KR20120035368A - METHOD FOR PREPARING α,β-UNSATURATED ALDEHYDE - Google Patents
METHOD FOR PREPARING α,β-UNSATURATED ALDEHYDE Download PDFInfo
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- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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Abstract
Description
본 발명은 α,β-불포화 알데히드의 제조방법에 관한 것으로, 보다 상세하게는 부반응이 적고 생성물의 선택도가 뛰어난 α,β-불포화 알데히드의 제조방법에 관한 것이다.
The present invention relates to a method for producing α, β-unsaturated aldehyde, and more particularly, to a method for preparing α, β-unsaturated aldehyde with less side reactions and excellent product selectivity.
알돌-축합 반응은 산업상 매우 중요한 반응인데, 이때 생성되는 α, β-불포화 카보닐 화합물은 특유의 반응성으로 인해 수 많은 유기 화합물의 합성을 위한 출발 물질 또는 중간체로 이용된다. Aldol-condensation reactions are very important industrially, in which the resulting α, β-unsaturated carbonyl compounds are used as starting materials or intermediates for the synthesis of many organic compounds due to their unique reactivity.
또한, α,β-불포화 알데히드는 수소화되어, 카르복실산으로 산화될 수 있는 포화 알데히드로 전환되는데, 이는 플라스틱용 윤활유, 건조제, 퍼에스테르 또는 안정제 등의 원료로 이용된다. In addition, α, β-unsaturated aldehydes are converted to saturated aldehydes which can be hydrogenated and oxidized to carboxylic acids, which are used as raw materials for plastic lubricants, desiccants, peresters or stabilizers.
또한, α,β-불포화 알데하이드를 완전히 수소화시키면, 세제 및 가소제의 제조에 이용되거나 용매로서 사용되는 1급 포화 알콜이 생성된다.In addition, complete hydrogenation of α, β-unsaturated aldehydes results in primary saturated alcohols used in the manufacture of detergents and plasticizers or as solvents.
상기 알돌-축합 반응은 산 또는 염기에 의해 촉진되는데, 산업적 공정에서는 염기, 특히 NaOH와 같은 무기 염기가 많이 사용된다.The aldol-condensation reaction is facilitated by acids or bases, and in industrial processes many bases, especially inorganic bases such as NaOH, are used.
독일특허 제3,530,839호는 n-부티르알데히드를 0.5 내지 5 중량％ 농도의 수산화나트륨 수용액을 사용하고, 초대기압 하에 100 내지 170 ℃의 유동관 내에서 체류 시간을 0.2 내지 5 분으로 반응시킨 다음, 60 ℃로 냉각시키고, 반응 생성물을 촉매 수용액과 유기상으로 분리한 후, 촉매 수용액의 일부분을 배출시켜 제거함과 동시에 새로운 촉매 용액으로 교체하여 유동관으로 재순환시키고 유기상으로부터 2-에틸헥스-2-엔알을 얻는 알돌-축합 반응을 개시하였다.German Patent No. 3,530,839 uses n-butyraldehyde in an aqueous solution of sodium hydroxide at a concentration of 0.5 to 5% by weight, and reacts the residence time to 0.2 to 5 minutes in a flow tube at 100 to 170 ° C. under superatmospheric pressure. After cooling to 占 폚, the reaction product was separated into the aqueous catalyst solution and the organic phase, and then a part of the aqueous catalyst solution was discharged and removed, and then replaced with a fresh catalyst solution to be recycled into a flow tube to obtain 2-ethylhex-2-enal from the organic phase. The condensation reaction was initiated.
그러나, 촉매 수용액의 일부를 배출시켜 제거함으로써 촉매가 다량 소비되고, 배출된 촉매 수용액은 유기 화합물을 함유하고 있으므로, 후처리하거나 또는 용출액 처리장치 내에서 처리해야 하므로, 추가 비용이 드는 문제가 있다.However, a large amount of catalyst is consumed by discharging and removing a part of the aqueous solution of the catalyst. Since the discharged aqueous solution of the catalyst contains an organic compound, it has to be post-treated or treated in an eluate treatment device, which causes additional cost.
