Biodiesel Production from Vegetable Oils and Animal Fat over Solid Acid Double-Metal Cyanide Catalysts

Biodiesel comprises of fatty acid alkyl esters prepared from vegetable oils or animal fat by esterification/transesterification with short-chain alcohols (methanol or ethanol, for example). It is a biodegradable renewable fuel. Its production is growing exponentially due to greater concerns about environmental protection and depletion of fossil fuel resources. Further, its production from non-edible oils and animal fat is more desirable than from edible oils due to lower cost of non-edible feedstocks and elimination of food verses fuel issues. Solid acid catalysts are ideal for conversion of such low-grade oils to biodiesel. Biodiesel from non-edible oils can be produced by two methods: (1) simultaneous esterification of fatty acids and transesterification of fatty acid glycerides and (2) hydrolysis of glycerides followed by esterification. This account reports the catalytic performance of solid, Fe–Zn double-metal cyanide (DMC) complexes and other acid catalysts in these transformations for biodiesel production. The factors influencing the catalytic performance of the solid acid catalysts in biodiesel production are discussed.     

酸性离子液体催化油酸酯化合成生物柴油简

酸性离子液体具有催化活性好、选择性高及易于回收等优点,是一种应用前景非常好的环境友好的酸性催化剂,在生物柴油合成反应中具有重大的理论意义和应用价值. 本文以油酸和甲醇为原料,探讨了7种不同酸性离子液体在生物柴油合成反应中的催化效应. 研究表明,离子液体酸性越强,催化酯化活性越高;引入磺酸基团可大大增强离子液体Brönsted酸性,使其在酯化反应中发挥溶剂/催化剂的双重作用,促进酯化反应向产物方向进行,达到高产率,因而1-丁基磺酸-3-甲基咪唑硫酸氢盐（[BHSO₃MIM]HSO₄）催化效果最好. 此外,系统研究了[BHSO₃MIM]HSO₄催化油酸与甲醇酯化反应,并采用响应面法优化了反应条件. 结果发现,该反应的最适醇酸摩尔比、催化剂用量、反应温度及反应时间分别为4：1,10%（基于油酸的质量）,130 ℃和4 h;在此条件下,生物柴油产率为97.7%. [BHSO₃MIM]HSO₄连续使用10批次后,仍能保持初始催化活性的95.6%,表现出极好的操作稳定性. 另外,利用该离子液体催化游离脂肪酸含量为72%的废油脂生产生物柴油,反应6 h可获得产率94.9%. 可见,[BHSO₃MIM]HSO₄在酯化生产生物柴油方面具有巨大的应用潜力.     

Developments in Titanium-Based Alkali and Alkaline Earth Metal Oxide Catalysts for Sustainable Biodiesel Production: A Review

Biodiesel represents a biodegradable, environmentally friendly, and renewable alternative to fossil fuels. Despite more than three decades of research, significant obstacles still hinder the widespread production of biodiesel. This current review elucidates both the potential and the existing challenges associated with homogeneous and heterogeneous catalysts in catalyzing biodiesel production, with a particular focus on alkali analogues, alkaline earth metal oxides, and titania-based catalysts. In particular, a comprehensive analysis is presented concerning alkali and alkaline earth-based titania (TiO₂) catalysts. Among these, the alkaline earth metal oxides, including lithium, calcium, and strontium when combined with titanium-based catalysts, exhibit superior catalytic activity compared to other metal oxides, owing to their heightened basicity. Consequently, this review offers a thorough and up-to-date insight into the potential of titania-based heterogeneous catalysts for advancing biodiesel production.     

