ADVANCES IN THE RESEARCH AND DEVELOPMENT OF ACRYLIC ACID PRODUCTION BIOMASS1 Xiaobo XUa, Jianping LINa and Peilin

CEN , a, a Institute of Bioengineering, Zhejiang University, Hangzhou 310027, China Received 19 July 2005; accepted 31 March 2006. Available online 24 September 2006.

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The shortage of petroleum has resulted in worldwide efforts to produce chemicals from renewable resources. Among these attempts, the possibility of producing acrylic acid from biomass has caught the eye of many researchers. Converting the carbohydrates first to lactic acid by fermentation and then dehydrating lactic acid to acrylic acid is hitherto the most effective way for producing acrylic acid from biomass. While the lactic acid fermentation has been commercialized since longer times, the dehydration process of lactic acid is still under development because of its low yield. Further efforts should be made before this process became economically feasible. Because of the existence of acrylic acid pathways in some microorganisms, strain improvement and metabolic engineering provides also a possibility to produce acrylic acid directly from biomass by fermentation.

PRODUCTION OF ACROLEIN AND ACRYLIC ACID THROUGH DEHYDRATION AND OXYDEHYDRATION OF GLYCEROL WITH MIXED OXIDE CATALYSTS J. Deleplanquea, , , J.-L. Duboisb, J.-F. Devauxb and W. Uedac, , a Unit de Catalyse et de Chimie du Solide, Universit Lille-Nord de France, Villeneuve dAscq, France b Centre de Recherche Rhne Alpes, ARKEMA, Pierre Bnite, France c Catalysis Research Center, Hokkaido University, Sapporo, Japan
Available online 16 May 2010.

Dehydration of glycerol solution and further oxidation have been investigated with different mixed oxide catalysts. Among them, iron phosphates were found to be highly active and selective toward acrolein. Glycerol conversion was nearly complete and acrolein yields reach 8090% after 5 h of test. Fresh and used catalysts were also characterized by different techniques (XRD, SEM, BET and TGADSC). Pure and well-defined structures were found more stable than relatively poor crystalline phase. Distribution of products changes during the deactivation of the catalyst, leading to by-products such as acetol, propanal and coke deposit on the surface of the catalyst, indicating a modification of the mechanism. Introducing some oxygen in the feed allowed decreasing the amount of those by-products, but oxidation products appeared such as acetic acid or COx on detriment of the yield in acrolein. Using appropriate mixed oxide catalysts such as molybdenum/tungsten vanadium based catalysts showed interesting performances to obtain acrylic acid directly from glycerol.

DEHYDRATION OF LACTIC ACID TO ACRYLIC ACID IN HIGH TEMPERATURE WATER AT HIGH PRESSURES Taku Michael Aidaa, , , Akira Ikarashia, Yuki Saitoa, Masaru Watanabeb, Richard Lee Smith Jr.a, b and Kunio Araia a Graduate School of Environmental Studies, Tohoku University, Sendai, Aramaki Aza Aoba 6-6-11, Aoba-ku, Sendai 980-8579, Japan b Research Center of Supercritical Fluid Technology, Tohoku University, Aramaki Aza Aoba 6-6-11, Aoba-ku, Sendai 980-8579, Japan
Received 20 May 2009; revised 12 June 2009; accepted 12 June 2009. Available online 23 June 2009.

Reaction of lactic acid was investigated with a flow apparatus in water at high temperatures (450 C) and high pressures (40100 MPa). The major products obtained from the reaction of lactic acid were acrylic acid, acetaldehyde, and the minor products were acetic acid and propionic acid. The maximum selectivity of acrylic acid was 44% at 23% lactic acid conversion that was obtained at 450 C, 100 MPa and a residence time of 0.8 s. The reaction kinetics could be modeled by considering two pathways defined as a dehydration pathway to acrylic acid and a combined reaction pathway that consisted of decarboxylation and decarbonylation to acetaldehyde. The data and the kinetic analysis consistently show that both dehydration and the combined decarboxylation and decarbonylation reactions continue to be promoted in supercritical water as pressure (water density) increases. However, high water densities increase the selectivity of the dehydration reaction.

O.V. Ignatova, S.M. Rogatchevab, O.V. Vasil'evab and V.V. Ignatova a Institute of Biochemistry and Physiology of Plants and Microorganisms, Russian Academy of Sciences, Entuziastov av., 13, Saratov 410015, Russia b Saratov State University, Saratov, Russia
Available online 18 May 2007.

SELECTIVE DETERMINATION OF ACRYLONITRILE, ACRYLAMIDE AND ACRYLIC ACID IN WASTE WATERS USING MICROBIAL CELLS The possibility of using the respiratory activity of microbial cells for the separate determination of acrylonitrile, acrylamide or acrylic acid in a mixture of these compounds has been demonstrated. The experiments were conducted using the two bacterial strains Brevibacterium sp. and Pseudomonas pseudoalcaligenes, possessing different enzyme systems of acrylonitrile and acrylamide metabolism. The conditionsto obtain high respiratory activity of Brevibacterium sp. cells for acrylamide and/or for acrylic acid and of P. pseudoalcaligenes cells for acrylonitrile have been optimized. For the quantitation of the mentioned compounds, the concentration dependences of the cell respiratory activity were established. They were linear in the concentration diapason 0.141.4 mM for acrylic acid, 0.14 1.0 mM for acrylamide and 0.020.10 mM for acrylonitrile. The selectivity of the cell respiratory activity for various organic amides, nitriles and acids has been studied.