Formik Asidin Çevre Dostu Bir Çözücü Kullanılarak Tepkimeli Özütleme Yöntemi ile Geri Kazanımı
Günümüzde pek çok karboksilik asit biyolojik üretim ortamlarından ve endüstriyel atık sulardangeri kazanılmaktadır. Tepkimeli özütleme, yüksek geri kazanım verimi, işlem basitliği, düşük enerjigereksinimi ve maliyeti nedeniyle diğer ayırma yöntemlerine tercih edilmiştir. Fakat organik fazlardazehirli organik seyrelticilerin kullanımı yöntemin en önemli dezavantajıdır. Bu çalışmada çevre dostu birçözücünün, ayçiçek yağının formik asidin sulu çözeltilerinden tepkimeli özütleme yöntemi ile gerikazanımı sırasında organik faz seyrelticisi olarak zehirli organik kimyasallar yerine kullanımıdeğerlendirilmiştir. Özütleyici olarak Alamine-336 kullanılmış ve ayçiçek yağı ile elde edilen sonuçlaroktanol ile elde edilen sonuçlarla karşılaştırılmıştır. Ayırma süreci 3 saatte dengeye ulaşmış ve gerikazanım verimi özütleyici yüzdesi ile birlikte artmıştır. Ayçiçek yağı seyreltici olarak kullanıldığındabaşlangıç asit derişimi geri kazanımı pozitif yönde etkilemiştir. Çalışılan değişken aralıklarında oktanolve ayçiçek yağı ile en yüksek geri kazanım verimleri sırasıyla %98,6 ve %82,6’dır. Bu çalışma formik asitgibi düşük molekül ağırlıklı karboksilik asitlerin tepkimeli özütleme ile ayçiçek yağı gibi çevre dostuçözücüler kullanılarak sulu çözeltilerden geri kazanılabileceğini göstermiştir.
RECOVERY OF FORMIC ACID BY REACTIVE EXTRACTION USING AN ENVIRONMENTALLYFRIENDLY SOLVENT
Today many carboxylic acids are recovered from biological production media andindustrial wastewaters. Reactive extraction is favored over other separation methods due to its highrecovery efficiency, ease of operation, low energy demand and reduced cost. However, use of toxicorganic diluents in the organic phases is the main disadvantage of the method. In this study, theappropriateness of an environmentally-friendly solvent, sunflower oil (SFO) to be used as organic phasediluent during the recovery of formic acid (FA) from aqueous solutions by reactive extraction wasevaluated. Alamine-336 was used as the extractant and the results obtained with SFO were comparedwith those obtained using octanol. The separation process reached an equilibrium in 3 hours and therecovery efficiency increased with the increase in extractant percentages. The initial FA concentrationpositively influenced the recovery when SFO was used as the diluent. In the ranges of the parametersstudied, the highest recovery values were 98.6% and 82.6% with octanol and SFO, respectively. Thisstudy shows that low molecular weight carboxylic acids, e.g. FA can be recovered from aqueoussolutions by reactive extraction using environmentally-friendly solvents such as SFO.
___
- 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.