocity (GHSV) were set based on 1-butene.
하기 표 1 에 기재된 GHSV, OBR(산소 대 부텐(O2/C4H8)의 몰비)과 부텐:질소의 몰비 1:12 조건하에서, 반응온도를 320℃로 유지하면서 하기 표 1 에 기재된 운전시간 동안 반응시켰고, 반응 후 생성물은 가스 크로마토그래피를 이용하여 분석하였다.The operations described in Table 1 below while maintaining the reaction temperature at 320 ° C. under the conditions of GHSV, OBR (molar ratio of oxygen to butene (O 2 / C 4 H 8 )) and butene: nitrogen, as described in Table 1 below. The reaction was carried out for a time, and after the reaction the product was analyzed using gas chromatography.
[시험예][Test Example]
상기 실시예 1 및 비교예 1 내지 6에서 사용된 금속 복합산화물 촉매 및 이의 반응 특성을 하기의 방법으로 측정하였고, 그 결과를 하기의 표 1에 나타내었다.The metal composite oxide catalyst used in Example 1 and Comparative Examples 1 to 6 and its reaction characteristics were measured by the following method, and the results are shown in Table 1 below.
* 촉매강도(kgf): 인장강도 측정장치로 수평방향으로 강도를 측정하였다.* Catalyst strength (kgf): The strength was measured in the horizontal direction by the tensile strength measuring device.
* 촉매 내 산소 감소율(%): EDX(Energy-dispersive X-ray spectroscopy)를 이용하여 측정하였다.Oxygen reduction rate (%) in the catalyst: It was measured using Energy-dispersive X-ray spectroscopy (EDX).
* 촉매강도 감소율(%): 하기 수학식 1을 이용하여 계산하였다.* Catalytic strength reduction rate (%): was calculated using the following equation (1).
[수학식 1][Equation 1]
촉매강도 감소율(%)=((반응 전 촉매강도-반응 후 촉매강도)/반응 전 촉매강도) X 100% Reduction in catalyst strength = ((catalytic strength before reaction-catalyst strength after reaction) / catalyst strength before reaction) X 100
* 선택도: 가스 크로마토그래피로 분석한 데이터를 가지고, 하기 수학식 2를 이용하여 계산하였다.* Selectivity: The data analyzed by gas chromatography were calculated using Equation 2 below.
[수학식 2][Equation 2]
선택도(%)=(생성된 1,3-부타디엔 몰수 / 반응한 1-부텐 몰수) X 100Selectivity (%) = (moles of 1,3-butadiene produced / moles of 1-butene reacted) X 100
| OBROBR | GHSV(h-1 BE)GHSV (h-1 BE) | 운전시간Driving time | 촉매내산소함량변화율Change rate of oxygen content in catalyst | 촉매강도감소율Reduction in catalyst strength | 강도burglar | ||
| 반응 전Before the reaction | 반응 후After the reaction | ||||||
| 실시예 1Example 1 | 1.81.8 | 3838 | 40hr40hr | <0.1%<0.1% | <0.1%<0.1% | 3.183.18 | 3.223.22 |
| 비교예 1Comparative Example 1 | 1.51.5 | 3838 | 40hr40hr | 19% 감소19% reduction | 32.7%32.7% | 3.183.18 | 2.142.14 |
| 비교예 2Comparative Example 2 | 1.01.0 | 7575 | 39days39days | 19% 감소19% reduction | 11.3%11.3% | 3.283.28 | 2.912.91 |
| 비교예 3 Comparative Example 3 | 1.01.0 | 7575 | 37days37days | 11% 감소11% reduction | 18.6%18.6% | 3.183.18 | 2.592.59 |
| OBROBR | GHSV(h-1 BE)GHSV (h-1 BE) | 운전시간Driving time | 전환율(%)% Conversion | 선택도(%)Selectivity (%) | 수율(%)yield(%) | |
| 실시예 1Example 1 | 1.81.8 | 3838 | 40hr40hr | 98.1598.15 | 90.4590.45 | 88.7888.78 |
| 비교예 4Comparative Example 4 | 2.32.3 | 3838 | 40hr40hr | 98.5398.53 | 86.0986.09 | 84.8284.82 |
상기 표 1에 나타낸 바와 같이, 본 발명에 따른 부타디엔 제조방법(실시예 1)은 촉매 내 산소함량과 촉매강도의 감소가 거의 관찰되지 않았고, 반대로, 종래기술이나, 비교예 1 내지 3과 같이 OBR이 1.8 미만인 경우 반응 중 촉매 격자 내의 산소가 빠져 나와 촉매의 강도가 저하됨을 확인할 수 있었다.As shown in Table 1, the butadiene production method according to the present invention (Example 1) was hardly observed a decrease in the oxygen content and the catalyst strength in the catalyst, on the contrary, OBR as in the prior art, but Comparative Examples 1 to 3 When less than 1.8, it was confirmed that oxygen in the catalyst lattice was released during the reaction, thereby decreasing the strength of the catalyst.