Soybean biodiesel methyl esters,free glycerin and acid number quantification by 1H nuclear magnetic resonance spectroscopy

Production of alternative fuels, such as biodiesel, from transesterification of vegetable oil driven by heterogeneous catalysts is a promising alternative to fossil diesel. However, achieving a successful substitution for a new renewable fuel depends on several quality parameters. ¹H NMR spectroscopy was used to determine the amount of methyl esters, free glycerin and acid number in the transesterification of soybean oil with methanol in the presence of hydrotalcite‐type catalyst to produce biodiesel. Reaction parameters, such as temperature and time, were used to evaluate soybean oil methyl esters rate conversion. Temperatures of 100 to 180 °C and times of 20 to 240 min were tested on a 1 : 12 molar ratio soybean oil/methanol reaction. At 180 °C/240 min conditions, a rate of 94.5 wt% of methyl esters was obtained, where free glycerin and free fatty acids were not detected. Copyright © 2012 John Wiley & Sons, Ltd.     

取代硫酸、氢氟酸等液体酸催化剂的途径

高效固体酸催化剂无论对现有工业生产, 还是从环保考虑, 都是十分重要的。特别是对那些使用液体酸诸如H₂SO₄、HF 和A lCl₃ 等为催化剂的液相酸工艺。近年来考虑到均相和多相酸催化反应中起决定作用的酸位(中心) 之间的类似性, 根据近代均相酸催化理论, 通过对不同酸位(L 酸、B 酸、超强酸) 本质的分析, 对强酸催化剂提出了一个统一的酸结构模型。以此为依据, 可对一些强酸催化剂进行剪裁。     

Esterification of Oleic Acid to Produce Biodiesel over 12-Tungstophosphoric Acid Anchored Two-dimensional Zeolite

Biodiesel has emerged as a non-toxic, biodegradable, and renewable fuel substitute that can be readily produced via the esterification reaction of free fatty acids. The present work explores the potential of 12-tungstophosphoric acid(TPA) anchored two-dimensional(2D) ITQ-2 zeolite(TPA/ITQ-2) as heterogeneous acid catalysts for biodiesel production. TPA/ITQ-2 material was prepared by swelling, delamination, and subsequent wetness incipient impregnation approach. The prepared catalysts were comprehensively characterized by powder X-ray diffraction, N₂ adsorption/desorption, temperature-programmed desorption of ammonia, flou-rier transform infrared spectroscopy, and transmission electron microscopy. The catalytic activity of TPA/ITQ-2 for biodiesel production was evaluated by the esterification reaction of oleate acid with methanol. Process parameters, such as reactant molar ratio and TPA loading were optimized. Due to the superior mass transfer and adequate stable acid sites, 2D TPA/ITQ-2 showed a higher catalytic activity and a better recyclable stability than the 3D and layered TPA/zeolites. This work will provide new opportunities for the design of 2D zeolite-based acid catalysts for biodiesel production.     

Selective Synthesis by Use of Lewis Acids in the Presence of Organocopper and Related Reagents. New Synthetic Methods (61)

Organometallic compounds with pronounced nucleophilicity such as organocopper and organolithium compounds, and powerful electrophiles, such as BF₃ and AlCl₃, are generally thought to be incompatible under normal, homogeneous reaction conditions. As a matter of course, it is anticipated that the two species cannot coexist and undergo transmetalation reactions. To our surprise, however, RCu and BF₃ are compatible at low temperature. RCu·BF₃ and related organocopper-Lewis acid reagents exhibit new and unique reactivities and selectivities: in conjugate additions, e.g., not only activation but also high regio-, stereo-, and chemo-selectivity as well as very high asymmetric induction is observed; allylic derivatives are alkylated regioselectively, and reaction towards carbonyl groups, imines, epoxides, aziridines, ethers, acetals, orthoformates, and pyridinium salts is in each case found to be selective. RLi·BF₃ and related organolithium-Lewis acid reagents also exhibit noteworthy selectivities and reactivities. These complex reagents are utilized in the key steps of the total synthesis of many important natural products, such as certain terpenes, steroids, and alkaloids.     

