RECOVERY OF FORMIC ACID BY REACTIVE EXTRACTION USING AN ENVIRONMENTALLYFRIENDLY SOLVENT

Year 2017, Volume: 5 Issue: 1, 26 - 37, 01.03.2017

Mustafa Esen Martı

https://doi.org/10.15317/Scitech.2017.67

Abstract

Today many carboxylic acids are recovered from biological production media and

industrial wastewaters. Reactive extraction is favored over other separation methods due to its high

recovery efficiency, ease of operation, low energy demand and reduced cost. However, use of toxic

organic diluents in the organic phases is the main disadvantage of the method. In this study, the

appropriateness of an environmentally-friendly solvent, sunflower oil (SFO) to be used as organic phase

diluent during the recovery of formic acid (FA) from aqueous solutions by reactive extraction was

evaluated. Alamine-336 was used as the extractant and the results obtained with SFO were compared

with those obtained using octanol. The separation process reached an equilibrium in 3 hours and the

recovery efficiency increased with the increase in extractant percentages. The initial FA concentration

positively influenced the recovery when SFO was used as the diluent. In the ranges of the parameters

studied, the highest recovery values were 98.6% and 82.6% with octanol and SFO, respectively. This

study shows that low molecular weight carboxylic acids, e.g. FA can be recovered from aqueous

solutions by reactive extraction using environmentally-friendly solvents such as SFO.    

Keywords

Formic acid, Reactive extraction, Sunflower oil, Alamine-336

Formik Asidin Çevre Dostu Bir Çözücü Kullanılarak Tepkimeli Özütleme Yöntemi ile Geri Kazanımı

Abstract

Günümüzde pek çok karboksilik asit biyolojik üretim ortamlarından ve endüstriyel atık sulardan

geri kazanılmaktadır. Tepkimeli özütleme, yüksek geri kazanım verimi, işlem basitliği, düşük enerji

gereksinimi ve maliyeti nedeniyle diğer ayırma yöntemlerine tercih edilmiştir. Fakat organik fazlarda

zehirli organik seyrelticilerin kullanımı yöntemin en önemli dezavantajıdır. Bu çalışmada çevre dostu bir

çözücünün, ayçiçek yağının formik asidin sulu çözeltilerinden tepkimeli özütleme yöntemi ile geri

kazanımı sırasında organik faz seyrelticisi olarak zehirli organik kimyasallar yerine kullanımı

değerlendirilmiştir. Özütleyici olarak Alamine-336 kullanılmış ve ayçiçek yağı ile elde edilen sonuçlar

oktanol ile elde edilen sonuçlarla karşılaştırılmıştır. Ayırma süreci 3 saatte dengeye ulaşmış ve geri

kazanım verimi özütleyici yüzdesi ile birlikte artmıştır. Ayçiçek yağı seyreltici olarak kullanıldığında

başlangıç asit derişimi geri kazanımı pozitif yönde etkilemiştir. Çalışılan değişken aralıklarında oktanol

ve ayçiçek yağı ile en yüksek geri kazanım verimleri sırasıyla %98,6 ve %82,6’dır. Bu çalışma formik asit

gibi düşük molekül ağırlıklı karboksilik asitlerin tepkimeli özütleme ile ayçiçek yağı gibi çevre dostu

çözücüler kullanılarak sulu çözeltilerden geri kazanılabileceğini göstermiştir.

