Production of octyl levulinate biolubricant over modified H-ZSM-5: Optimization by response surface methodology

The present study highlighted the use of modified H-ZSM-5 (Meso-HZ-5) as heterogeneous catalyst for the synthesis of octyl levulinate biolubricant by catalytic esterification of biomass derived renewable levulinic acid (LA) with n-octanol. The process variables such as catalyst loading (X₁), n-octanol to LA molar ratio (X₂) and reaction temperature (X₃) were optimized through response surface methodology (RSM), using Box-Behnken model. Analysis of variance was performed to determine the adequacy and significance of the quadratic model. The yield of octyl levulinate was obtained to be 99% at optimum process parameters. The developed quadratic model was found to be adequate and statistically accurate with correlation value (R²) of 0.9971 to predict the yield of octyl levulinate biolubricant. The study was also extended on the validation of theoretical and experimental data, including catalyst reusability.     

稻壳炭基固体酸催化剂的制备及其催化酯化反应性能

以热解稻壳炭为原料, 浓硫酸为磺化剂制备了固体酸催化剂. 采用X射线衍射、X射线光电子能谱、元素分析、孔结构分析和热重-质谱联用等手段对其进行了表征. 以油酸和甲醇的酯化为探针反应, 考察了磺化温度和时间对催化剂活性的影响, 探讨了反应条件对油酸转化率的影响, 并对所制催化剂的稳定性进行了研究. 结果表明, 制备该催化剂的适宜磺化温度和时间分别为90℃和0.25 h, 在该条件下制得的催化剂为无定形碳结构, 磺酸基密度为0.7 mmol/g. 该催化剂表现出较高的催化酯化反应活性, 在催化剂用量为5%、甲醇/油酸摩尔比为4、酯化温度和时间分别为110℃和2 h的条件下, 油酸的酯化率可达98.7%. 该催化剂具有较好的稳定性, 经7次连续反应后, 油酸的酯化率仍可达96.0%.     

Kinetics,mass transfer,and thermodynamic and statistical modeling study for esterification of valeric acid with n‐butanol: Homogeneous and heterogeneous catalysis

The esterification of valeric acid with n‐butanol was studied with homogeneous and heterogeneous catalysts. The activity and performance of homogeneous p‐toluenesulfonic acid and heterogeneous cation exchange resin catalysts Amberlyst 36, Indion 190, and Amberlite IRC‐50 were evaluated. The pseudo‐homogeneous kinetic model was used to investigate the kinetic parameters of homogeneous‐ and heterogeneous‐catalyzed esterification. The UNIFAC (universal functional activity coefficient) approach was used to study the nonideality of the esterification reaction. The reaction was statistically modeled and optimized by the application of response surface methodology. The effects of independent variables such as reaction temperature, initial molar ratio, and catalyst loading on the conversion of valeric acid were investigated. The optimized conditions for the esterification reaction catalyzed by Amberlyst‐36 were found as temperature 360.4 K, initial molar ratio 3.8, and catalyst loading 6.7 wt%. The predicted conversion (89%) at these optimized conditions is in good agreement with the experimental conversion (87.3 ± 1.6%).     

Esterification of caprylic acid with alcohol over nano-crystalline sulfated zirconia

The catalytic activity of nano-crystalline sulfated zirconia catalyst, prepared by sol–gel method and characterized by various analytical tools, was evaluated for the esterification of caprylic acid with different short chain alcohols. The lower concentration of catalyst (0.5 wt%) exhibited 96–98% conversion of caprylic acid with methanol and 100% selectivity for methyl caprylate at 60 °C. The conversion was decreased with increasing carbon chain of alcohols namely with ethanol, n-propanol and n-butanol at 60 °C but increased significantly (91–98%) at higher reaction temperature. The selectivity for respective alkyl caprylate was observed to be 100% irrespective of the alcohol used. The activity of the catalyst was slightly decreased with successive five reaction cycles due to the water formed during the reaction.     

Recyclable CuMgAl hydrotalcite for oxidative esterification of aldehydes with alkylbenzenes

A series of hydrotalcite-like compounds with various Cu:Mg:Al molar ratios were prepared by the co-precipitation method. The catalytic performance for oxidative esterification of aldehydes was investigated. X-ray diffraction, N₂ adsorption–desorption (BET), hydrogen temperature-programmed reduction (H₂-TPR), X-ray photoelectron spectroscopy, the scanning electron microscope (SEM), the transmission electron microscope and atomic absorption spectrometry were used to characterize the catalysts. The results showed that the benzyl benzoate product was obtained in good to excellent yield using tert-butyl peroxybenzoate as oxidant at 90°C under air atmosphere over Cu₂Mg₁Al₁-LDH catalyst. The catalyst can be recovered and used with 45% conversion after recycling five times. The oxidative esterification reaction in the heterogeneous system is environmentally friendly.

The Cu₂Mg₁Al₁-LDH catalyst prepared by co-precipitation method showed high catalytic activity for oxidative esterification of aldehydes. 81.0% yield of benzyl benzoate with benzaldehyde and toluene as reactants was obtained using tert-butyl peroxybenzoate as oxidant at 90°C under air atmosphere over Cu₂Mg₁Al₁-LDH catalyst. The catalyst can be recovered and used with 45% conversion after recycling five runs. The oxidative esterification reaction in the heterogeneous system is environmentally friendly.     