Synthesis of micronized CaO assisted by NH4HCO3 with Ca(OH)2 and its application in heterogeneously catalyzing transesterification reaction for producing biodiesel

Micronized CaO with pores was synthesized by calcining the reaction product CaCO₃ from NH₄HCO₃ and Ca(OH)₂. Scanning electron microscopy, X‐ray diffraction, energy dispersive X‐ray spectroscopy, X‐ray fluorescence, Fourier transform infrared spectroscopy, and Brunauer–Emmett–Teller analysis were used to characterize CaO, which confirmed that after calcining at 800°C for 2 hr, CaCO₃ was completely converted into porous micronized CaO with a surface area of about 7.295 m²/g and a particle size of 0.5–1.5 μm. The porous CaO microparticles were used as heterogeneous catalysts for producing biodiesel from transesterification of soybean oil and methanol. The influences of reaction time, calcined temperature, and reusability of CaO were explored. The experiments showed that CaO has high catalytic activity for transesterification reaction, and the yield of biodiesel reaches more than 98% under the conditions of methanol/oil mole ratio of 9, and the catalyst amount (catalyst/oil) of 3% after reaction for 2.5 hr. The CaO catalyst can be recycled easily and it also has the advantage of low pollution. Simple synthetic route, low cost, high catalytic activity, good reusability, and great potential for industrialization are the advantages of the porous micronized CaO catalyst that was proposed in this work.     

Silica gel and polystyrene supported aluminum chloride as heterogeneous catalysts for the preparation of α‐aminophosphonates

Silica gel supported aluminum chloride (SiO₂‐AlCl₃) and cross‐linked polystyrene‐supported aluminum chloride (PS‐AlCl₃) are environment‐ friendly heterogeneous catalysts for the condensation of amines and aldehydes with diethyl phosphite to afford α‐aminophosphonates. These solid acid catalysts are stable (as bench top catalysts) and can be easily recovered and reused without appreciable change in their efficiency. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:418–422, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20629     

Biodiesel production via esterification of oleic acid catalyzed by MnO2@Mn(btc) as a novel and heterogeneous catalyst

The main objective of this study is to develop efficient and environmentally benign heterogeneous catalysts for biodiesel production. For this purpose, a heterogeneous MnO₂@Mn(btc) catalyst was prepared by the solvothermal method, and the prepared catalyst was tested for the esterification of oleic acid. Various techniques such as X‐ray diffraction, scanning and transmission electron microscopy, Brunauer–Emmett–Teller (BET) method, infrared spectroscopy, thermogravimetry, and NH₃‐TPD (temperature programmed desorption) analysis were employed for the characterization of the solid catalyst. The solid catalyst with MnO₂@Mn(btc) loading of 15% showed high catalytic activity and long durability in the esterification of oleic acid, in which the fatty acid methyl ester yield reached 98% consecutively for at least five cycles under mild conditions.     

[Bmim]BF4-immobilized rhenium-catalyzed highly efficient oxygenation of aldimines to oxaziridines using solid peroxides as oxidants

Various rhenium-based catalysts immobilized in [bmim]BF₄ were found to be efficient for oxygenation of various aldimines to the corresponding oxaziridines in excellent yields under mild conditions using solid peroxides like UHP, SPC and SPB as oxidants. Among the various rhenium-based catalysts studied, MTO was found to be most efficient. The reusability and recyclability of MTO immobilized in [bmim]BF₄ was established by using it for three subsequent cycles for oxygenation of benzylidine-tert-butylamine using UHP as oxidant.     

Clean synthesis of biodiesel over solid acid catalysts of sulfonated mesopolymers

FDU-15-SO₃H, a solid acid material prepared from the sulfonation of FDU-15 mesoporous polymer, has been demonstrated to serve as an efficient catalyst in the esterification of palmitic acid with methanol as well as in the transesterification of fatty acid-edible oil mixture. FDU-15-SO₃H achieved an acid conversion of 99.0% when the esterification was carried out at 343 K with a methanol/palmitic acid molar ratio of 6:1 and 5 wt% catalyst loading. It was capable of giving 99.0% yield of fatty acid methyl esters (FAME) when the transesterification of soybean oil was performed at 413 K and the methanol/oil weight ratio of 1:1. FDU-15-SO₃H was further applied to the transesterification/esterification of the oil mixtures with a varying ratio of soybean oil to palmitic acid, which simulated the feedstock with a high content of free fatty acids. The yield of FAME reached 95% for the oil mixtures containing 30 wt% palmitic acid. This indicated the sulfonated mesopolymer was a potential catalyst for clean synthesis of fuel alternative of biodiesel from the waste oil without further purification.     

