REACTIVE EXTRACTION OF SUCCINIC ACID USING NATURAL DILUENT

Transcription

1 REATIVE EXTRATION OF SUINI AID USING NATURAL DILUENT Rakesh Shantaram Mekade 1, Rashmi S. Deshpande 1Post Graduate Student, Department of hemical Engineering, Sinhgad ollege of Engineering, Pune. Associate Professor, Department of hemical Engineering, Sinhgad ollege of Engineering, Pune. ABSTRAT: Reactive extraction of carboxylic acids from fermentation broth is an important process because it offers higher selectivity as compared to other processes for recovery. Reactive extraction with natural diluent further makes the process more eco-friendly. In this work, extraction of succinic acid by using aliquat 336, a quaternary amine, in natural diluents like sunflower oil and soybean oil has been studied and the results compared with the ones obtained with n-butanol as a diluent. The experiments were carried out at various concentrations of succinic acid and aliquat 336. The acid concentration was varied from.1 to.5 moles/lit by keeping Aliquat 336 concentrations constant at.5 moles/lit, for both the diluents. Physical extraction was also carried out by using these diluents. The parameters such as distribution coefficient, extraction efficiency, and equilibrium complexation constant were studied. The order of degree of extraction was found to be n-butanol > sunflower oil > soybean oil. KEYWORDS: Reactive Extraction, Natural Diluents, Aliquat 336. HOW TO ITE THIS ARTILE: Mekade RS, Deshpande RS. Reactive extraction of succinic acid using natural diluent. J. Technological Advances and Scientific Res. 15; 1(4): , DOI: 1.146/jtasr/15/4. INTRODUTION: With increasing environmental concerns, interest in production of chemicals by green routes is increasing. Use of fermentation technology for the production of carboxylic acids is on the rise. Recovery of these acids by the well-established methods like distillation, adsorption, membrane separation and extraction has its own limitations because of the lower concentration of the acid in the fermentation broth. Reactive extraction offers a more efficient alternative in terms of selectivity, ease of scale-up and ease of recovery of the carboxylic acid. [1-4] Succinic acid is one such carboxylic acid which is commercially produced from maleic anhydride a petroleum product. This process is costly. Hence production of succinic acid by fermentation has a large potential to become industrially important. It s extraction from the broth by reactive extraction followed by a simple recovery process (Back extraction) would make it more cost effective. Reactive extraction of a component from its aqueous solution involves the use of an organic extractant which selectively reacts with the target compound and forms a compound which is extracted into the organic phase. The extractants are generally viscous and require diluents to facilitate the mass transfer process. These diluents are organic compounds like alcohols with partial miscibility or very low miscibility with water like butanol, decanol, etc. or components like hexane, ketones and chlorinated hydrocarbons. [5-11] These chemical diluents are toxic and if they can be replaced by natural diluents like oils (Sunflower, Soyabean, Rice Bran, Palm Oils) the entire process would become more eco-friendly. Financial or Other, ompeting Interest: None. Submission , Peer Review , Acceptance , Published orresponding Author: Rakesh Shantaram Mekade, Maharana Pratap Nagar, Mangaon, Raigad rakya_1@rediffmail.com DOI:1.146/jtasr/15/4. This would also prevent the addition of toxic elements to the fermentation broth. [,7] Reactive extraction (RE) of succinic acid using various extractants and diluents has been studied by many researchers. Extractants such as phosphorus-bonded oxygen donor extractant and high molecular weight aliphatic amines are used for extraction. Long-chain aliphatic amines such as Amberlite LA-, tri-n-octylamine and aliquat 336 are most widely used for the carboxylic acid extraction in the presence of diluents like cyclohexane, iso-octane, MIBK, 1-octanol, toluene, hexane and -octane. In this work, reactive extraction of succinic acid from aqueous solutions by using Aliquat 336 as an extractant and sunflower oil and soyabean oil as diluents was studied. The results were compared with n-butanol as a diluent. [1] MATERIALS: The aqueous phase was made by diluting succinic acid of AR grade with distilled water. Sodium Hydroxide (AR Grade) was used for estimation of the acid. Organic phase was made by using Aliquat 336 (Methyltricaprylammonium chloride), a quaternary amine, of AR Grade and natural diluents such as sunflower oil and soybean oil which are available as commercial cooking oil, n- Butanol of AR grade was used. EXPERIMENTAL PROEDURE: Equal volumes of aqueous and organic phases were shaken for a sufficient length of time to ensure attainment of equilibrium. The two phases were separated by using a separating funnel. The aqueous phase was analyzed by titration against freshly prepared NaOH solution. The initial concentration of succinic acid was varied from.1mol/lit to.5mol/lit to obtain the equilibrium data keeping the concentration of Aliquat 336 at.5 mol/lit. The next set of experiments was conducted for studying the effect of change in volume ratio. Two sets were conducted 1) Volume ration of aqueous:organic= and aqueous:organic=.5. Experiments using sunflower oil as diluent were conducted for comparison between physical and reactive extraction. J. Technological Advances and Scientific Res./ eissn , pissn / Vol. 1/ Issue 4/ Oct-Dec. 15 Page 313

