Optimization of biodiesel production from trap grease via acid catalysis

As a kind of waste collected from restaurants, trap grease is a chemically challenging feedstock for biodiesel production for its high free fatty acid (FFA) content. A central composite design was used to evaluate the effect of methanol quantity, acid concentration and reaction time on the synthesis of biodiesel from the trap grease with 50% free fatty acid, while the reaction temperature was selected at 95 degrees C. Using response surface methodology, a quadratic polynomial equation was obtained for ester content by multiple regression analysis. Verification experiments confirmed the validity of the predicted model. To achieve the highest ester content of crude biodiesel (89.67%), the critical values of the three variables were 35.00 (methanol-to-oil molar ratio), 11.27 wt% (catalyst concentration based on trap grease) and 4.59 h (reaction time). The crude biodiesel could be purified by a second distillation to meet the requirement of biodiesel specification of Korea.

Biodiesel production by acid catalysis with heteropolyacids supported on activated carbon fibers

Different catalysts, based on heteropolyacids supported on activated carbon fibers, have been prepared for palmitic acid esterification reaction. The influence of the catalyst (heteropolyacid) and the support on the catalytic activity have been analyzed. The results prove that an adequate combination of both is required to achieve the most suitable catalysts. Regarding to the heteropolyacid, phosphomolybdic acid seems to be the most suitable appropriate taking into account its lowest leaching. About the support, it must show an optimum microporosity, which must be wide enough to allow the entrance and exit of the reagents and products but not too wide in order to avoid the leaching of the catalyst. In addition, both decreasing of the catalytic activity and its recovery over several cycles have been analyzed.

Enhancing itaconic acid production by Aspergillus terreus

Aspergillus terreus is successfully used for industrial production of itaconic acid. The acid is formed from cis-aconitate, an intermediate of the tricarboxylic (TCA) cycle, by catalytic action of cis-aconitate decarboxylase. It could be assumed that strong anaplerotic reactions that replenish the pool of the TCA cycle intermediates would enhance the synthesis and excretion rate of itaconic acid. In the phylogenetic close relative Aspergillus niger, upregulated metabolic flux through glycolysis has been described that acted as a strong anaplerotic reaction. Deregulated glycolytic flux was caused by posttranslational modification of 6-phosphofructo-1-kinase (PFK1) that resulted in formation of a highly active, citrate inhibition-resistant shorter form of the enzyme. In order to avoid complex posttranslational modification, the native A. niger pfkA gene has been modified to encode for an active shorter PFK1 fragment. By the insertion of the modified A. niger pfkA genes into the A. terreus strain, increased specific productivities of itaconic acid and final yields were documented by transformants in respect to the parental strain. On the other hand, growth rate of all transformants remained suppressed which is due to the low initial pH value of the medium, one of the prerequisites for the accumulation of itaconic acid by A. terreus mycelium. © 2010 Springer-Verlag.

Catalysis and temperature dependence on the formation of ZnO nanoparticles and of zinc acetate derivatives prepared by the sol-gel route

The chemical and structural nature of powders prepared from the zinc acetate-derived precursor using the sol-gel route is discussed. The influence of the synthesis temperature and of the hydrolytic catalyst on the structural features of the powder is focused on the basis of X-ray powder diffraction (XRPD) and extended X-ray absorption fine structure (EXAFS) measurements and complemented with density and thermoanalysis (TG-DTA) results. EXAFS and XRPD results show that no-washed nanoparticulate powders are composed of a mixture of ZnO (wurtzite), zinc acetate, and zinc hydroxyacetate. The latter has a layered structure typical of hydroxy double salts (HDS). The main component of no-washed powders is always unreacted zinc acetate solid but the relative amount of the zinc-based compounds depends on the nature of the hydrolytic catalyst, hydrolysis ratio, and of synthesis temperature. According to the proportion of the three zinc-based compounds, three families of powders could be distinguished. The amount of ZnO nanoparticles (1.6 +/- 0.6 nm) decreases as the synthesis temperature increases, as the hydrolysis ratio decreases, or by changing from basic to acid catalysis. This finding suggests that the formation of zinc compounds is controlled by the equilibrium between hydrolysis-condensation and complexation-reprecipitation reactions.