A quasi-stable molybdenum sub-oxide with abundant oxygen vacancies that promotes CO2 hydrogenation to methanol

Production of methanol from anthropogenic carbon dioxide (CO₂) is a promising chemical process that can alleviate both the environmental burden and the dependence on fossil fuels. In catalytic CO₂ hydrogenation to methanol, reduction of CO₂ to intermediate species is generally considered to be a crucial step. It is of great significance to design and develop advanced heterogeneous catalysts and to engineer the surface structures to promote CO₂-to-methanol conversion. We herein report an oxygen-defective molybdenum sub-oxide coupled with Pt nanoparticles (Pt/H_xMoO_3−y) which affords high methanol yield with a methanol formation rate of 1.53 mmol g_-cat⁻¹ h⁻¹ in liquid-phase CO₂ hydrogenation under relatively mild reaction conditions (total 4.0 MPa, 200 °C), outperforming other oxide-supported Pt catalysts in terms of both the yield and selectivity for methanol. Experiments and comprehensive analyses including in situ X-ray absorption fine structure (XAFS), in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and density functional theory (DFT) calculations reveal that both abundant surface oxygen vacancies (V_O) and the redox ability of Mo species in quasi-stable H_xMoO_3−y confer the catalyst with enhanced adsorption and activation capability to subsequently transform CO₂ to methanol. Moreover, the Pt NPs act as H₂ dissociation sites to regenerate oxygen vacancies and as hydrogenation sites for the CO intermediate to finally afford methanol. Based on the experimental and computational studies, an oxygen-vacancy-mediated “reverse Mars–van Krevelen (M–vK)” mechanism is proposed. This study affords a new strategy for the design and development of an efficient heterogeneous catalyst for CO₂ conversion.

Oxygen-defective molybdenum sub-oxide coupled with Pt nanoparticles affords high methanol yield in liquid-phase CO₂ hydrogenation via reverse Mars–van Krevelen mechanism.     

Experimental comparison of performance and emission characteristics of 4-stroke CI engine operated with Roselle and Jatropha biodiesel blends

The environmental degradation, combined with the continuous depletion of the world's fossil fuel reserves, has forced the search for alternative fuels. This study was performed to investigate the performance of novel biodiesels in the CI engine. The experiments were performed at three different compressions ratios (16:1, 17:1, 18:1) and four loading conditions (25%, 50%, 75%, 100%). Different types of fuels such as jatropha biodiesel (JB), roselle biodiesel (RB), and ternary biodiesel (TB) were prepared and analyzed. The thermal performance of different fuels was analyzed in terms of brake thermal efficiency (BTE), brake specific fuel consumption (BSFC), and exhaust gas temperature (EGT). The emission characteristics such as CO₂ emission, NO_x emission, and smoke emission were analyzed for all types of fuels. The results of these fuels in the engine were compared with mineral diesel (MD). The BTE was increased with increasing compression ratios and loads for all types of fuels. The BSFC was increased with increasing compression ratios but decreased with increasing loads. The increase in emission of NO_x was observed at higher compression ratios and loads. However, the CO₂ emission was decreased at higher loads and lower compression ratio. The performance curves achieved with a 20% jatropha biodiesel blend showed results that were approximate to those obtained with pure MD. The comparative analysis between different fuels showed that JB exhibit higher thermal performance as compared to other biodiesels. Therefore, JB can be a better alternative to conventional fuel.     