Keywords

Formik asit, Tepkimeli özütleme, Ayçiçek yağı, Alamine-336

References

• Cai, W., Zhu, S., Piao, X., 2001, “Extraction Equilibria of Formic And Acetic Acids from Aqueous Solution by Phosphate Containing Extractants”, Journal of Chemical and Engineering Data, Vol. 46, pp. 1472-1475.
• Chen, H. L., Juang, R. S., 2008, “Recovery and Separation of Surfactin from Pretreated Fermentation Broths by Physical and Chemical Extraction”, Biochemical Engineering Journal, Vol. 38 (1), pp. 39–46.
• Datta, D., Martı, M. E., Uslu, H., Kumar, S., 2016, “Extraction of Levulinic Acid Using Tri-n-butyl Phosphate and Tri-n-octylamine in 1-octanol: Column Design”, Journal of the Taiwan Institute of Chemical Engineers, Vol. 66, pp. 407-413.
• Gorden, J., Zeiner, T., Sadowski, G., Brandenbusch, C., 2016, “Recovery of Cis, Cis-muconic Acid from Organic Phase After Reactive Extraction”, Separation and Purification Technology, Vol. 169, pp. 1- 8.
• Gu, Z., Glatz, B. A., Glatz, C. E., 1998, “Propionic Acid Production by Extractive Fermentation. I. Solvent Considerations”, Biotechnology and Bioengineering, Vol. 57 (4), pp. 454-461.
• Harington, T., Hossain, Md. M., 2008, “Extraction of Lactic Acid into Sunflower Oil and Its Recovery into An Aqueous Solution”, Desalination, Vol. 218, pp. 287-296.
• İnce, E., Kırbaşlar, Ş. İ., Şahin, S., 2007, “Liquid-liquid Equilibria for Ternary Systems of water+formic acid+dibasic Esters”, Journal of Chemical and Engineering Data, Vol. 52 (5), pp. 1889-1893.
• İnci, İ., Hasdemir, M., Bilgin, M., Aydın, A., 2000, “Laktik Asitin Alamin-336 ile Çeşitli Seyreltici Çözücüler Kullanılarak Ekstraksiyonunun İncelenmesi”, Turkish Journal of Engineering and Environmental Sciences, Vol. 24, pp. 45-51.
• Kertes, A. S., King, C. J., 1986, “Extraction Chemistry of Fermentation Product Carboxylic Acids”, Biotechnology and Bioengineering, Vol. 28 (2), pp. 269-282.
• Keshav, A., Wasewar, K. L., Chand, S., 2009, “Reactive Extraction of Propionic Acid using Tri-n- Octylamine, Tri-n-butyl Phosphate and Aliquat 336 in Sunflower Oil as Diluent”, Journal of Chemical Technology and Biotechnology, Vol. 84 (4), pp. 484-489.
• Keshav, A., Norge, P., Wasewar, K. L., 2012, “Reactive Extraction of Citric Acid Using Tri-n-octylamine in Nontoxic Natural Diluents: Part 1—Equilibrium Studies from Aqueous Solutions”, Applied Biochemistry and Biotechnology, Vol. 167 (2), pp. 197–213.
• Lopez-Garzon, C. S., Straathof, A. J., 2014, “Recovery of Carboxylic Acids Produced by Fermentation”, Biotechnology Advances, Vol. 32 (5), pp. 873-904.
• Martı, M. E., 2010, Reactive Extraction of Pyruvic Acid From Aqueous Single and Mixed Acid Solutions, PhD Thesis, Middle East Technical University, Graduate School of Natural and Applied Sciences, Ankara.
• Martı, M. E., Gürkan, T., Doraiswamy, L. K., 2011, “Equilibrium and Kinetic Studies for Reactive Extraction of Pyruvic Acid with Trioctylamine in 1-octanol”, Industrial and Engineering Chemistry Research, Vol. 50 (23), pp. 13518-13525.
• Martı, M. E., Oflaz, K., 2013, “Formik Asidin Alamıne-336 Ve Çeşitli Çözücülerle Tepkimeli Özütlenmesi”, Selçuk Üniversitesi Mühendislik, Bilim ve Teknoloji Dergisi, Vol. 1 (3), pp. 1-8.
• Martı, M. E., Gürkan, T., 2015, “Selective Recovery of Pyruvic Acid From Two and Three Acid Aqueous Solutions by Reactive Extraction”, Separation and Purification Technology, Vol. 156 (2), pp. 148- 157.
• Martı, M. E., Zeidan, H., Uslu, H., 2016, “Reactive Extraction of Pimelic (heptanedioic) Acid from Dilute Aqueous Solutions Using Trioctylamine in decan-1-ol”, Fluid Phase Equilibria, Vol. 417, pp. 197- 202.
