2-HEMA (CH2=C(CH3)-COO-(CH2)2-OH, 2-hydroxyethyl methacrylate)는 코팅 산업에서 현재 주로 이용되고 있는데, 4-하이드록시부틸 아크릴레이트 (CH2=CH-COO-(CH2)4-OH, 4-HBA)는 2-HEMA에 비해 내광성, 내약품성, 그리고 내긁힘성 등이 뛰어날 뿐 만 아니라, 환경 친화적 코팅제로서 소비가 계속 증가될 것으로 기대된다.
4-HBA를 제조하기 위해 고체 산 촉매에서 ...
2-HEMA (CH2=C(CH3)-COO-(CH2)2-OH, 2-hydroxyethyl methacrylate)는 코팅 산업에서 현재 주로 이용되고 있는데, 4-하이드록시부틸 아크릴레이트 (CH2=CH-COO-(CH2)4-OH, 4-HBA)는 2-HEMA에 비해 내광성, 내약품성, 그리고 내긁힘성 등이 뛰어날 뿐 만 아니라, 환경 친화적 코팅제로서 소비가 계속 증가될 것으로 기대된다.
4-HBA를 제조하기 위해 고체 산 촉매에서 아크릴산 (AA)과 1,4-부탄디올 (1,4-BD)의 에스테르화 반응을 수행하였는데, Amberlyst 15 촉매는 Amberlyst 35나 DOWEX HCR-S(E) 촉매에 비해 활성이 매우 높았다. 따라서, Amberlyst 15 촉매를 대상으로 에스테르화 반응 kinetics를 조사하였는데, Quasi-homogeneous 모델을 반응 모델로 선정하였다. 먼저, stirring speed를 300 rpm에서 750 rpm으로 변경하여 external mass transfer 영향이 없음을 확인하였다. 또한 반응의 활성화 에너지를 구하기 위해, 반응 온도를 100 ℃에서 120 ℃로 변화시켰는데 계산된 반응 활성화 에너지는 4-HBA와 1,4-BDDA (1,4-butanediol diacrylate, 부생성물) 생산에 있어서 각각 58.3 kJ/mol, 86.7 kJ/mol이었다. 반응 속도에 대한 촉매 농도 영향을 조사하기 위해 촉매 농도를 0.0043 g/ml에서 0.0171 g/ml로 변화시켰다. 따라서, Amberlyst 15 촉매에서 4-HBA 생산을 위한 에스테르화 반응에 대해, Quasi-homogeneous 모델을 이용하여 반응 온도와 촉매 농도 영향이 모두 포함된 반응 속도식을 계산할 수 있었다.
반응 속도 증가와 고수율의 4-HBA를 얻기 위해 batch 반응 증류 공정을 수행하였다. 반응 영역에서 부산물인 물을 제거하기 위해 반응 압력은 760 mmHg 이하로 유지시켰는데, 진공 (400~760 mmHg)에서의 조업에서 반응물과 생성물의 고분자화를 방지하기 위해 공기 발포 (air-bubbling)을 병행하였다. 반응 속도는 반응 압력에 크게 의존하였으며, 특히 1,4-BD 반응 속도는 반응 압력에 대한 영향이 크게 나타났다. 결국 반응 증류 공정에 의한 반응 속도 증가로 인해, 최종적으로 고순도 4-HBA를 얻을 수 있었다.
반응 증류 공정 후에, 반응 생성물인 AA, 4-HBA, 그리고 1,4-BDDA에서 4-HBA를 분리하기 위해 추출 공정을 수행하였다. 4-HBA는 분자 구조 내에 하이드록시 (-OH) 기능기가 존재하여 물과 강한 친화성이 있는 것으로 판단되었으며, 물을 추출 용매로 선정하였으며, 또한 싸이클로헥산을 또 다른 추출 용매로 선정하였다. 상평형 실험 결과, 4-HBA는 물에 선택적으로 용해되었으며, 1,4-BDDA는 싸이클로헥산에 선택적으로 용해되었다. 결국 원료, 물, 그리고 싸이클로헥산의 유속을 각각 2.1 ml/min, 7.0 ml/min, 5.1 ml/min로 하는 추출 공정으로 90 % 이상의 고순도 4-HBA를 얻을 수 있었다.
