Article pubs.acs.org/IECR
Fumaric Acid Recovery and Purification from Fermentation Broth by Activated Carbon Adsorption Followed with Desorption by Acetone Kun Zhang,† Lijie Zhang,‡ and Shang-Tian Yang*,† †
William G. Lowrie Department of Chemical and Biomolecular Engineering, The Ohio State University, 140 West 19th Avenue, Columbus, Ohio 43210, United States ‡ Department of Pharmacy and Bioengineering, Chongqing University of Technology, No. 4 XingSheng Road, Chongqing, China 400050 ABSTRACT: To develop an economic and efficient recovery and purification method for fermentation-produced fumaric acid, an integrated process was developed by adsorption with activated carbon, followed with acetone desorption. Activated carbon possessed a high adsorption capacity for fumaric acid (∼200 mg/g) at a lower pH (1, reflecting that fumaric acid was favorably adsorbed by activated carbon under the three pH values studied. Overall, considering the model suitability on fumaric acid solution at pH 3 and the highly heterogeneous surface16 of activated carbon with the presence of mesoporosity as discussed before, the Freunlich model gave a better correlation for fumaric acid adsorption onto activated carbon. However, because the study was focused on the low-concentration fumaric acid (10 against glucose and malic acid, respectively (data not shown). 3.2. Desorption of Fumaric Acid by Acetone. The desorption process for fumaric acid adsorbed on activated
Figure 3. Effects of glucose (A) and malic acid (B) on fumaric acid adsorption by activated carbon (fumaric acid initial concentration = 5.5 g/L).
carbon was investigated. In an unreported experiment, the effects of different desorption solutions (water, H2SO4) were studied. Water can wash away ∼35% of fumaric acid from activated carbon, whereas ∼75% of fumaric acid can be removed by using H2SO4, with 25% remaining. The desorption yields were low for both water and H2SO4. Acetone has been found to effectively strip lactic acid out of activated carbon with a high recovery yield, indicating a high affinity of acetone by the activated carbon surface.18 Thus, desorption of fumaric acid using acetone was attempted. After desorption, acetone was removed by evaporation and recovered by condensation; meanwhile, fumaric acid powders were formed on the glass wall. The effects of acetone volume and temperature on the desorption process were studied, with results shown in Table 2. The desorption yield was defined as the fraction of adsorbed Table 2. Effects of Temperature and Acetone Volume on Fumaric Acid Desorption from 2 g of Wet Activated Carbon temperature (°C)
acetone volume (mL)
desorption yielda
± ± ± ± ± ± ± ±
50 100 150 200 100 100 100 100
0.80 0.85 0.87 0.90 0.77 0.83 0.86 0.98
33 33 33 33 22 33 41 47
1 1 1 1 1 1 1 1
a
Desorption yield: the fraction of adsorbed fumaric acid recovered by desorption with acetone.
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dx.doi.org/10.1021/ie501559f | Ind. Eng. Chem. Res. 2014, 53, 12802−12808
Industrial & Engineering Chemistry Research
Article
132 mg/g due to unsaturated activated carbon adsorption, the fumaric acid concentration in the effluent was well controlled under 98%. This adsorption process is more efficient and cost-effective compared with the current method using acid precipitation.
process was applied to the case of recovery from fermentation broth. The sweeping water washed out not only these soluble impurities but also the yellow pigments of the broth. The purity of the final product reached >98%. The water sweeping process can be further improved by using cold water, in which fumaric acid has a lower solubility, or by double sweeping. 3.5. Comparative Study with Conventional Process. A simple comparative study was performed between the novel precipitation−adsorption process developed in this study and the conventional process9 for fumaric acid separation from fermentation broth. Figure 7 illustrates the simplified flowcharts
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AUTHOR INFORMATION
Corresponding Author
*(S.-T.Y.) Tel: (614) 292-6611. Fax: (614) 292-3769. E-mail:
[email protected]. Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This research was supported by the United Soybean Board and the Consortium for Plant Biotechnology Research through a U.S. Department of Energy grant.
Figure 7. Flowchart of the fumaric acid recovery and purification processes using the conventional (dashed box) and new precipitation− adsorption (solid box) methods.
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REFERENCES
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of the two processes. The procedures before crystallization were the same for the two processes: the fermentation broth was acidified, heated, and filtered. For the conventional method, fumaric acid crystallization was carried out at 5 °C by using chilled water with a higher crystallization yield and higher operational cost. After being separated from the aqueous solution by filtration, the crystal was dried in a rotary dryer with the final product obtained. The filtrate was regarded as liquid waste. For the current method, fumaric acid crystallization was carried out at room temperature by using cooling water with a lower crystallization yield but lower cost. The crystal was obtained in the same way as in the precipitation method. However, the filtrate passed through a packed-bed column filled with activated carbon to adsorb the residual fumaric acid, which was then desorbed from the column with acetone. The acetone solution containing fumaric acid was then heated at 70 °C to completely boil off acetone, which was recovered by condensation for future reuse. The fumaric acid powder was washed to remove soluble impurities. The packed-bed column and the crystallization tank, as well as the activated carbon and acetone, could be considered as capital investments due to their reusability, whereas the loss of the materials during each batch as consumables. Overall, although the precipitation−adsorption process required additional capital investments (activated carbon, acetone, fixed-bed column, vessel for acetone evaporation, etc.), the process had the following advantages, especially on reducing the operational cost and increasing product quality. First, by operating the crystallization process at room temperature, the cooling cost can be reduced due to the use of cooling water instead of chilled water. Second, by targeting the filtrate for fumaric acid recovery, the cost of liquid waste treatment for the filtrate was avoided. Third, with the adsorption process, the overall recovery yield of the separation process can be significantly enhanced with an improved purity and product quality of the final crystals. 12807
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