SAXS study of monodispersed silica nanospheres obtained by an amino acid route

Spherical silica nanoparticles were prepared using a basic amino acid catalysis route and the kinetics of the particles growth was investigated by small angle X-ray scattering (SAXS). L-arginine was used in the polar aqueous phase as the basic catalyst whereas the tetraethylorthosilicate (TEOS) was dissolved in the cyclohexane oil phase as the silicate monomer source. The SAXS measurements were taken in the aqueous phase at different reaction times. A high degree of monodispersity was clearly evidenced for the spherical nanoparticles as a result of the pronounced high-order oscillations observed in the SAXS curves. The SAXS data show that the particles number density remains unchanged since both the particle size as well as the volume fraction gradually increase. This process was discussed based on a reaction-controlled addition of monomer species at the surface of the growing particles. Consequently, the monodispersed spherical nanoparticles radius can as such be finely tuned from 7 to 12 nm by varying the reaction time. (C) 2010 Elsevier B.V. All rights reserved.

Sustainable processes using heterogeneous acid catalysts. Some examples of industrial interest.

In recent years the need for the design of more sustainable processes and the development of alternative reaction routes to reduce the environmental impact of the chemical industry has gained vital importance. Main objectives especially regard the use of renewable raw materials, the exploitation of alternative energy sources, the design of inherently safe processes and of integrated reaction/separation technologies (e.g. microreactors and membranes), the process intensification, the reduction of waste and the development of new catalytic pathways. The present PhD thesis reports results derived during a three years research period at the School of Chemical Sciences of Alma Mater Studiorum-University of Bologna, Dept. of Industrial Chemistry and Materials (now Dept. of Industrial Chemistry “Toso Montanari”), under the supervision of Prof. Fabrizio Cavani (Catalytic Processes Development Group). Three research projects in the field of heterogeneous acid catalysis focused on potential industrial applications were carried out. The main project, regarding the conversion of lignocellulosic materials to produce monosaccharides (important intermediates for production of biofuels and bioplatform molecules) was financed and carried out in collaboration with the Italian oil company eni S.p.A. (Istituto eni Donegani-Research Center for non-Conventional Energies, Novara, Italy) The second and third academic projects dealt with the development of green chemical processes for fine chemicals manufacturing. In particular, (a) the condensation reaction between acetone and ammonia to give triacetoneamine (TAA), and (b) the Friedel-Crafts acylation of phenol with benzoic acid were investigated.

First-principle studies of intermolecular and intramolecular catalysis of protonated cocaine

We have performed a series of first-principles electronic structure calculations to examine the reaction pathways and the corresponding free energy barriers for the ester hydrolysis of protonated cocaine in its chair and boat conformations. The calculated free energy barriers for the benzoyl ester hydrolysis of protonated chair cocaine are close to the corresponding barriers calculated for the benzoyl ester hydrolysis of neutral cocaine. However, the free energy barrier calculated for the methyl ester hydrolysis of protonated cocaine in its chair conformation is significantly lower than for the methyl ester hydrolysis of neutral cocaine and for the dominant pathway of the benzoyl ester hydrolysis of protonated cocaine. The significant decrease of the free energy barrier, ∼4 kcal/mol, is attributed to the intramolecular acid catalysis of the methyl ester hydrolysis of protonated cocaine, because the transition state structure is stabilized by the strong hydrogen bond between the carbonyl oxygen of the methyl ester moiety and the protonated tropane N. The relative magnitudes of the free energy barriers calculated for different pathways of the ester hydrolysis of protonated chair cocaine are consistent with the experimental kinetic data for cocaine hydrolysis under physiologic conditions. Similar intramolecular acid catalysis also occurs for the benzoyl ester hydrolysis of (protonated) boat cocaine in the physiologic condition, although the contribution of the intramolecular hydrogen bonding to transition state stabilization is negligible. Nonetheless, the predictability of the intramolecular hydrogen bonding could be useful in generating antibody-based catalysts that recruit cocaine to the boat conformation and an analog that elicited antibodies to approximate the protonated tropane N and the benzoyl O more closely than the natural boat conformer might increase the contribution from hydrogen bonding. Such a stable analog of the transition state for intramolecular catalysis of cocaine benzoyl-ester hydrolysis was synthesized and used to successfully elicit a number of anticocaine catalytic antibodies.