Application of a Chitosan-Immobilized Talaromyces thermophilus Lipase to a Batch Biodiesel Production from Waste Frying Oils

Waste frying oil, which not only harms people’s health but also causes environmental pollution, can be a good alternative to partially substitute petroleum diesel through transesterification reaction. This oil contained 8.8 % of free fatty acids, which cause a problem in a base-catalyzed process. In this study, synthesis of biodiesel was efficiently catalyzed by the covalently immobilized Talaromyces thermophilus lipase and allowed bioconversion yield up to 92 % after 24 h of reaction time. The optimal molar ratio was four to six parts of methanol to one part of oil with a biocatalyst loaded of 25 wt.% of oil. Further, experiments revealed that T. thermophilus lipase, immobilized by a multipoint covalent liaison onto activated chitosan via a short spacer (glutaraldehyde), was sufficiently tolerant to methanol. In fact, using the stepwise addition of methanol, no significant difference was observed from the one-step whole addition at the start of reaction. The batch biodiesel synthesis was performed in a fixed bed reactor with a lipase loaded of 10 g. The bioconversion yield of 98 % was attained after a 5-h reaction time. The bioreactor was operated successfully for almost 150 h without any changes in the initial conversion yield. Most of the chemical and physical properties of the produced biodiesel meet the European and USA standard specifications of biodiesel fuels.     

Production of Biodiesel Through Esterification Reaction Using Choline Exchanging Polytungstoboronic Acids as Temperature-Responsive Catalysts

High proton content polytungstoboronic acid H₇BW₁₁TiO₄₀ (abbreviated as H₇BW₁₁Ti) had been prepared through titanium mono-substituted of H₅BW₁₂O₄₀, which was evaluated in esterification of palmitic acid with methanol. H₇BW₁₁Ti could promote esterification reaction with almost 100% conversion of 417 mol/mol h TOF within very short time of 1 h at methanol/acid ratio of 25:1 under reaction temperature of 65?°C, which was attributed to the higher Brønsted acidity and cooperation of Lewis acidic site generating from Ti substituent. Limitation by its homogeneous performance, solidification of H₇BW₁₁Ti was designed via partial exchanging protons with choline cation (abbreviated as Ch⁺) to prepare a series of [(CH₃)₃NCH₂CH₂OH]_nH_7?nBW₁₁TiO₄₀ (abbreviated as Ch_nH_7?nBW₁₁Ti, n?=?0?~?7). Among all solid catalysts, the highest efficiency had been achieved by with 99.0% conversion and 429 mol/mol h TOF within 50 min at 65?°C at methanol/acid ratio of 15:1. The comparable activity was attributed to the cooperation of Ch⁺—self-assembling to form nanoreactor with amphiphilic surrounding to concentrate substrates and to resist to water-poison, temperature-responsive property to control form changing between heterogeneous to homogenous. This temperature-responsive HPA catalyst was available for production of biodiesel through esterification reaction. In addition, Separation of such heteropolyacid catalysts was easy by the lowering the reaction temperature to room temperature without appreciable loss of its high performance, which were reused for more than six times.     

Reactivity of Metal Catalysts in Glucose–Fructose Conversion

A joint experimental and computational study on the glucose–fructose conversion in water is reported. The reactivity of different metal catalysts (CrCl₃, AlCl₃, CuCl₂, FeCl₃, and MgCl₂) was analyzed. Experimentally, CrCl₃ and AlCl₃ achieved the best glucose conversion rates, CuCl₂ and FeCl₃ were only mediocre catalysts, and MgCl₂ was inactive. To explain these differences in reactivity, DFT calculations were performed for various metal complexes. The computed mechanism consists of two proton transfers and a hydrogen‐atom transfer; the latter was the rate‐determining step for all catalysts. The computational results were consistent with the experimental findings and rationalized the observed differences in the behavior of the metal catalysts. To be an efficient catalyst, a metal complex should satisfy the following criteria: moderate Brønsted and Lewis acidity (pK_a=4–6), coordination with either water or weaker σ donors, energetically low‐lying unoccupied orbitals, compact transition‐state structures, and the ability for complexation of glucose. Thus, the reactivity of the metal catalysts in water is governed by many factors, not just the Lewis acidity.     