추출 생성물인 AA, 4-HBA, 그리고 물에서 4-HBA를 회수하기 위해 증류 공정을 수행하였다. 4-HBA의 끓는점이 AA와 물에 비해 상당히 높기 때문에 4-HBA 회수를 위한 증류 공정이 매우 바람직하였다. AA와 4-HBA는 고온에서 쉽게 고분자화가 나타나기 때문에, 고분자화를 방지하기 위해 진공 증류 공정을 이용하여 조업 온도를 낮췄다. 4-HBA 회수를 위한 증류 공정은 2 단계 조업으로 운전하였다. 50 mmHg, 70 ℃ 운전에서는 물이 선택적으로 제거되었으며, 30 mmHg, 80 ℃ 운전에서는 AA가 제거되었다. 최종적으로 고순도 4-HBA를 reboiler에서 얻을 수 있었는데, 이는 증류 컬럼 온도의 급격한 상승으로 확인할 수 있었다.
반응과 분리 공정을 결합한 4-HBA 생산을 위한 전체 공정을 개발하였는데, 전제 공정에 대한 물질 수지도 계산하였다. 계산 결과, 원료 12.545 kg/hr 공급으로 인해 하루에 4-HBA, 104.3 kg을 얻을 수 있었으며, 더욱이 1,4-BDDA도 제품으로 생산할 경우 개발 공정에 대한 제품 수율은 85.7 wt.%에 달했다.
2-HEMA (CH2=C(CH3)-COO-(CH2)2-OH, 2-hydroxyethyl methacrylate)는 코팅 산업에서 현재 주로 이용되고 있는데, 4-하이드록시부틸 아크릴레이트 (CH2=CH-COO-(CH2)4-OH, 4-HBA)는 2-HEMA에 비해 내광성, 내약품성, 그리고 내긁힘성 등이 뛰어날 뿐 만 아니라, 환경 친화적 코팅제로서 소비가 계속 증가될 것으로 기대된다.
4-HBA를 제조하기 위해 고체 산 촉매에서 아크릴산 (AA)과 1,4-부탄디올 (1,4-BD)의 에스테르화 반응을 수행하였는데, Amberlyst 15 촉매는 Amberlyst 35나 DOWEX HCR-S(E) 촉매에 비해 활성이 매우 높았다. 따라서, Amberlyst 15 촉매를 대상으로 에스테르화 반응 kinetics를 조사하였는데, Quasi-homogeneous 모델을 반응 모델로 선정하였다. 먼저, stirring speed를 300 rpm에서 750 rpm으로 변경하여 external mass transfer 영향이 없음을 확인하였다. 또한 반응의 활성화 에너지를 구하기 위해, 반응 온도를 100 ℃에서 120 ℃로 변화시켰는데 계산된 반응 활성화 에너지는 4-HBA와 1,4-BDDA (1,4-butanediol diacrylate, 부생성물) 생산에 있어서 각각 58.3 kJ/mol, 86.7 kJ/mol이었다. 반응 속도에 대한 촉매 농도 영향을 조사하기 위해 촉매 농도를 0.0043 g/ml에서 0.0171 g/ml로 변화시켰다. 따라서, Amberlyst 15 촉매에서 4-HBA 생산을 위한 에스테르화 반응에 대해, Quasi-homogeneous 모델을 이용하여 반응 온도와 촉매 농도 영향이 모두 포함된 반응 속도식을 계산할 수 있었다.
반응 속도 증가와 고수율의 4-HBA를 얻기 위해 batch 반응 증류 공정을 수행하였다. 반응 영역에서 부산물인 물을 제거하기 위해 반응 압력은 760 mmHg 이하로 유지시켰는데, 진공 (400~760 mmHg)에서의 조업에서 반응물과 생성물의 고분자화를 방지하기 위해 공기 발포 (air-bubbling)을 병행하였다. 반응 속도는 반응 압력에 크게 의존하였으며, 특히 1,4-BD 반응 속도는 반응 압력에 대한 영향이 크게 나타났다. 결국 반응 증류 공정에 의한 반응 속도 증가로 인해, 최종적으로 고순도 4-HBA를 얻을 수 있었다.
반응 증류 공정 후에, 반응 생성물인 AA, 4-HBA, 그리고 1,4-BDDA에서 4-HBA를 분리하기 위해 추출 공정을 수행하였다. 4-HBA는 분자 구조 내에 하이드록시 (-OH) 기능기가 존재하여 물과 강한 친화성이 있는 것으로 판단되었으며, 물을 추출 용매로 선정하였으며, 또한 싸이클로헥산을 또 다른 추출 용매로 선정하였다. 상평형 실험 결과, 4-HBA는 물에 선택적으로 용해되었으며, 1,4-BDDA는 싸이클로헥산에 선택적으로 용해되었다. 결국 원료, 물, 그리고 싸이클로헥산의 유속을 각각 2.1 ml/min, 7.0 ml/min, 5.1 ml/min로 하는 추출 공정으로 90 % 이상의 고순도 4-HBA를 얻을 수 있었다.