An eight-connected metal organic framework based on Cu(5) clusters: Synthesis, structure, magnetic and catalytic properties

A reaction of copper acetate, 5-nitroisophthalic acid in a water-methanol mixture under solvothermal condition results in a new metal-organic framework compound, [Cu(5)(mu(3)-OH)(2)(H(2)O)(6){(NO(2))-C(6)H(3)-(COO)(2)}(4)]center dot 5H(2)O, (1). The compound contains Cu5 pentameric cluster units connected by 5-nitro isophthalate (NIPA) moieties forming a CdCl(2)-like layer, which are further connected by another NIPA moiety forming the three-dimensional structure. The water molecules in (1) can be reversibly adsorbed. The removal of water accompanies a change in the colour as well as a structural re-organization. Magnetic studies suggest strong antiferromagnetie correlations between the Cu5 cluster units. The compound (1) exhibits heterogeneous Lewis acid catalysis for the cyanosilylation of imines with more than 95 % selectivity. Compound (1) has been characterized by IR, UV-vis, TGA, powder XRD studies.

Defect-Free Hyperbranched Polydithioacetal via Melt Polymerization

Degree of branching (DB) describes the level of structural perfection of a hyperbranched polymer when compared to its defect-free analogue, namely the dendrimer. The strategy most commonly used to achieve high DB values, specifically while using AB(2) type self-condensations, is to design an AB2 monomer wherein the reaction of the first B-group leads to an enhancement of the reactivity of the second one. In the present study, we show that an AB2 monomer carrying a dimethylacetal unit and a thiol group undergoes a rapid self-condensation in the melt under acid-catalysis to yield a hyperbranched polydithioacetal with no linear defects. NMR studies using model systems reveal that the intermediate monothioacetal is relatively unstable under the polymerization conditions and transforms rapidly to the dithioacetal; because this second step occurs irreversibly during polymer formation, it leads to a defect-free hyperbranched polydithioacetal. TGA studies of the polymerization process provided some valuable insights into the kinetics of polymerization. An additional virtue of this approach is that the numerous terminal dimethylacetal groups are very labile and can be quantitatively transformed by treatment with a variety of functional thiols; the terminal dimethylacetals were, thus, reacted with various thiols, such as dodecanethiol, benzyl mercaptan, ethylmercaptopropionate, and so on, to demonstrate the versatility of these systems as sulfur-rich hyperscaffolds to anchor different kinds of functionality on their periphery.

Glycosidic bond hydrolysis in septanosides: a comparison of mono-, di-, and 2-chloro-2-deoxy-septanosides

A kinetic study of the hydrolytic stabilities of mono-, di-, and 2-chloro-2-deoxy septanosides, under acid-catalysis, is reported herein. A comparison of mono-and diseptanosides, shows that the glycosidic bond in the disaccharide is more stable than the monosaccharide. Further the glycosidic bond at the reducing end hydrolyzes almost twice as faster than that of the non-reducing end of the disaccharide. 2-Chloro-2-deoxy septanoside is found to be the most stable and its glycosidic bond hydrolysis occurs at elevated temperatures only. The orientation of the exo-cyclic hydroxymethyl group and the inductive effect are suggested to play a role in the rates of hydrolysis. (C) 2014 Elsevier Ltd. All rights reserved.

Heterogeneous catalysts for biodiesel production

The production of biodiesel is greatly increasing due to its enviromental benefits. However, production costs are still rather high, compared to petroleum-based diesel fuel. The introduction of a solid heterogeneous catalyst in biodiesel production could reduce its price, becoming competitive with diesel also from a financial point of view. Therefore, great research efforts have been underway recently to find the right catalysts. This paper will be concerned with reviewing acid and basic heterogeneous catalyst performances for biodiesel production, examining both scientific and patent literature.