또한, 유럽특허 제634,994호는 a) 출발 알데히드와 촉매 수용액을 비단열 조건하에 교반 반응기 내에 주입하는 단계; b) 교반 반응기로부터 수득한 반응 혼합물을 증류관의 중간 부분에 도입하는 단계; c) 증류관 상부의 유기층(출발물질과 수증기)과 하부의 수성층(촉매 수용액, 생성물 및 부산물)으로 분리되는 단계; d) 수성층의 일부를 배출시키는 단계; e) 유기층을 반응기로 재순환시키는 단계; f) 증류관 하부의 수성층을 하부 생성물로 수득하는 단계; g) 하부 생성물을 냉각시키는 단계; h) 냉각된 하부 생성물을 생성물, 고분자량의 부산물 및 소량의 촉매 용액이 함유된 상부의 유기상과, 염 형태의 부산물로서 생성된 카르복실산이 함유되어 있는 하부의 촉매 수용액으로 분리하는 단계; i) 촉매 수용액을 반응기로 재순환시키는 단계; 및 j) 상부의 유기상을 배출시키는 단계;를 포함하는 연속적인 알돌-축합 반응을 개시하였다.In addition, EP 634,994 comprises: a) injecting starting aldehyde and aqueous catalyst solution into a stirred reactor under non-insulated conditions; b) introducing the reaction mixture obtained from the stirred reactor into the middle portion of the distillation tube; c) separating the organic layer (starting material and water vapor) at the top of the distillation tube and the aqueous layer (aqueous catalyst solution, product and by-products) at the bottom; d) draining a portion of the aqueous layer; e) recycling the organic layer to the reactor; f) obtaining an aqueous layer at the bottom of the distillation tube as the bottom product; g) cooling the bottom product; h) separating the cooled bottom product into an upper organic phase containing the product, a high molecular weight by-product and a small amount of catalyst solution and a lower aqueous catalyst solution containing the carboxylic acid produced as a by-product in salt form; i) recycling the aqueous catalyst solution to the reactor; And j) draining the upper organic phase.
그러나, 반응 혼합물의 증류에 에너지가 필요하고, 하부 생성물을 냉각시키기 위해서는 냉각 매질이 필요하며, 증류 단계에서 촉매상에 존재하는 반응 혼합물은 열적 응력을 받아 카니자로(cannizzaro reaction) 반응에 의한 부산물 생성이 용이해져 수율이 저하되고, 최종 조생성물은 세정 없이 장치로부터 분리되는데, 소량의 촉매를 여전히 함유하여 저장기간 동안 생성물의 품질을 악화시키며, 이를 화학 합성, 예를 들면, 수소화 반응 등에 사용하는 경우 심각한 문제를 일으킬 수 있다.However, energy is required for the distillation of the reaction mixture, a cooling medium is required to cool the bottom product, and the reaction mixture present on the catalyst in the distillation step is thermally stressed to produce by-products from the cannizzaro reaction. This facilitates lowering yields, and the final crude product is separated from the apparatus without washing, which still contains a small amount of catalyst, which degrades the quality of the product during storage, which is used for chemical synthesis, e.g. hydrogenation, etc. It can cause serious problems.
따라서, 부반응이 적고 생성물에 대한 선택성이 높아 효율성 및 경제성이 뛰어난 α,β-불포화 알데히드의 제조방법의 개발이 시급한 실정이다.
Therefore, there is an urgent need to develop a method for producing α, β-unsaturated aldehyde, which has low side reactions and high selectivity to products, which is highly efficient and economical.
상기와 같은 종래기술의 문제점을 해결하고자, 본 발명은 부반응이 적고 생성물의 선택도가 뛰어난 α,β-불포화 알데히드의 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 method for producing α, β-unsaturated aldehyde having less side reactions and excellent product selectivity.
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 알돌-축합 반응을 이용한 α,β-불포화 알데히드의 제조방법에 있어서, 상기 알돌-축합 반응은 알데히드 및 0.2 내지 2.0 % NaOH 수용액을 포함하여 90 내지 130 ℃에서 실시되되, 상기 알데히드와 상기 NaOH 수용액의 중량비(알데히드:NaOH 수용액)는 1.0:0.6 내지 1.0:1.7인 것을 특징으로 하는 α,β-불포화 알데히드의 제조방법을 제공한다.
In order to achieve the above object, the present invention is a method for producing α, β-unsaturated aldehyde using an aldol-condensation reaction, the aldol-condensation reaction is 90 to 130 ℃ including aldehyde and 0.2 to 2.0% NaOH aqueous solution Although carried out in, the weight ratio of the aldehyde and the NaOH aqueous solution (aldehyde: aqueous NaOH solution) provides a method for producing α, β-unsaturated aldehyde, characterized in that 1.0: 0.6 to 1.0: 1.7.