추출 생성물인 AA, 4-HBA, 그리고 물에서 4-HBA를 회수하기 위해 증류 공정을 수행하였다. 4-HBA의 끓는점이 AA와 물에 비해 상당히 높기 때문에 4-HBA 회수를 위한 증류 공정이 매우 바람직하였다. AA와 4-HBA는 고온에서 쉽게 고분자화가 나타나기 때문에, 고분자화를 방지하기 위해 진공 증류 공정을 이용하여 조업 온도를 낮췄다. 4-HBA 회수를 위한 증류 공정은 2 단계 조업으로 운전하였다. 50 mmHg, 70 ℃ 운전에서는 물이 선택적으로 제거되었으며, 30 mmHg, 80 ℃ 운전에서는 AA가 제거되었다. 최종적으로 고순도 4-HBA를 reboiler에서 얻을 수 있었는데, 이는 증류 컬럼 온도의 급격한 상승으로 확인할 수 있었다.
반응과 분리 공정을 결합한 4-HBA 생산을 위한 전체 공정을 개발하였는데, 전제 공정에 대한 물질 수지도 계산하였다. 계산 결과, 원료 12.545 kg/hr 공급으로 인해 하루에 4-HBA, 104.3 kg을 얻을 수 있었으며, 더욱이 1,4-BDDA도 제품으로 생산할 경우 개발 공정에 대한 제품 수율은 85.7 wt.%에 달했다.
2-HEMA (CH2=C(CH3)-COO-(CH2)2-OH, 2-hydroxyethyl methacrylate) has been widely used as a coating agent in the coating industry. However, 4-hydroxybutyl acrylate (CH2=CH-COO-(CH2)4-OH, 4-HBA) has better properties such as luster-resistance, chemical-resistance, and scratch-resistance than 2-HEMA, and...
2-HEMA (CH2=C(CH3)-COO-(CH2)2-OH, 2-hydroxyethyl methacrylate) has been widely used as a coating agent in the coating industry. However, 4-hydroxybutyl acrylate (CH2=CH-COO-(CH2)4-OH, 4-HBA) has better properties such as luster-resistance, chemical-resistance, and scratch-resistance than 2-HEMA, and furthermore it is known to be an environmentally-benign product. Thus, its consumption is expected grow rapidly.
Esterification of acrylic acid (AA) with 1,4-butanediol (1,4-BD) was carried out over a solid acid catalyst to produce 4-hydroxybutyl acrylate (4-HBA). The Amberlyst 15 catalyst was more active for the reaction than other ion exchanged resin catalysts such as Amberlyst 35 and DOWEX HCR-S(E). The quasi-homogeneous model was chosen to express the esterification reaction kinetics over Amberlyst 15. The stirring speed was changed from 300 rpm to 750 rpm and the reaction rate showed no influence of external mass transfer. The reaction temperature was varied from 100 ℃ to 120 ℃ to calculate activation energies of the reactions. The calculated activation energies were 58.3 kJ/mol and 86.7 kJ/mol for 4-HBA and 1,4-BDDA (1,4-butanediol diacrylate, byproduct) production, respectively. The catalyst concentration was also changed from 0.0043 g/ml to 0.0171 g/ml to find out its effect on the rate constant. The complete kinetic equation of esterification to produce 4-HBA over the Amberlyst 15 catalyst based on the quasi-homogeneous model was developed.
Batch reactive distillation mode over the Amberlyst 15 was developed to increase the reaction rate and to obtain the high yield of 4-HBA. The reaction pressure below 760 mmHg was used to remove the by-product water from the reaction zone. The air-bubbling operation was successfully applied to prevent the polymerization of reactants and products under the vacuum condition (400 ~ 760 mmHg). The reaction rates were strongly dependent on the reaction pressure, especially, the reaction rate of 1,4-BD disappearance. The increased reaction rates by the reactive distillation enabled to produce high purity 4-HBA.
After the reactive distillation process, extraction proceeded to separate the 4-HBA from the reaction products which was mainly composed of unreacted AA, 4-HBA, and 1,4-BDDA. Firstly water was considered as a good extraction solvent because 4-HBA has strong affinity to water due to its hydroxyl functional group compared to 1,4-BDDA. As two-components extraction solvent was more effective for the extraction efficiency, cyclohexane was also used as the other extraction solvent. 4-HBA was selectively dissolved in water and 1,4-BDDA was selectively dissolved in cyclohexane. Finally, 4-HBA purity above 90 % was obtained with the extraction process in which the flowrates of feed, water, and cyclohexane were controlled to 2.1 ml/min, 7.0 ml/min, and 5.1 ml/min, respectively.
