Transesterification Catalysts from Iron Doped Hydrotalcite-like Precursors: Solid Bases for Biodiesel Production

Macala, Gerald S.; Robertson, Andrew W.; Johnson, Charles L.; Day, Zachary B.; Lewis, Robert S.; White, Mark G.; Iretskii, Alexei V.; Ford, Peter C.

doi:10.1007/s10562-008-9480-y

Cited by 94 publications

(69 citation statements)

References 15 publications

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“…Upon calcination, the resulting PMOs have large surface areas, while long-range order characteristic of the hydrotalcite structure is lost. 7 Our exploratory studies 30 in this regard used dihydrobenzofuran (DHBF) as a very simple model for lignin. The advantage of DHBF is that the carbon framework remains intact, thereby making the products easier to track.…”

Section: Accounts Of Chemical Researchmentioning

confidence: 99%

Catalytic Conversion of Nonfood Woody Biomass Solids to Organic Liquids

2014

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CONSPECTUS: This Account outlines recent efforts in our laboratories addressing a fundamental challenge of sustainability chemistry, the effective utilization of biomass for production of chemicals and fuels. Efficient methods for converting renewable biomass solids to chemicals and liquid fuels would reduce society's dependence on nonrenewable petroleum resources while easing the atmospheric carbon dioxide burden. The major nonfood component of biomass is lignocellulose, a matrix of the biopolymers cellulose, hemicellulose, and lignin. New approaches are needed to effect facile conversion of lignocellulose solids to liquid fuels and to other chemical precursors without the formation of intractable side products and with sufficient specificity to give economically sustainable product streams. We have devised a novel catalytic system whereby the renewable feedstocks cellulose, organosolv lignin, and even lignocellulose composites such as sawdust are transformed into organic liquids. The reaction medium is supercritical methanol (sc-MeOH), while the catalyst is a copper-doped porous metal oxide (PMO) prepared from inexpensive, Earth-abundant starting materials. This transformation occurs in a single stage reactor operating at 300−320°C and 160−220 bar. The reducing equivalents for these transformations are derived by the reforming of MeOH (to H 2 and CO), which thereby serves as a "liquid syngas" in the present case. Water generated by deoxygenation processes is quickly removed by the water−gas shift reaction. The Cu-doped PMO serves multiple purposes, catalyzing substrate hydrogenolysis and hydrogenation as well as the methanol reforming and shift reactions. This one-pot "UCSB process" is quantitative, giving little or no biochar residual. Provided is an overview of these catalysis studies beginning with reactions of the model compound dihydrobenzofuran that help define the key processes occurring. The initial step is phenyl−ether bond hydrogenolysis, and this is followed by aromatic ring hydrogenation. The complete catalytic disassembly of the more complex organosolv lignin to monomeric units, largely propyl-cyclohexanol derivatives is then described. Operational indices based on 1 H NMR analysis are also presented that facilitate holistic evaluation of these product streams that within several hours consist largely of propyl-cyclohexanol derivatives. Lastly, we describe the application of this methodology with several types of wood (pine sawdust, etc.) and with cellulose fibers. The product distribution, albeit still complex, displays unprecedented selectivity toward the production of aliphatic alcohols and methylated derivatives thereof. These observations clearly indicate that the Cu-doped solid metal oxide catalyst combined with sc-MeOH is capable of breaking down the complex biomass derived substrates to markedly deoxygenated monomeric units with increased hydrogen content. Possible implementations of this promising system on a larger scale are discussed.

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Section: Accounts Of Chemical Researchmentioning

confidence: 99%

Catalytic Conversion of Nonfood Woody Biomass Solids to Organic Liquids

2014

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“…The XRD patterns of all of the synthesized hydrotalcites ( Figure 2) show typical reflections of a layered doublehydroxide structure, [1,2,10] indicated by the values at 2q % 12, 23, 35, 39, 46, 60, and 628. For HT-carbonate and HT-oxalate, the diffraction patterns consist of sharp, symmetric and intense basal reflections at low 2q values, corresponding to successive orders of the interlayer spacing and broader reflections at higher 2q values.…”