상기에서 살펴본 바와 같이, 본 발명에 따르면 부반응이 적고 생성물의 선택도가 뛰어난 α,β-불포화 알데히드의 제조방법을 제공하는 효과가 있다.
As described above, according to the present invention, there is an effect of providing a method for preparing α, β-unsaturated aldehyde having less side reactions and excellent product selectivity.
도 1은 본 발명에 따른 α,β-불포화 알데히드의 제조방법이 적용된 반응장치의 일례를 개략적으로 도시한 장치도이다.1 is an apparatus diagram schematically showing an example of a reaction apparatus to which a method for preparing α, β-unsaturated aldehyde according to the present invention is applied.
이하 본 발명을 상세하게 설명한다. Hereinafter, the present invention will be described in detail.
본 발명의 α,β-불포화 알데히드의 제조방법은 알돌-축합 반응을 이용한 α,β-불포화 알데히드의 제조방법에 있어서, 상기 알돌-축합 반응은 알데히드 및 0.2 내지 2.0 % NaOH 수용액을 포함하여 90 내지 130 ℃에서 실시되되, 상기 알데히드와 상기 NaOH 수용액의 중량비(알데히드:NaOH 수용액)는 1.0:0.6 내지 1.0:1.7인 것을 특징으로 한다.
In the method for preparing α, β-unsaturated aldehyde of the present invention, a method for preparing α, β-unsaturated aldehyde using an aldol-condensation reaction, wherein the aldol-condensation reaction includes an aldehyde and an aqueous solution of 0.2 to 2.0% NaOH in a range of 90 to It is carried out at 130 ℃, the weight ratio of the aldehyde and the aqueous NaOH solution (aldehyde: aqueous NaOH solution) is characterized in that 1.0: 0.6 to 1.0: 1.7.
상기 알돌-축합 반응은 대칭 알돌-축합 반응인 것이 바람직할 수 있는데, 구체적인 반응예를 하기 그림 1에 기재하였다.The aldol-condensation reaction may be preferably a symmetric aldol-condensation reaction, a specific reaction example is shown in Figure 1 below.
[그림 1][Figure 1]
상기 알데히드는 노르말 알데히드인 것이 바람직하고, 보다 바람직하게는 N-부티르알데히드이다.The aldehyde is preferably normal aldehyde, more preferably N-butyraldehyde.
상기 NaOH 수용액은 0.2 내지 2.0 % NaOH 수용액일 수 있고, 바람직하게는 0.3 내지 1.8% NaOH 수용액이며, 보다 바람직하게는 0.8 내지 1.0 % NaOH 수용인데, 이 범위 내에서 2-에틸헥센알(2-ethylhexenal)의 수율이 높게 나타나는 효과가 있다.The NaOH aqueous solution may be 0.2-2.0% NaOH aqueous solution, preferably 0.3-1.8% NaOH aqueous solution, more preferably 0.8-1.0% NaOH aqueous solution, and 2-ethylhexenal (2-ethylhexenal within this range). ), The yield is high.
상기 % NaOH 수용액은 중량% NaOH 수용액을 의미한다.The% NaOH aqueous solution means a weight% NaOH aqueous solution.
상기 알데히드와 상기 NaOH 수용액의 중량비(알데히드:NaOH 수용액)는 1.0:0.6 내지 1.0:1.7일 수 있고, 바람직하게는 1.0:1.0 내지 1.0:1.3이며, 2-에틸헥센알(2-ethylhexenal)의 수율이 높게 나타나는 효과가 있다.The weight ratio of the aldehyde and the aqueous NaOH solution (aldehyde: aqueous NaOH solution) may be 1.0: 0.6 to 1.0: 1.7, preferably 1.0: 1.0 to 1.0: 1.3, the yield of 2-ethylhexenal (2-ethylhexenal) This has a high effect.
상기 알돌-축합 반응은 90 내지 130 ℃에서 실시되는 것이 바람직하고, 보다 바람직하게는 100 내지 110 ℃에서 실시되는 것인데, 이 범위 내에서 미반응된 n-부탄알의 양이 증가하지 않으며, 탄소수 12개 이상의 고비점 성분의 발생량이 적어 2-에틸헥센알(2-ethylhexenal)의 수율을 높이는 효과가 있다.The aldol-condensation reaction is preferably carried out at 90 to 130 ℃, more preferably to be carried out at 100 to 110 ℃, within this range the amount of unreacted n-butanal does not increase, carbon number 12 Less generation of more than one high boiling point component has the effect of increasing the yield of 2-ethylhexenal (2-ethylhexenal).