Distillation was progressed to recover 4-HBA from AA, 4-HBA, and water mixtures which were products of the extraction. The distillation was desirable process for 4-HBA recovery because the boiling point of 4-HBA was expected much higher than those of AA and water. As AA and 4-HBA were easily polymerized at high temperatures, vacuum distillation was used to decrease the operation temperature resulting prevention of the polymerization. In the distillation, two steps were progressed to recover 4-HBA. In the first step, water was preferentially removed at 50 mmHg and 70 ℃, and AA was removed at 30 mmHg and 80 ℃ in the second step. Finally pure 4-HBA was obtained in the reboiler, which was confirmed by the sudden increase of column temperature.
The whole process for 4-HBA production was developed on the base of reaction and separation processes, and mass balance was also calculated for the whole process. 104.3 kg of 4-HBA can be produced in a day with 12.545 kg/hr of feed. Furthermore, if 1,4-BDDA is also considered as another product, the product yield of the process comes to 85.7 wt.%.
2-HEMA (CH2=C(CH3)-COO-(CH2)2-OH, 2-hydroxyethyl methacrylate) has been widely used as a coating agent in the coating industry. However, 4-hydroxybutyl acrylate (CH2=CH-COO-(CH2)4-OH, 4-HBA) has better properties such as luster-resistance, chemical-resistance, and scratch-resistance than 2-HEMA, and furthermore it is known to be an environmentally-benign product. Thus, its consumption is expected grow rapidly.
Esterification of acrylic acid (AA) with 1,4-butanediol (1,4-BD) was carried out over a solid acid catalyst to produce 4-hydroxybutyl acrylate (4-HBA). The Amberlyst 15 catalyst was more active for the reaction than other ion exchanged resin catalysts such as Amberlyst 35 and DOWEX HCR-S(E). The quasi-homogeneous model was chosen to express the esterification reaction kinetics over Amberlyst 15. The stirring speed was changed from 300 rpm to 750 rpm and the reaction rate showed no influence of external mass transfer. The reaction temperature was varied from 100 ℃ to 120 ℃ to calculate activation energies of the reactions. The calculated activation energies were 58.3 kJ/mol and 86.7 kJ/mol for 4-HBA and 1,4-BDDA (1,4-butanediol diacrylate, byproduct) production, respectively. The catalyst concentration was also changed from 0.0043 g/ml to 0.0171 g/ml to find out its effect on the rate constant. The complete kinetic equation of esterification to produce 4-HBA over the Amberlyst 15 catalyst based on the quasi-homogeneous model was developed.
Batch reactive distillation mode over the Amberlyst 15 was developed to increase the reaction rate and to obtain the high yield of 4-HBA. The reaction pressure below 760 mmHg was used to remove the by-product water from the reaction zone. The air-bubbling operation was successfully applied to prevent the polymerization of reactants and products under the vacuum condition (400 ~ 760 mmHg). The reaction rates were strongly dependent on the reaction pressure, especially, the reaction rate of 1,4-BD disappearance. The increased reaction rates by the reactive distillation enabled to produce high purity 4-HBA.
After the reactive distillation process, extraction proceeded to separate the 4-HBA from the reaction products which was mainly composed of unreacted AA, 4-HBA, and 1,4-BDDA. Firstly water was considered as a good extraction solvent because 4-HBA has strong affinity to water due to its hydroxyl functional group compared to 1,4-BDDA. As two-components extraction solvent was more effective for the extraction efficiency, cyclohexane was also used as the other extraction solvent. 4-HBA was selectively dissolved in water and 1,4-BDDA was selectively dissolved in cyclohexane. Finally, 4-HBA purity above 90 % was obtained with the extraction process in which the flowrates of feed, water, and cyclohexane were controlled to 2.1 ml/min, 7.0 ml/min, and 5.1 ml/min, respectively.
Distillation was progressed to recover 4-HBA from AA, 4-HBA, and water mixtures which were products of the extraction. The distillation was desirable process for 4-HBA recovery because the boiling point of 4-HBA was expected much higher than those of AA and water. As AA and 4-HBA were easily polymerized at high temperatures, vacuum distillation was used to decrease the operation temperature resulting prevention of the polymerization. In the distillation, two steps were progressed to recover 4-HBA. In the first step, water was preferentially removed at 50 mmHg and 70 ℃, and AA was removed at 30 mmHg and 80 ℃ in the second step. Finally pure 4-HBA was obtained in the reboiler, which was confirmed by the sudden increase of column temperature.
The whole process for 4-HBA production was developed on the base of reaction and separation processes, and mass balance was also calculated for the whole process. 104.3 kg of 4-HBA can be produced in a day with 12.545 kg/hr of feed. Furthermore, if 1,4-BDDA is also considered as another product, the product yield of the process comes to 85.7 wt.%.
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