苯乙酮、氨甲酸酯参与的直接Mannich反应

Mannich反应是有机化学中最重要的碳-碳键形成反应，其产物是合成手性胺的通用中间体。间接Mannich反应使用不稳定的预制烯醇等当体，以未修饰的酮为给体的直接方法将增强Mannich反应的效率。针对低活性苯乙酮、氨甲酸酯参与的直接Mannich反应，研究工作将更具挑战性。 在前期实验中，我们发现Lewis酸-NbCl5可高效催化苯乙酮、芳香醛、芳香胺三组分直接Mannich反应，反应在环境温度下进行，高收率获得Mannich碱。这是以苯乙酮参与的Mannich反应中，实现催化量Lewis酸催化的首次报道。该方法高效且操作简单。但就底物而言，对易去保护、低活性的氨甲酸酯类底物收率较低。我们设想Brønst酸可解决此类底物问题。令人高兴的是，杂多酸可高效催化芳香酮、芳香醛、氨甲酸酯三组分直接Mannich反应，反应在环境温度下进行，高收率获得N-保护的β-氨基酮。该方法底物范围广泛，普适性强且催化剂便宜。 基于杂多酸在苯乙酮、氨甲酸酯为底物直接Mannich反应中的高效性，我们设想杂多酸与功能化的手性有机小分子-手性伯胺组装可解决催化剂回收问题，同时实现不对称催化。实验结果表明，非共价键固载手性伯胺不能有效催化苯乙酮为底物的直接Mannich反应，无论是对映选择性还是收率均较低。随后，我们以丙二酸酯及α-氨基砜为底物，以增强底物活性，同时绕开亚胺的不稳定性。辛可宁伯胺以氢键双活化底物，有效催化原位产生氨甲酸酯类亚胺与丙二酸酯的Mannich反应，高收率获得Mannich碱，ee值中等。 我们采用逐步解决问题的策略解决Mannich反应中的部分问题并在Lewis酸催化、Brønst酸催化、非共价键固载手性伯胺催化及手性伯胺氢键催化的直接Mannich反应中做出了有益探索。 The Mannich reactions are among the most fundamental carbon-carbon bond forming reactions in organic chemistry, and the reaction products are versatile intermediates in the synthesis of chiral amines. The indirect Mannich reaction uses preformed enolate equivalents. However the preformed enolates are unstable. Thus, a direct methodology based on unmodified ketone donors would enhance the efficiency of the Mannich reaction. Especially researches for the directed Mannich reactions of acetophenone, carbamate, which own lower activities, will be more challengeable. In the initial experiments, we found an efficient Lewis acid-NbCl5 which could catalyze three-component Mannich-type reaction of acetophenone, aromatic aldehydes and aromatic amines at ambient temperature in high yields. This is the first report that use catalytic amount of Lewis acid in the Mannich reactions of .acetophenone. The method reported is not only simple to operate but also efficient. However, as far as amines are concerned, the substrates of carbamates which can be deprotected more easily and less reactive than amines give low yields. We envisaged that Brønsted acid would resolve this problem. Pleasingly, heteropoly acids (HPA) efficiently catalyzed one-pot three-component Mannich reactions of aryl aldehydes, aryl ketones, and carbamates at ambient temperature and afforded the corresponding N-protected β-amino ketones in good to excellent yields. This method provides a novel and improved modification of three-component Mannich reactions in terms of a wide scope of aldehydes, ketones and carbamates, economic viability. Based on the high efficiency of heteropoly acids in the Mannich reaction of acetophenone and carbamates, we envisaged that if HPA were combined with functionalized chiral organocatalysts–chiral primary amines the assemblies may be able to act as recoverable asymmetric organocatalysts. The results of exprimentals showed that noncovalently supported heterogeneous chiral primary amine couldn’t effectively catalyze the Mannich reactions which own two the substrate of acetophenone regardless of enantioselectivity and yield. Then, we employed malonates and α-amido sulfones as substrates to enhance reactivity of substrates and circumvent the instability of imines. A moderately enantioselective and highly yield Mannich reaction with in situ generation of carbamate-protected imines from stable α-amido sulfones catalyzed by cinchonine primary amine catalyst was developed. It is noteworthy that cinchonine primary amine can dual activate substrates through H-bond activation and thus promote the reaction. We applied step-by-step-strategy to resolve some problems in the Mannich reactions and did some instructive explorations in Lewis acid catalysis, Brønst acid catalysis, noncovalently supported heterogeneous chiral primary amine catalysis and chiral primary amine as hydrogen-bond catalysis.