2 The same set of varying concentration of succinic acid was first extracted without using Aliquat 336 and then with Aliquat 336 (.5 mol/lit.) The solutions of Aliquat 336 were made in sunflower oil, soyabean oil and butanol for different sets of readings. RESULTS AND DISUSSION: Distribution coefficient which is the ratio of concentration of acid in organic phase to the concentration of acid in aqueous phase is an important parameter in extraction. It is given by the equation: K D A / A (1) where the over bar indicated concentration in the organic phase. In the first set of experiments concentration of Aliquat 336 was kept constant (.5M) and concentration of succinic acid was varied from (.1-.5 M) using all the three diluents. The extraction efficiency (Eq.) and the distribution coefficient were calculated. The loading factor (z) given by Eq. (3) indicates the amount of acid present in the organic phase at equilibrium per mole of extractant taken initially. / A 1 % E () / S A z A (3) Where A is the initial concentration of the acid in aqueous phase. The equilibrium complexation constant (KE) gives the strength of interaction between the acid and extractant. When the value of z<.5 indicating a 1:1 interaction between the acid and amine, it is given by: z 1 z (4) K E A When the value of z >.5 indicating a :1 interaction between the acid and amine, it is given by: z z K E A (5) Slope of the plot of z/1-z vs A or of z/-z vs A gives the value of the equilibrium complexation constant (KE). The results are shown in the table 1 A mol/lit A mol/lit A mol/lit %E KD z z/1-z z/-z A Diluent: Sunflower Oil Diluent: SoyabeanOil Diluent: n-butanol Table 1: Results of RE with concentration of Aliquat mol/lit and varying concentration of succinic acid Figure 1 shows the plot of the concentration of succinic acid in the organic phase vs that in the aqueous phase. It can be seen that as the concentration in the aqueous phase increase the concentration in the organic phase increases. Figure below shows the variation of percentage extraction with varying concentration of succinic acid in the aqueous phase at equilibrium. Fig.1: Variation of concentration of succinic In organic phase versus aqueous phase Fig. : Variation of % extraction with concenitration of succinic acid in aqueous phase J. Technological Advances and Scientific Res./ eissn , pissn / Vol. 1/ Issue 4/ Oct-Dec. 15 Page 314

3 It can be seen that the performance of butanol is better than sunflower oil which gives better results than soyabean oil. But at higher concentrations their performances are comparable. Figures 3 and 4 show a plot of z/(1-z) vs A and z/(-z) vs seen that z/(-z) vs soyabean oil. A. It can be A shows a better fit. The slope gives the value of KE: for butanol, for sunflower oil and 4.59 for Fig. 3: Plot of z/(1-z) vs concentration of succinic acid in the aqueous phase Fig. 4: Plot of z/(-z) vs square of concentration of succinic acid in aqueous phase In the second set of experiments the initial concentration of Aliquat 336 was maintained constant (.5 mol/lit) and the concentration of succinic acid was varied and two volume ratios were used with one diluent sunflower oil The results are shown in Table. J. Technological Advances and Scientific Res./ eissn , pissn / Vol. 1/ Issue 4/ Oct-Dec. 15 Page 315