Diastereoselective, large scale synthesis of β-amino acids via asymmetric enamide hydrogenation as α2δ ligands for the treatment of generalized anxiety disorder and insomnia

The syntheses of β-amino acids 1 and 2 are presented by means of an alternative route to the asymmetric Michael-addition route reported in the preceding article. These two compounds, which bind to the α2δ subunit of calcium channels and have important medical applications, have been prepared on multi-kilogram scale in our pilot plant through a new approach that introduces the chirality at the β-carbon via asymmetric hydrogenation of an enamide precursor. Two Rh-based catalysts, (R)-mTCFP-Rh(COD)BF₄ and (R)-binapine-Rh(COD)BF₄, were found to be superior in this transformation and gave very high diastereoselectivities. The process development for catalyst selection is described.     

Microwave-Assisted Ionic Liquid-Catalyzed Selective Monoesterification of Alkylphosphonic Acids—An Experimental and a Theoretical Study

It is well-known that the P-acids including phosphonic acids resist undergoing direct esterification. However, it was found that a series of alkylphoshonic acids could be involved in monoesterification with C₂–C₄ alcohols under microwave (MW) irradiation in the presence of [bmim][BF₄] as an additive. The selectivity amounted to 80–98%, while the isolated yields fell in the range of 61–79%. The method developed is a green method for P-acid esterification. DFT calculations at the M062X/6–311+G (d,p) level of theory (performed considering the solvent effect of the corresponding alcohol) explored the three-step mechanism, and justified a higher enthalpy of activation (160.6–194.1 kJ·mol⁻¹) that may be overcome only by MW irradiation. The major role of the [bmim][BF₄] additive is to increase the absorption of MW energy. The specific chemical role of the [BF₄] anion of the ionic liquid in an alternative mechanism was also raised by the computations.     

η3-Allylnickel alkoxides and their use as homogeneous and heterogeneous catalysts for the dimerization of olefins

η³-Allylnickel alkoxides {η³-C₃H₅NiOR}₂ (R = Me, Et, i-Pr, Ph, SiPh₃) may be activated by gaseous boron trifluoride (BF₃) to give active catalysts for the dimerization of propene in homogeneous phase. In CH₂Cl₂ at ?20 °C catalytic turnover numbers of 5000 mol propene(mol Ni)^?1h^?1 were measured. The nature of the OR group influences both the catalytic activity and the oligomerization product distribution. The ratio of methylpentenes to dimethylbutenes in the dimer fraction may be controlled by the presence of additional phosphine ligands at the nickel atom. The nickel alkoxide precursor was heterogenized on alumina to give {Al₂O₃}–O–Ni–(η³-C₃H₅). Subsequent activation using gaseous BF₃ generates a powerful heterogeneous olefin dimerization catalyst which converts 50 × 10³ mol propene (mol Ni)^?1 at ?10° to ?5°C in a batchwise process and 143 × 10³ mol propene (mol Ni)^?1 continuously to give 75% dimers and 25% higher oligomers. The solvent-free treatment of oxide supports, e.g. alumina or silica, with gaseous BF₃ produces strong ‘solid acids’. The activated hydroxyl groups on the support surface serve as effective anchor sites for organometallic complexes to form heterogenous catalysts. By reaction of Ni(cod)₂ with {Al₂O₃}O(BF₃)H or {SiO₂}O(BF₃)H, η¹, η²-cyclo-octenylnickel–O fragments may be fixed to the surface. In the absence of halogenated solvents, the resulting catalysts, e.g. {SiO₂}O–(BF₃)–Ni–(η¹, η²-C₈H₁₃), dimerize propene continuously at +5°C at the rate of 800 × 10³ mol liquid propene (mol Ni)^?1.