상기 알돌-축합 반응은 1 내지 10 bar에서 실시되는 것일 수 있고, 바람직하게는 2 내지 4 bar에서 실시되는 것인데, 이 범위 내에서 반응물인 n-부탄알의 증기압 이상의 압력으로 반응물이 기화하지 않아 액상 알돌반응에 효과적이며, 4 bar를 초과하는 높은 압력은 알돌반응에 불필요하다.The aldol-condensation reaction may be carried out at 1 to 10 bar, preferably at 2 to 4 bar, the reaction does not vaporize at a pressure above the vapor pressure of the n-butanal reactant within this range liquid Effective for aldol reactions, high pressures above 4 bar are unnecessary for aldol reactions.
상기 알돌-축합 반응은 0.1 내지 1.0 시간 동안 실시될 수 있고, 바람직하게는 0.2 내지 0.5 시간 동안 실시되는 것인데, 이 범위 내에서 미반응된 n-부탄알을 일정 수준으로 유지하면서, 탄소수 12개 이상의 고비점 화합물를 감소시킬수 있어 2-에틸헥센알(2-ethylhexenal)의 수율을 높이는 효과가 있다.The aldol-condensation reaction may be carried out for 0.1 to 1.0 hours, preferably for 0.2 to 0.5 hours, while maintaining an unreacted n-butanal at a certain level within this range, having at least 12 carbon atoms It can reduce the high boiling point compound, thereby increasing the yield of 2-ethylhexenal.
상기 알돌-축합 반응에 사용되는 반응기의 형태는 연속식 반응기(CSTR)가 바람직한데, 이 경우 반응물인 n-부탄알과 촉매를 포함한 수용액의 혼합을 용이하게 하여, 반응이 일어나는 수용액 상으로 반응물인 n-부탄알의 물질전달이 원할이 일어나고, 알돌반응의 반응열 제어가 용이한 효과가 있다.
The type of reactor used for the aldol-condensation reaction is preferably a continuous reactor (CSTR), in which case it is easy to mix the reactant n-butanal with an aqueous solution including a catalyst, and the reactant is in the aqueous phase in which the reaction takes place. The mass transfer of n-butanal takes place, and the heat of reaction of the aldol reaction is easily controlled.
하기 도 1은 본 발명의 α,β-불포화 알데히드의 제조방법이 적용되는 반응장치(100)의 구체적인 일례를 나타낸다. 다만, 당업자에게 지극히 당연한 반응온도 제어수단, 반응압력 조절수단 등은 생략되었다.1 shows a specific example of the reaction apparatus 100 to which the method for producing α, β-unsaturated aldehyde of the present invention is applied. However, the reaction temperature control means, the reaction pressure control means, etc., which are very natural to those skilled in the art, have been omitted.
반응원료 공급배관(1)을 통해 출발물질인 알데히드 및 NaOH 수용액이 알돌-축합 반응기(10)로 투입되고, 소정 온도, 압력 및 시간 하에 알돌-축합 반응이 실시된 후, 생성된 혼합물이 배출관(2)을 통해 증류 컬럼(20)으로 유입된다. The starting material aldehyde and NaOH aqueous solution are introduced into the aldol-
증류 컬럼(20)으로 유입된 생성 혼합물 중에서 비점이 낮은 알데히드와 일부 α,β-불포화 알데히드 등은 상부배관(3)을 거쳐 알데히드/생성물 분리기(30)로 이동된 다음, 알데히드는 회수배관(4)을 통해 알돌-축합 반응기(10)로 재순환되고, 생성물인 α,β-불포화 알데히드는 배출배관(7)을 통해 수득된다. Low boiling aldehydes and some α, β-unsaturated aldehydes and the like in the product mixture introduced into the
한편, 증류 컬럼(20)으로 유입된 생성 혼합물 중에서 비점이 높은 NaOH 수용액과 α,β-불포화 알데히드 등은 하부배관(5)을 거쳐 촉매용액/생성물 분리기(40)로 이동된 다음, 촉매용액은 회수배관(6)을 통해 알돌-축합 반응기(10)로 재순환되고, 생성물인 α,β-불포화 알데히드는 배출배관(8)을 통해 수득된다.