또한, 비교예 4과 같이 OBR이 2.2를 초과하는 경우 부타디엔 선택도가 크게 감소함을 확인할 수 있었다.In addition, as in Comparative Example 4, when the OBR exceeds 2.2, butadiene selectivity was confirmed to be greatly reduced.
Claims (7)
- 부텐과 산소를 금속 복합산화물 촉매가 내장된 반응기에 투입하고 산화 탈수소화 반응시켜 부타디엔을 제조하는 방법에 있어서,In the method for producing butadiene by introducing butene and oxygen into a reactor containing a metal composite oxide catalyst and oxidative dehydrogenation reaction,상기 부텐과 산소의 몰비가 1.8 내지 2.2인 것을 특징으로 하는The molar ratio of butene and oxygen is characterized in that 1.8 to 2.2부타디엔 제조방법.Butadiene manufacturing method.
- 제1항에 있어서,The method of claim 1,상기 부텐은 1-부텐인 것을 특징으로 하는The butene is characterized in that 1-butene부타디엔 제조방법.Butadiene manufacturing method.
- 제1항에 있어서,The method of claim 1,상기 산화 탈수소화 반응은 기체공간속도(GHSV)가 30 내지 80 h- 1BE인 것을 특징으로 하는The oxidative dehydrogenation reaction is characterized in that the gas space velocity (GHSV) is 30 to 80 h - 1 BE부타디엔 제조방법.Butadiene manufacturing method.
- 제1항에 있어서,The method of claim 1,상기 금속 복합산화물 촉매는 하기 화학식 1The metal composite oxide catalyst may be represented by the following Chemical Formula 1[화학식 1][Formula 1]MoaBibFecCodEeOyMoaBibFecCodEeOy(상기 식에서, E는 니켈, 나트륨, 칼륨, 루비듐 및 세슘으로 이루어진 군으로부터 선택되는 1종 이상인 것이며; 상기 a, b, c, d, e는 a가 12인 경우, b, c, d, e는 각각 0.1 내지 10, 0.1 내지 10, 1 내지 20, 0 내지 5이고; 상기 y는 다른 성분에 의해 원자가를 맞추기 위해 정해지는 값이다.)로 표시되는 금속 복합산화물을 포함하는 것을 특징으로 하는Wherein E is at least one selected from the group consisting of nickel, sodium, potassium, rubidium and cesium; wherein a, b, c, d and e are b, c, d, e when a is 12 Are 0.1 to 10, 0.1 to 10, 1 to 20, 0 to 5, respectively; y is a value determined to match valence by other components).부타디엔 제조방법.Butadiene manufacturing method.
- 제1항에 있어서,The method of claim 1,상기 반응은 스팀, 이산화탄소 및 질소로 이루어진 군으로부터 선택된 1종 이상을 더 포함하는 것을 특징으로 하는The reaction is characterized in that it further comprises one or more selected from the group consisting of steam, carbon dioxide and nitrogen부타디엔 제조방법.Butadiene manufacturing method.
- 제5항에 있어서,The method of claim 5,상기 반응은 부텐, 산소, 스팀 및 질소의 몰비가 1:1.8~2.2:1~12:10~30인 것을 특징으로 하는The reaction is characterized in that the molar ratio of butene, oxygen, steam and nitrogen is 1: 1.8 ~ 2.2: 1 ~ 12:10 ~ 30부타디엔 제조방법.Butadiene manufacturing method.
- 제1항에 있어서,The method of claim 1,상기 반응기는 관형 반응기, 조형 반응기, 유동상 반응기 또는 고정상 반응기인 것을 특징으로 하는The reactor is characterized in that the tubular reactor, tank reactor, fluidized bed reactor or fixed bed reactor부타디엔 제조방법.Butadiene manufacturing method.
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| EP15853645.8A EP3059219B1 (en) | 2014-12-16 | 2015-11-25 | Butadiene production method |
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