Noncovalent functionalization of multiwalled carbon nanotubes: Application in hybrid nanostructures

We developed a reproducible, noncovalent strategy to functionalize multiwalled carbon nanotubes (MWNTs) via embedding nanotubes in polysiloxane shells. (3-Aminopropyl)triethoxysilane molecules adsorbed to the nanotube surfaces via hydrophobic interactions are polymerized simply by acid catalysis and form a thin polysiloxane layer. On the basis of the embedded MWNTs, negatively charged gold nanoparticles are anchored to the nanotube surfaces via electrostatic interactions between the protonated amino groups and the gold nanoparticles. Furthermore, these gold nanoparticles can further grow and magnify along the nanotubes through heating in HAuCl4 aqueous solution at 100 degrees C; as a result these nanoparticles are joined to form continuous gold nanowires with MWNTS acting as templates.

Convergence of products from Povarov and von Miller reactions: approaches to helquinoline

Yttrium triflate or triflic acid catalysed Povarov reaction of methyl anthranilate with ethyl vinyl ether, both as aldehyde surrogate and as alkene, gave the desired 2-methyl-4-ethoxytetrahydroquinoline diastereoisomers as the major products along with four component coupling von Miller adducts. A proton NMR-study, using yttrium triflate as catalyst, revealed that the cis-diastereoisomers were the initial major products in both the Povarov and von Miller reactions but that these isomerised to the trans-diastereoisomers under the reaction conditions. Two distinct pathways for forming von Miller adducts were uncovered with the initial Povarov products being converted to von Miller adducts under the reaction conditions. Replacement of the 4-ethoxy with a 4-methoxy group under acidic conditions gave predominantly the trans-diastereoisomer, which was subsequently converted to a cis/trans mixture of the tetrahydroquinoline antibiotic helquinoline. It was also possible to convert the von Miller products to Povarov products under acidic conditions

Catalytic routes to convert saccharides to furanic aldehydes

The conversion of plant biomass-derived carbohydrates (preferably non-edible) into added-value products is envisaged to be at the core of the future biorefineries. Carbohydrates are the most abundant natural organic polymers on Earth. This work deals with the chemical valorisation of plant biomass, focusing on the acid-catalysed conversion of carbohydrates (mono and polysaccharides) to furanic aldehydes, namely 2-furaldehyde (Fur) and 5-hydroxymethyl-2-furaldehyde (Hmf), which are valuable platform chemicals that have the potential to replace a variety of oil derived chemicals and materials. The investigated reaction systems can be divided into two types depending on the solvent used to dissolve the carbohydrates in the reaction medium: water or ionic liquid-based systems. The reaction temperatures were greater than 150 ºC when the solvent was water, and lower than 150 º C in the cases of the ionic liquid-based catalytic systems. As alternatives to liquid acids (typically used in the industrial production of Fur), solid acid catalysts were investigated in these reaction systems. Aiming at the identification of (soluble and insoluble) reaction products, complementary characterisation techniques were used namely, FT-IR spectroscopy, liquid and solid state NMR spectroscopy, TGA, DSC and GC´GC-ToFMS analyses. Complex mixtures of soluble reaction products were obtained and different types of side reactions may occur. The requirements to be put on the catalysts for these reaction systems partly depend on the type of carbohydrates to be converted and the reaction conditions used. The thermal stability is important due to the fact that formation of humins and catalyst coking phenomena are characteristically inherent to these types of reactions systems leading to the need to regenerate the catalyst which can be effectively accomplished by calcination. Special attention was given to fully inorganic nanoporous solid acids, amorphous or crystalline, and consisting of nano to micro-size particles. The investigated catalysts were silicoaluminophosphates, aluminosilicates and zirconium-tungsten mixed oxides which are versatile catalysts in that their physicochemical properties can be fine-tuned to improve the catalytic performances in the conversion of different substrates (e.g. introduction of mesoporosity and modification of the acid properties). The catalytic systems consisting of aluminosilicates as solid acids and water as solvent seem to be more effective in converting pentoses and related polysaccharides into Fur, than hexoses and related polysaccharides into Hmf. The investigated solid acids exhibited fairly good hydrothermal stabilities. On the other hand, ionic liquid-based catalytic systems can allow reaching simultaneously high Fur and Hmf yields, particularly when Hmf is obtained from D-fructose and related polysaccharides; however, catalyst deactivation occurs and the catalytic reactions take place in homogeneous phase. As pointed out in a review of the state of the art on this topic, the development of truly heterogeneous ionic liquid-based catalytic systems for producing Fur and Hmf in high yields remains a challenge.