Meanwhile, NaOH aqueous solution having high boiling point and α, β-unsaturated aldehyde, etc. in the product mixture introduced into the
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]
실시예 1Example 1
반응물인 n-부탄알(순도 99.8% 이상, LG화학)과 1.8% NaOH 수용액 각 10kg을 각각의 원료탱크에 충진하였다. 1L 용량의 CSTR 반응기 내에는 1.8% NaOH 수용액과 2-에틸헥센알을 순서대로 각각 330g씩 정량하여 주입하였다. 이후, CSTR 반응기를 질소로 가압하여 반응기내가 2bar를 유지하도록 하였고, CSTR 반응기의 교반기를 500rpm으로 교반하면서 반응기의 온도를 130℃까지 상승시켰다. 반응기 내부의 온도가 반응온도 +/- 1.0 ℃ 내외로 안정화되었을 때, 교반속도를 1500rpm으로 상승시켰다. 이후, 다이아프램 펌프를 이용하여 반응물인 n-부탄알과 NaOH 수용액을 각각 1.28kg/hr, 1.04kg/hr의 속도로 정량하여 CSTR 반응기 내로 공급하였고, 반응기내의 액상의 높이가 일정하게 유지 되도록 반응물의 투입과 동시에 레벨 조절 밸브를 통해 생성물을 회수하였다. 반응물의 공급 후 매 1시간 마다 생성물을 샘플링하였는데, 샘플은 약 30g을 취하였으며, 샘플링 후 분별 깔때기를 이용하여 1시간 동안 물층과 유기층을 분리하고, 분리된 물층은 0.1N 농도의 HCl을 이용하여 적정하여 NaOH 농도 측정을 실시하였고, 유기층은 가스크로마토그래피를 이용하여 성분분석을 실시하였다. 이때 성분분석은 하기 시험예에 기재된 방법으로 실시하였고, 그 결과는 하기의 표 1에 나타내었다.
Reactants n-butanal (purity 99.8% or more, LG Chem) and each 10 kg of 1.8% aqueous NaOH solution were filled in each raw tank. In a 1 liter CSTR reactor, 330 g of 1.8% NaOH aqueous solution and 2-ethylhexenal were sequentially dosed and injected. Thereafter, the CSTR reactor was pressurized with nitrogen to maintain 2 bar in the reactor, and the temperature of the reactor was raised to 130 ° C. while stirring the stirrer of the CSTR reactor at 500 rpm. When the temperature inside the reactor was stabilized at around +/- 1.0 ° C, the stirring speed was increased to 1500 rpm. Then, using a diaphragm pump, the reactants n-butanal and NaOH aqueous solution were quantitated at a rate of 1.28 kg / hr and 1.04 kg / hr, respectively, and fed into the CSTR reactor, and the reactants to maintain a constant liquid level in the reactor. The product was recovered through the level control valve at the same time as the addition of. The product was sampled every 1 hour after the supply of the reactants. About 30 g of the sample was taken, and after sampling, the water layer and the organic layer were separated using a separatory funnel for 1 hour, and the separated water layer was prepared by using 0.1 N HCl. The titration was carried out to measure the NaOH concentration, and the organic layer was subjected to component analysis using gas chromatography. At this time, the component analysis was carried out by the method described in the following test example, the results are shown in Table 1 below.
실시예 2Example 2
상기 실시예 1에서 반응온도가 110℃인 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. Except that the reaction temperature is 110 ℃ in Example 1 was carried out in the same manner as in Example 1.
실시예 3Example 3
상기 실시예 1에서 반응온도가 90℃인 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. Except that the reaction temperature in Example 1 was 90 ℃ was carried out in the same manner as in Example 1.
실시예 4Example 4
상기 실시예 1에서 1.4% NaOH 수용액을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. Except for using a 1.4% NaOH aqueous solution in Example 1 was carried out in the same manner as in Example 1.
실시예 5Example 5
상기 실시예 1에서 1.4% NaOH 수용액을 사용하고, 반응온도가 110℃인 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. 1.4% NaOH aqueous solution was used in Example 1, and the reaction was carried out in the same manner as in Example 1, except that the reaction temperature was 110 ° C.
실시예 6Example 6
상기 실시예 1에서 1.4% NaOH 수용액을 사용하고, 반응온도가 90℃인 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. 1.4% NaOH aqueous solution was used in Example 1, and the reaction was carried out in the same manner as in Example 1, except that the reaction temperature was 90 ° C.
실시예 7Example 7
상기 실시예 1에서 1.2% NaOH 수용액을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. Except for using the 1.2% NaOH aqueous solution in Example 1 was carried out in the same manner as in Example 1.