• Martı, M. E., 2016, “Solvent Modification Effect on The Physical And Chemical Extraction of Acetic Acid”, Separation Science and Technology, Vol. 51 (11), pp. 1806-1816.
• Qin, W., Li, Z., Dai, Y., 2003, “Extraction of Monocarboxylic Acids With Trioctylamine: Equilibria and Correlation of Apparent Reactive Equilibrium Constant”, Industrial and Engineering Chemistry Research, Vol. 42 (24), pp. 6196-6204.
• Rasrendra, C. B., Girisuta, B., Van de Bovenkamp, H. H., Winkelman, J. G. M., Leijenhorst, E. J., Venderbosch, R. H., Windt, M., Heeres, H. J., 2011, “Recovery of Acetic Acid from an Aqueous Pyrolysis Oil Phase by Reactive Extraction Using Tri-n-octylamine”, Chemical Engineering Journal, Vol. 176-177, pp. 244-252.
• Reyhanitash, E., Zaalberg, B., Kersten, S. R. A., Schuur, B., 2016, “Extraction of Volatile Fatty Acids from Fermented Wastewater”, Separation and Purification Technology, Vol. 161, pp. 61-68.
• San-Martin, M., Pazos, C., Coca, J., 1992, “Reactive Extraction of Lactic Acid with Alamine-336 in The Presence of Salts and Lactose”, Journal of Chemical Technology and Biotechnology, Vol. 54 (1), pp. 1-6.
• Straathof, A. J. J., 2014, “Transformation of Biomass into Commodity Chemicals Using Enzymes or Cells” Chemical Reviews, Vol. 114 (3), pp. 1871–1908.
• Şenol, A., 2000, “Extraction Equilibria of Formic and Levulinic Acids Using Alamine 308/Diluent and Conventional Solvent Systems”, Separation and Purification Technology, Vol. 21 (1-2), pp. 165– 179.
• Tamada, J. A., Kertes, A. S., King, C. J., 1990, “Extraction of Carboxylic Acids with Amine Extractants. 1. Equilibria and Law of Mass Action Modeling”, Industrial and Engineering Chemistry Research, Vol. 29 (7), pp. 1319-1326.
• Uslu, H., 2009, “Reactive Extraction of Formic Acid by Using Tri octyl amine (TOA)”, Separation Science and Technology, Vol. 44 (8), pp. 1784–1798.
• Uslu, H., Gemici, A., Gök, A., Kırbaşlar, İ., 2014, “Reactive Extraction of (E)-butenedioic Acid (fumaric acid) by Nontoxic Diluents”, Journal of Chemical and Engineering Data, Vol. 59 (11), pp. 3767−3772.
• Uslu, H., Yankov, D., Wasewar, K. L., Azizian, S., Ullah, N., Ahmad, W., 2015, “Separation of Organic and Inorganic Compounds for Specific Applications” Journal of Chemistry, Vol. 2015, Article ID: 698259, pp. 1-3.
• Waghmare, M. D., Wasewar, K. L., Sonawane, S. S., Shende, D. Z., 2011, “Natural Nontoxic Solvents for Recovery of Picolinic Acid by Reactive Extraction”, Industrial and Engineering Chemistry Research, Vol. 50 (23), pp. 13526–13537.
• Waghmare, M. D., Wasewar, K. L., Sonawane, S. S., Shende, D. Z., 2013, “Reactive Extraction of Picolinic and Nicotinic Acid by Natural Non-toxic Solvent”, Separation and Purification Technology, Vol. 120, pp. 296-303.
• Wasewar, K. L., Heesink, B. M., Versteeg, G. F., Pangarkar, V. G., 2002, “Reactive Extraction of Lactic Acid Using Alamine-336 in MIBK: Equilibria and Kinetics”, Journal of Biotechnology, Vol. 97 (1), pp. 59-68.
• Wasewar, K. L., Yawalkar, A. A., Moulijn, J. A., Pangarkar, V. G., 2004, “Fermentation of Glucose to Lactic Acid Coupled With Reactive Extraction: A review”, Industrial and Engineering Chemistry Research, Vol. 43 (19), pp. 5969-5982.
• Wasewar, K. L., Shende, D., Keshav, A., 2011, “Reactive Extraction of Itaconic Acid Using Tri-n-butyl Phosphate and Aliquat 336 in Sunflower Oil as A Non-toxic diluent”, Journal of Chemical Technology and Biotechnology, Vol. 86 (2), pp. 319-323.
• Yang, S. T., Huang, H., Tay, A., Qin, W., De Guzman, L., San Nicolas, C., 2007, Extractive Fermentation for The Production of Carboxylic Acids, S. T. Yang (Ed.), Bioprocessing for value-added products from renewable resources: New technologies and applications, 1. Edition, Elsevier, New York, pp. 421.