(444c) Optimal Simultaneous Production of Bio-Ibutene and Bioethanol From Switchgrass

Authors: 
Martín, M., University of Salamanca
Grossmann, I. E., Carnegie Mellon University



Ibutene is an important intermediate that has been typically produced from the cracking of the C4 fraction of crude oil. It is the basis for the production of a common additive to gasoline in search for a cleaner burning fuel, the methyl-tert-butyl ether (MTBE), as well as a monomer for the polymerization such as butyl rubber. Its importance can be somehow reflected in its price, around $2/kg. However, the dependency on the crude oil and the already limited availability due to the large number of applications has increased the need for new sources of this chemical. Ibutene has recently been used as intermediate for the production of oxygenated diesel substitutes from glycerol (Chen et al 2011, Vlad et al 2010, Martín & Grossmann 2013). In this application the main drawbacks are, on the one hand, the production of diesel substitutes using a fossil fuel based intermediate and, on the other hand, the economics since from the energy and water consumption standpoint its use for the enhanced production of diesel substitutives is competitive with the process that directly sells the glycerol as byproduct.

In this work, we propose the optimal flowsheet for the production of ibutene from switchgrass. A superstructure embedding a number of alternatives is proposed. Two technologies are considered for switchgrass pretreatment, dilute acid and ammonia fibre explosion (AFEX) so that the structure of the grass is broken down. Surface response models are developed for predicting the effect of the operating conditions on the yield of each pretreatment. Next, enzymatic hydrolysis follows any of the pretreaments to obtain fermentable sugars, mainly xylose and glucose. Ibutene is obtained by fermentation of the sugars. However xylose cannot be easily converted, and thus we also evaluate the possibility of using it to produce bioethanol. Next the ibutene has to be separated mainly from CO2 for which, PSA or membrane separation are considered while in case ethanol is produced, a multi-effect distillation column followed by molecular sieves are used to dehydrate the ethanol. The problem is formulated as an MINLP with simultaneous optimization and heat integration based on Duran and Grossmann’s model (1986). Finally, an economic evaluation is performed.

The most promising process involves the use of dilute acid pretreatment and membrane purification of the ibutene. The production of ibutene using renewable sources is feasible, and may be competitive for its use to generate diesel substitutes for glycerol etherification. However, the decision related to the production of ibutene alone or the simultaneous production of ibutene and ethanol depends on the prices for bioethanol and for switchgrass. For low and current biomass cost the production of ethanol ad ibutene is interesting for bioethanol process above $1/gal.

References:

Chen, P., Min, M., Chen, Y., Wang, L., Li, Y., Chen, Q., Wang, C., Wan, Y., Wang, X., Cheng, Y., Deng, S., Hennessy, K., Lin, X., Liu, Y., Wang, Y., Martinez, B., Ruan, R., 2009. Review of the biological and engineering aspects of algae to fuels approach. Int. J. Agric. Biol. Eng. 2, 1–30.

Duran, M.A.; Grossmann, I.E. (1986) Simultaneous optimization and heat integration of chemical processes. AIChE, J., 32, 123-138

Martín, M., Grossmann, I.E. (2013) Simultaneous dynamic optimization and heat integration for the co-production of diesel substitutes: Biodiesel (FAME & FAEE) and  glycerol ethers from algae oil. To be Submitted

Vlad, E., Bildea, C.S. and Bozga, G., 2010, Integrated design and control of glycerol etherification processes, Bull. Inst. Pol. Iasi, LVI (LX), 4, 139-148.