실시예 8Example 8
상기 실시예 1에서 1.2% NaOH 수용액을 사용하고, 반응온도가 110℃인 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. 1.2% NaOH aqueous solution was used in Example 1, and the reaction was carried out in the same manner as in Example 1 except that the reaction temperature is 110 ℃.
실시예 9Example 9
상기 실시예 1에서 1.2% NaOH 수용액을 사용하고, 반응온도가 90℃인 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. A 1.2% aqueous NaOH solution was used in Example 1, and the reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 90 ° C.
실시예 10Example 10
상기 실시예 1에서 0.8% NaOH 수용액을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. Except for using a 0.8% NaOH aqueous solution in Example 1 was carried out in the same manner as in Example 1.
실시예 11Example 11
상기 실시예 1에서 0.8% NaOH 수용액을 사용하고, 반응온도가 110℃인 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. Except for using a 0.8% NaOH aqueous solution in Example 1, and the reaction temperature was 110 ℃ was carried out in the same manner as in Example 1.
실시예 12Example 12
상기 실시예 1에서 0.8% NaOH 수용액을 사용하고, 반응온도가 90℃인 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. Except for using a 0.8% NaOH aqueous solution in Example 1, except that the reaction temperature is 90 ℃ was carried out in the same manner as in Example 1.
실시예 13Example 13
상기 실시예 1에서 0.4% NaOH 수용액을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. Except for using a 0.4% NaOH aqueous solution in Example 1 was carried out in the same manner as in Example 1.
실시예 14 Example 14
상기 실시예 1에서 0.4% NaOH 수용액을 사용하고, 반응온도가 110℃인 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. 0.4% NaOH aqueous solution was used in Example 1, except that the reaction temperature was 110 ℃ was carried out in the same manner as in Example 1.
실시예 15Example 15
상기 실시예 1에서 0.4% NaOH 수용액을 사용하고, 반응온도가 90℃인 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. 0.4% NaOH aqueous solution was used in Example 1, except that the reaction temperature was 90 ℃ was carried out in the same manner as in Example 1.
실시예 16Example 16
상기 실시예 1에서 0.2% NaOH 수용액을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. Except for using a 0.2% NaOH aqueous solution in Example 1 was carried out in the same manner as in Example 1.
실시예 17Example 17
상기 실시예 1에서 0.2% NaOH 수용액을 사용하고, 반응온도가 110℃인 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. 0.2% NaOH aqueous solution was used in Example 1, except that the reaction temperature was 110 ℃ was carried out in the same manner as in Example 1.
실시예 18Example 18
상기 실시예 1에서 0.2% NaOH 수용액을 사용하고, 반응온도가 90℃인 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. 0.2% NaOH aqueous solution was used in Example 1, and the reaction was carried out in the same manner as in Example 1, except that the reaction temperature was 90 ° C.
비교예 1Comparative Example 1
상기 실시예 1에서 0.1% NaOH 수용액을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.Except for using the 0.1% NaOH aqueous solution in Example 1 was carried out in the same manner as in Example 1.
비교예 2Comparative Example 2
상기 실시예 1에서 반응온도가 150℃인 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.Except that the reaction temperature in Example 1 was 150 ℃ was carried out in the same manner as in Example 1.
비교예 3Comparative Example 3
상기 실시예 1에서 반응온도가 80℃인 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.Except that the reaction temperature is 80 ℃ in Example 1 was carried out in the same manner as in Example 1.
실시예 19Example 19
상기 실시예 1에서 0.8% NaOH 수용액을 사용하고, 반응온도를 100℃로 하며, NaOH 수용액의 공급속도를 1.02kg/hr(알데히드와 NaOH 수용액의 중량비(알데히드:NaOH 수용액)=1.28:1.02, NaOH 수용액/알데히드=0.8)로 한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. In Example 1, using a 0.8% NaOH aqueous solution, the reaction temperature is 100 ℃, the feed rate of the NaOH aqueous solution is 1.02kg / hr (weight ratio of aldehyde and NaOH aqueous solution (aldehyde: NaOH aqueous solution) = 1.28: 1.02, NaOH A solution was carried out in the same manner as in Example 1, except that aqueous solution / aldehyde = 0.8).