4 A mol/lit A mol/lit A mol/lit %E KD z Diluent: Sunflower Oil, Volume ratio: (Aq. : Org) Diluent: Sunflower Oil, Volume ratio:.5 (Aq. : Org) Table : Results of RE with fixed concentration of Aliquat 336 (.5 ml/lit) and varying concentration of succinic acid, at two different volume ratios (Diluent: sunflower oil) It can be observed that the increase in the ratio of organic phase to aqueous phase leads to a significant increase in the %E and KD. The third set of experiments was conducted for comparing the reactive extraction process with the physical one. The results are shown in the Table 3. A mol/lit A mol/lit A mol/lit %E KD z Diluent: Sunflower Oil, Physical Extraction Diluent: Sunflower Oil, Reactive Extraction, S =.5 mol/lit Table 3: Results of comparison of RE with physical extraction in sunflower oil. ONLUSION: The study on the effect of diluent and nature of diluent has confirmed that naturally available diluents are nearly as efficient as compared to conventional chemical diluents. Sunflower oil was found to be more effective diluent than soybean oil, and its performance was found comparable to that of n-butanol. The distribution coefficients (KD) and the degree of extraction (%E) is found to increase with an increase in the initial acid concentrations. The % extraction increases with increase in volume of organic phase. Efficient separation was obtained when volume ratio was.5. Extraction up to 7.43% was obtained. Physical extraction is compared with reactive extraction, reactive extraction is found more effective than the physical extraction for separation of succinic acid. Physical extraction gives maximum extraction up to 11.11% and reactive extraction gives 51.3% extraction. NOMENLATURE: A - oncentration of succinic acid S - Initial concentration of aliquat 336 A - oncentration of succinic acid in aqueous phase A - - oncentration of succinic acid in organic phase S - oncentration of aliquat 336 in aqueous phase S - - oncentration of aliquat 336 in organic phase %E - Degree of extraction (%) Kd(D) - Distribution coefficient of succinic acid z - Loading Factor REFERENES: 1. Yeon Ki Hong. Won Hi Hong, Dong Hoon Han, Application of Reactive Extraction to Recovery of arboxylic Acids. Biotechnol. Bioprocess Eng. 1 Dec.; 6: Swarnkar A., Keshav A., Das A.K., Soni A.B., Modeling of the Recovery of itric Acid Using Aliquat 336 in Natural Diluents. Int. J. of Scientific Eng. And Res., 14 Nov.; (11): Wasewar K.L., Heesink A.B.M., Versteef G.F., Pangarkar V.G., Equilibria and Kinetics for Reactive Extraction. J hem Technol Biotechnol. Aug.; 77: Wasewar K.L., Shende D.Z., Equilibrium Study of Reactive Extraction of aproic Acid in MIBK and Xylene. Engineering. 1 June; 3: Sushil Kumar, Kamsonlian S., homal N., Equilibrium Study oo Reactive Extraction of Nicotinic Acid from Aqueous Solution. Int. J. of hem. Engg. And Applications. 14 Dec.; 5(6): Wangab K., han Z., Ma Y., Lei., Jin S., Y., Mahmood I., Hua., Liu H., Equilibrium Study on Reactive Extraction of Propionic Acid with N193 in different diluents. Fluid Phase Equilibria. 9, Feb.; 78: J. Technological Advances and Scientific Res./ eissn , pissn / Vol. 1/ Issue 4/ Oct-Dec. 15 Page 316

5 7. Athankar K.K., Varma M.N., Shende D.Z., hang K.Y., Wasewar K.L., Reactive Extraction of Phenylacetic Acid with Tri-n-butyl Phosphate in Benzene, Hexanol and Rice Bran Oil at 98 K. J. of hem. Engg. Data. 13, Oct.; 58: Datta D., Sushil Kumar, Modeling and Optimization of Recovery Process of Glycolic Acid Using Reactive Extraction. Int. J. of hem. Engg. And Applications. 1 April; 3(): Ganorkar P.V., Jadhav S.M., Gaikwad S.G., Reactive Extraction of Nicotinic Acid with Tri-iso-octylamine (TIOA) in 1-Deacnol. Int. J. of Adv. Tech. in Engg. And Sc., 14 Nov.; (11): J. Technological Advances and Scientific Res./ eissn , pissn / Vol. 1/ Issue 4/ Oct-Dec. 15 Page 317