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Chapter 27 : Biorefineries for Solvents: the MixAlco Process

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Biorefineries for Solvents: the MixAlco Process, Page 1 of 2

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Abstract:

From ethanol to vegetable oils, solvents have always been extremely important to the chemical industry from its inception. Until the advent of the petrochemical industry, solvents were biologically derived. With the petrochemical revolution, more extensive production, more variety, and more efficient solvents became economically feasible. ABE fermentation by , for instance, allows for mainly four solvents, namely, ethanol, acetone, butanol, and acetic acid (other minor products being acetoin and butyric acid). An alternative for the production of alcohol solvents is the thermochemical platform, which converts syngas (carbon monoxide and hydrogen) produced from the gasification of biomass, into Fischer-Tropsch (F-T) fuels and mixed alcohols through catalysis. Methanogenesis can be inhibited by maintaining a low pH; however, low pH also inhibits the production of the desired carboxylic acids. For the fermentation in the MixAlco process, methane analogs, such as bromoform or iodoform, are preferred as methane inhibitors. The ketones obtained from dry distillation of the calcium carboxylate salts may be sold as such, or they may be further converted by hydrogenation into secondary alcohols. The wide diversity of products that the MixAlco process allows meeting the diverse solvent demand that the petrochemical industry has created. When technology is fully established and large plants are built, it will be possible to pay more for the biomass and grow crops specifically for energy and chemical production, which will be mostly processed into alcohols for the fuel market.

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27

Key Concept Ranking

Methyl Ethyl Ketone
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Figures

Image of Figure 1.
Figure 1.

Brief carboxylate/carboxylic acid-based chemical flowchart.

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27
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Image of Figure 2.
Figure 2.

Flow diagram of the MixAlco process when CaCO is used as buffering agent (for details on acid springing, refer to the text).

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27
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Image of Figure 3.
Figure 3.

Flow diagram of the MixAlco process when NHHCO is used as buffering agent (for details on acid springing, refer to the text).

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27
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Image of Figure 4.
Figure 4.

Biomass lime/air pretreatment.

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27
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Image of Figure 5.
Figure 5.

Delignification during lime pretreatment of sugarcane bagasse with and without air at 50°C ( ).

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27
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Image of Figure 6.
Figure 6.

Countercurrent laminar-flow fermentor.

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27
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Image of Figure 7.
Figure 7.

Sketch of the round-robin system operation.

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27
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Image of Figure 8.
Figure 8.

Vapor compression evaporator.

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27
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Image of Figure 9.
Figure 9.

Thermal conversion to ketones of calcium carboxylate salts from MixAlco fermentation ( ).

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27
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Image of Figure 10.
Figure 10.

Secondary alcohols production by ketone hydrogenation.

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27
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Image of Figure 11.
Figure 11.

Acid springing system for calcium carboxylate salts.

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27
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Image of Figure 12.
Figure 12.

Acid springing system for ammonium carboxylate salts.

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27
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Image of Figure 13.
Figure 13.

Gas phase catalytic ketonization of carboxylic acids.

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27
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Image of Figure 14.
Figure 14.

Esterification of ammonium salts and hydrogenolysis of esters.

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27
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References

/content/book/10.1128/9781555815547.ch27
1. Agbogbo, F. K. 2005. Anaerobic fermentation of rice straw and chicken manure to carboxylic acids. Ph.D. dissertation. Texas A&M University, College Station.
2. Agbogbo, F. K., and, M. T. Holtzapple. 2007. Fixed-bed fermentation of rice straw and chicken manure using a mixed culture of marine mesophilic microorganisms. Bioresour. Technol. 98:15861595.
3. Aldrett-Lee, S. 2000. Catalytic hydrogenation of liquid ketones with emphasis on gas-liquid mass transfer. Ph.D. dissertation. Texas A&M University, College Station.
4. Atchison, J. E., and, J. R. Hettenhaus. 2004. Innovative Methods for Corn Stover Collecting, Handling, Storing and Transporting (NREL/ SR-510-33893). National Renewable Energy Laboratory (NREL), Golden, CO. http://www.nrel.gov/docs/fy04osti/33893.pdf.
5. Bradley, M. W.,, N. Harris, and, K. Turner. November. 1982. Process for Hydrogenolysis of Carboxylic Acid Esters. Patent WO 82/03854.
6. Filachione, E. M.,, E. J. Costello, and, C. H. Fisher. 1951. Preparation of esters by reaction of ammonium salts with alcohols. J. Am. Chem. Soc. 73:52655267.
7. Granda Cotlear, C. B. 2004. Sugarcane juice extraction and preservation, and long-term lime pretreatment of bagasse. Ph.D. dissertation. Texas A&M University, College Station.
8. Kim, S. 2004. Lime pretreatment and enzymatic hydrolysis of corn stover. Ph.D. dissertation. Texas A&M University, College Station.
9. Klass, D. L. 1998. Biomass for Renewable Energy, Fuels, and Chemicals, p. 431. Academic Press, San Diego, CA.
10. Lara-Ruiz, J. H. J. 2005. An advanced vapor-compression desalination system. Ph.D. dissertation. Texas A&M University, College Station.
11. Maiorella, B. L. 1985. Ethanol. In M. Young (ed.), Comprehensive Biotechnology, vol. 3. Pergamon Press, Oxford, United Kingdom.
12. Martin, S. A., and, J. M. Macy. 1985. Effects of monensin, pyromellitic diimide and 2-bromoethanesulfonic acid on rumen fermentation in vitro. J. Anim. Sci. 60:544550.
13. National Renewable Energy Laboratory (NREL). 2006. Equipment Design and Cost Estimation for Small Modular Biomass Systems, Synthesis Gas Cleanup, and Oxygen Separation Equipment—Task 9: Mixed Alcohols from Syngas—State of Technology. Contract No. DE-AC36-99-GO10337, subcontract report NREL/SR-510-39947. National Renewable Energy Laboratory, Golden, CO. http://www.nrel.gov/docs/fy06osti/39947.pdf.
14. Sierra Ramirez, R. 2005. Long-term lime pretreatment of poplar wood. M.S. thesis. Texas A&M University, College Station.
15. Thanakoses, P. 2002. Conversion of bagasse and corn stover to mixed carboxylic acids using a mixed culture of mesophilic microorganisms. Ph.D. dissertation. Texas A&M University, College Station.
16. Verser, D., and, T. Eggeman. 2005. Process for producing ethanol. U.S. patent 6,927,048. http://www.zeachem.com.
17. Williamson, S.A. 2000. Conversion of carboxylate salts to carboxylic acids via reactive distillation. M.S. thesis. Texas A&M University, College Station.
18. Yeh, H. 2002. Pyrolytic decomposition of carboxylate salts. M.S. thesis. Texas A&M University, College Station.

Tables

Generic image for table
Table 1.

Typical carboxylic acid profiles when using different buffers and temperatures

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27
Generic image for table
Table 2.

Some of the chemicals that can be produced using the MixAlco process

Citation: Granda C, Holtzapple M. 2008. Biorefineries for Solvents: the MixAlco Process, p 347-360. In Wall J, Harwood C, Demain A (ed), Bioenergy. ASM Press, Washington, DC. doi: 10.1128/9781555815547.ch27

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