실시예 20Example 20
상기 실시예 19에서 NaOH 수용액의 공급속도를 1.28kg/hr(알데히드와 NaOH 수용액의 중량비(알데히드:NaOH 수용액)=1.28:1.28, NaOH 수용액/알데히드=1.0)로 한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. Example 1 except that the feed rate of the NaOH aqueous solution in Example 19 was 1.28kg / hr (weight ratio of aldehyde and NaOH aqueous solution (aldehyde: NaOH aqueous solution) = 1.28: 1.28, NaOH aqueous solution / aldehyde = 1.0) It was carried out in the same manner as.
실시예 21Example 21
상기 실시예 19에서 NaOH 수용액의 공급속도를 1.53kg/hr(알데히드와 NaOH 수용액의 중량비(알데히드:NaOH 수용액)=1.28:1.53, NaOH 수용액/알데히드=1.2)로 한 것을 제외하고는 상기 실시예 20과 동일한 방법으로 실시하였다. Example 20 except that the feed rate of the NaOH aqueous solution in Example 19 was 1.53kg / hr (weight ratio of aldehyde and NaOH aqueous solution (aldehyde: NaOH aqueous solution) = 1.28: 1.53, NaOH aqueous solution / aldehyde = 1.2) It was carried out in the same manner as.
비교예 4Comparative Example 4
상기 실시예 20에서 NaOH 수용액의 공급속도를 0.64kg/hr(알데히드와 NaOH 수용액의 중량비(알데히드:NaOH 수용액)=1.28:0.64, NaOH 수용액/알데히드=0.5)로 한 것을 제외하고는 상기 실시예 20과 동일한 방법으로 실시하였다. Except that the feed rate of the NaOH aqueous solution in Example 20 was 0.64kg / hr (weight ratio of aldehyde and NaOH aqueous solution (aldehyde: NaOH aqueous solution) = 1.28: 0.64, NaOH aqueous solution / aldehyde = 0.5) It was carried out in the same manner as.
비교예 5 Comparative Example 5
상기 실시예 20에서 NaOH 수용액의 공급속도를 2.56kg/hr(알데히드와 NaOH 수용액의 중량비(알데히드:NaOH 수용액)=1.28:2.56, NaOH 수용액/알데히드=2.0)로 하는 것을 제외하고는 상기 실시예 20과 동일한 방법으로 실시하였다.
Except that the feed rate of the aqueous NaOH solution in Example 20 is 2.56kg / hr (weight ratio of aldehyde and NaOH aqueous solution (aldehyde: NaOH aqueous solution) = 1.28: 2.56, NaOH aqueous solution / aldehyde = 2.0) It was carried out in the same manner as.
[시험예][Test Example]
상기 실시예에서 제조된 α,β-불포화 알데히드의 조성 및 함량을 기체 크로마토그래피 질량 분광분석법(HP 5890, 휴렛팩커드사)으로 측정 및 분석하였다. 측정된 조성으로부터 하기 수학식 1 내지 3을 이용하여 반응물인 n-부탄알의 전환율, 2-ehtylhexenal 선택도 및 수율을 계산하였고, 그 결과를 하기의 표 1에 나타내었다.
The composition and content of the α, β-unsaturated aldehyde prepared in the above examples were measured and analyzed by gas chromatography mass spectrometry (HP 5890, Hewlett-Packard). The conversion rate, 2-ehtylhexenal selectivity and yield of the reactant n-butanal were calculated using the following Equations 1 to 3 from the measured composition, and the results are shown in Table 1 below.
상기 표 1에 나타낸 바와 같이, 본 발명에 따른 α,β-불포화 알데히드의 제조방법(실시예 1 ~21)은 NaOH 수용액의 농도, 반응온도 및 알데히드와 NaOH 수용액의 함량비가 본 발명의 범위를 벗어나는 경우(비교예 1~5)에 비하여 n-부탄알 전환율, 2-에틸헥센알의 선택도 및 수율이 모두 높음을 확인할 수 있었다. As shown in Table 1, the production method of α, β-unsaturated aldehyde according to the present invention (Examples 1 to 21) is a concentration of the NaOH aqueous solution, the reaction temperature and the content ratio of the aldehyde and NaOH aqueous solution is beyond the scope of the present invention Compared with the case (Comparative Examples 1-5), it was confirmed that n-butanal conversion, selectivity and yield of 2-ethylhexenal were all high.