Section: Resultsmentioning

confidence: 99%

“…[5][6][7][8][9] The attention hydrotalcite-derived mixed oxides have gained is mainly due to the fact that their catalytic properties can be set and adjusted by the composition of the hydrotalcite precursors during synthesis. Parameters influencing the catalytic properties of hydrotalcite-derived mixed oxides are the nature and ratio of cations within the cationic layers and the nature of anions in the interlayer region of the hydrotalcite precursor as well as the temperature of thermal decomposition, [6,[10][11][12][13] which affects the basic site density. [14] The influence of the composition of brucite-type layers in hydrotalcite precursors on the catalytic activity of derived mixed oxides has already been investigated.…”

Section: Introductionmentioning

confidence: 99%

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Impact of Organic Interlayer Anions in Hydrotalcite Precursor on the Catalytic Activity of Hydrotalcite‐Derived Mixed Oxides

Meyer¹,

Roessner²,

Rakoczy³

et al. 2010

ChemCatChem

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A series of hydrotalcite‐derived mixed oxides containing different organic interlayer anions in the hydrotalcite precursors have been synthesized and studied as catalysts in the transesterification of glycerol trioctanoate with methanol. There are significant differences in the catalytic activity of these mixed oxides, indicating a great impact of interlayer anions in hydrotalcite precursors. Generally, anions with high charge density and, therefore, high content within the interlayer of the hydrotalcites lead to higher catalytic activity in the derived mixed oxides in contrast to anions with low charge density. An influence of interlayer anions on the structural properties of the hydrotalcites, such as interlayer distance, which is determined by X‐ray diffraction analysis, and on the surface area and pore volume of the corresponding mixed oxides, which are determined by nitrogen adsorption, is obtained. Furthermore, interlayer anions had a significant effect on the thermal stability of the hydrotalcite structure as well as on the pore size distribution of derived mixed oxides.

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“…Mixed oxides samples Mg:Al 3:1 and Mg:Al 3:1 + 10% Fe were prepared from layered double hydroxides (LDH) hydrotalcites and were synthesized according to the procedure described in the literature [16]. Hydrotalcite, molar ratio Mg: 2 O was added slowly along with 100 ml of an aqueous solution containing 0.349 mol NaOH and 0.067 mol Na 2 CO 3 .…”

Section: Methodsmentioning

confidence: 99%

Co-production of butyrate methyl ester and triacetylglycerol from tributyrin and methyl acetate

Battistel

Calaprice

Gualdi

et al. 2011

Applied Catalysis A: General

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a b s t r a c tThe simultaneous synthesis of butyric acid methyl ester, the shortest component of the FAME (fatty acid methyl esters) family, and glycerol triacetate (TAG) from glycerol tributyrate (tributyrin) and methyl acetate was studied as a function of several reaction parameters, such as type of catalyst, temperature and products distribution. The reaction is an interesterification, a multistep consecutive ester interchange catalyzed by either acid or base catalyst. Under optimized conditions, a complete tributyrin conversion and an almost quantitative butyric acid methyl ester accumulation were achieved. The other reaction product, TAG, formed by the complete acetylation of the glycerol moiety, reached almost 70% yield, whereas the mono-and di-acetylated intermediates accumulated in the order of 5-8% and 24-27%, respectively. Similar final conversions and products yields were obtained with either acid or base homogeneous catalysts, suggesting that the final products mixture did not depend on the type of catalysis but might be limited by equilibrium conditions. In spite of similar final yields, base catalysis needed shorter reaction times (minutes instead of hours) and lower temperature (60 • C instead of 130 • C) with respect to the best acid catalyst. On the other hand, unlike heterogeneous basic catalysts, which showed low activity, a heterogeneous acid catalyst almost as active as the homogenous counterpart was found.

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Transesterification Catalysts from Iron Doped Hydrotalcite-like Precursors: Solid Bases for Biodiesel Production

Cited by 94 publications

References 15 publications

Catalytic Conversion of Nonfood Woody Biomass Solids to Organic Liquids

Catalytic Conversion of Nonfood Woody Biomass Solids to Organic Liquids

Impact of Organic Interlayer Anions in Hydrotalcite Precursor on the Catalytic Activity of Hydrotalcite‐Derived Mixed Oxides

Co-production of butyrate methyl ester and triacetylglycerol from tributyrin and methyl acetate

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