참고로, NaOH 수용액 농도가 본 발명의 범위를 벗어나는 경우(비교예 1) n-부탄알 전환율 및 2-에틸헥센알의 수율이 현저히 낮아졌고, 반응온도가 본 발명의 범위를 벗어나는 경우(비교예 2 및 3) 2-에틸헥센알의 선택도와 수율이 크게 저하되거나 n-부탄알 전환율과 2-에틸헥센알의 수율이 크게 저하되었으며, 알데히드와 NaOH 수용액의 중량비가 본 발명의 범위를 벗어나는 경우(비교예 4 및 5) n-부탄알 전환율과 2-에틸헥센알의 수율이 현저히 떨어지거나 2-에틸헥센알의 선택도와 수율이 현저히 떨어짐을 확인할 수 있었다.
For reference, when the NaOH aqueous solution concentration is out of the range of the present invention (Comparative Example 1) n-butanal conversion and 2-ethylhexenal yield is significantly lowered, the reaction temperature is outside the scope of the present invention (Comparative Example) 2 and 3) When the selectivity and yield of 2-ethylhexenal are greatly reduced or the yield of n-butanal conversion and 2-ethylhexenal are greatly reduced, and the weight ratio of aldehyde and aqueous NaOH solution is outside the scope of the present invention ( Comparative Examples 4 and 5) It was confirmed that the conversion of n-butanal and the yield of 2-ethylhexenal were remarkably decreased or the selectivity and yield of 2-ethylhexenal were remarkably decreased.
1: 반응원료 공급배관 2: 반응생성혼합물 배출관
3: 상부배관 4: 알데히드 회수배관
5: 하부배관 6: 촉매용액 회수배관
7, 8: 생성물 배출배관
10: 알돌-축합 반응기 20: 증류 컬럼
30: 알데히드/생성물 분리기 40: 촉매용액/생성물 분리기1: reaction raw material supply pipe 2: reaction product mixture discharge pipe
3: upper piping 4: aldehyde recovery piping
5: bottom line 6: catalyst solution return line
7, 8: product discharge piping
10: aldol-condensation reactor 20: distillation column
30: aldehyde / product separator 40: catalyst solution / product separator
Claims (7)
상기 알데히드와 상기 NaOH 수용액의 중량비(알데히드:NaOH 수용액)는 1.0:0.6 내지 1.0:1.7인 것을 특징으로 하는
α,β-불포화 알데히드의 제조방법. In the method for producing α, β-unsaturated aldehyde using an aldol-condensation reaction, the aldol-condensation reaction is carried out at 90 to 130 ℃ including an aldehyde and 0.2 to 2.0% NaOH aqueous solution,
The weight ratio (aldehyde: NaOH aqueous solution) of the aldehyde and the NaOH aqueous solution is characterized in that 1.0: 0.6 to 1.0: 1.7
Method for producing α, β-unsaturated aldehyde.
상기 알돌-축합반응은, 대칭 알돌-축합반응인 것을 특징으로 하는
α,β-불포화 알데히드의 제조방법.The method of claim 1,
The aldol-condensation reaction is characterized in that the symmetrical aldol-condensation reaction
Method for producing α, β-unsaturated aldehyde.
상기 알데히드는, 노르말 알데히드인 것을 특징으로 하는
α,β-불포화 알데히드의 제조방법.The method of claim 1,
The aldehyde is characterized in that the normal aldehyde
Method for producing α, β-unsaturated aldehyde.
상기 NaOH 수용액은, 0.8 내지 1.0 % NaOH 수용액인 것을 특징으로 하는
α,β-불포화 알데히드의 제조방법.The method of claim 1,
The NaOH aqueous solution is characterized in that 0.8 to 1.0% NaOH aqueous solution
Method for producing α, β-unsaturated aldehyde.
상기 알데히드와 상기 NaOH 수용액의 중량비는, 1.0:1.0 내지 1.0: 1.3인 것을 특징으로 하는
α,β-불포화 알데히드의 제조방법.The method of claim 1,
The weight ratio of the aldehyde and the NaOH aqueous solution is 1.0: 1.0 to 1.0: 1.3
Method for producing α, β-unsaturated aldehyde.
상기 알돌-축합 반응은, 1 내지 10 bar에서 실시되 것을 특징으로 하는
α,β-불포화 알데히드의 제조방법.The method of claim 1,
The aldol-condensation reaction, characterized in that carried out at 1 to 10 bar
Method for producing α, β-unsaturated aldehyde.
상기 알돌-축합 반응은, 연속식 반응기(CSTR)에 의하여 실시되는 것을 특징으로 하는
α,β-불포화 알데히드의 제조방법.
The method of claim 1,
The aldol-condensation reaction, characterized in that carried out by a continuous reactor (CSTR)
Method for producing α, β-unsaturated aldehyde.
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