Preparation and characterization of Ag@AgCl-doped fly ash cenospheres for photocatalytic applications

A plasmonic photocatalyst composite based on Ag@AgCl and fly ash cenospheres was successfully prepared through a two-step method. X-ray diffraction analysis, scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy, and diffuse reflectance ultraviolet–visible spectroscopy were used to determine the structure and optical properties of the Ag@AgCl-doped fly ash cenospheres (denoted Ag@AgCl/FAC). SEM micrographs showed that Ag@AgCl was well deposited on the surface of the fly ash cenospheres. Photocatalytic experiment results showed that the degradation ratio increased with increasing dosage of Ag@AgCl/fly ash cenospheres; proper concentration of pollutant was important for the photocatalytic reaction for given amount of catalyst. Moreover, improved degradation of rhodamine B was observed at acidic conditions under visible-light irradiation. This excellent catalytic ability is mainly attributed to the formation of Ag nanoparticles on the surface of the fly ash cenospheres and the high separation efficiency of photoelectron–hole pairs.     

Production of octyl levulinate biolubricant over modified H-ZSM-5： Optimization by response surface methodology

The present study highlighted the use of modified H-ZSM-5 （Meso-HZ-5） as heterogeneous catalyst for the synthesis of octyl levulinate biolubricant by catalytic esterification of biomass derived renewable levulinic acid （LA） with n-octanol. The process variables such as catalyst loading （X1）, n-octanol to LA molar ratio （X2） and reaction temperature （X3） were optimized through response surface methodology （RSM）, using Box-Behnken model. Analysis of variance was performed to determine the adequacy and significance of the quadratic model. The yield of octyl levulinate was obtained to be 99% at optimum process parameters. The developed quadratic model was found to be adequate and statistically accurate with correlation value （R2） of 0.9971 to predict the yield of octyl levulinate biolubricant. The study was also extended on the validation of theoretical and experimental data, including catalyst reusability.     

Aluminum phosphate-based solid acid catalysts: Facile synthesis,characterization and their application in the esterification of propanoic acid with n-butanol

Novel solid acid catalysts synthesized from aluminum phosphate were prepared via a precipitation method and a subsequent sulfating treatment. Their catalytic performances for the esterification of propanoic acid with n-butanol were investigated. The as-prepared catalysts were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption–desorption, Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), temperature programmed desorption of ammonia (NH₃-TPD), infrared spectroscopy of adsorbed pyridine, and other techniques. Experimental results of esterification reactions indicated that the calcination temperature can significantly affect the catalytic performances and the catalyst calcined at 500 °C (SO₄²⁻/AlPO₄-500) exhibited the highest activity. The effects of different reaction conditions including reaction time, reaction temperature, catalyst amount and alcohol/acid molar ratio were studied in detail. The maximum propanoic acid conversion of 91% was achieved under optimum reaction conditions. Furthermore, the as-prepared SO₄²⁻/AlPO₄-500 catalysts were tested for their reusability in repeated reaction cycles and could be effectively regenerated by a simple reactivation method.     

Kinetics of catalyzed esterification of acetic acid with n-butanol using carbonized agro-waste

The objective of this research work was to investigate the kinetics of esterification of acetic acid with n-butanol through the variation of experimental parameters. The reaction mixture was catalyzed heterogeneously by a sulfonated catalyst in batch mode of operation. The catalyst was prepared from abundantly available agro-waste, Cajanus cajan husk by chemical activation process, which produces a carbon-based solid catalyst with high surface area. The catalyst was characterized by a Brunauer-Emmet-Teller surface analyzer and Fourier transform infrared spectroscopy to know the surface morphology. Process parameters such as contact time, reaction temperature, and catalyst loading, which can influence the extent of conversion of reactants, were studied. Furthermore, the kinetic investigation was also carried out to estimate the kinetic parameters for uncatalyzed and catalyzed reaction using the second-order pseudo-homogeneous (P-H), Eley-Rideal (E-R), and Langmuir-Hinshelwood (LH) kinetic models for this research work. The kinetic parameters such as activation energy, preexponential factor, and the thermodynamic parameters such as enthalpy and entropy were estimated for uncatalyzed and catalyzed reactions using these three models. The process conditions were optimized for catalyzed and uncatalyzed reactions to obtain the maximum product yield by minimizing root mean square error of each experimental data using the MS-excel solver tool. Thus, this study reveals the high potential of an agro-waste, Cajanus cajan husk as raw material for the synthesis of catalyst. The results show that the E-R model is more appropriate for predicting the dynamic data of an esterification reaction, as the forward rate of reaction estimated using the E-R model are more modified than P-H and L-H models.     

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.     

Optimization of process conditions for biodiesel production over CaO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZrO<Subscript>2</Subscript> catalyst using response surface methodology

CaO–Al₂O₃/ZrO₂ mixed oxide catalyst was prepared using free-solvent method. The catalyst was characterized using X-ray diffraction, BET surface area, acidity index (obtained by titration method), and scanning electron microscopy (SEM). With calcium aluminate and calcium zirconate been successfully formed, the mix exhibited small crystal size, high acidity, and large surface area, pore size, and pore volume, making it a catalyst of choice for biodiesel production. The activity of catalyst was evaluated in the course of esterification of oleic acid as well as transesterification of waste cooking oil (WCO) into biodiesel. Based on a four-variable central composite design (CCD), response surface methodology (RSM) was used to optimize effective variables on oleic acid conversion. The optimum yield of 94.68% was obtained at the following set of optimum conditions: reaction temperature of 120 °C, methanol/oleic acid molar ratio of 15.64, catalyst concentration of 2.94 wt%, and reaction time of 4 h; the result was in excellent agreement with the predicted values. Furthermore, under the optimum conditions, the catalyst succeeded to convert 93.48% of WCO into biodiesel.     

磁性纳米固体超强酸的合成、表征及性能

首次制备了SO₄^2-/Co_0.5Fe_2.5O₄-ZrO₂磁性固体超强酸,利用TEM,DTA,XRD和FTIR等手段研究了Co_0.5Fe_2.5O₄磁性基质对ZrO₂的粒子大小、晶化温度与结构的影响.考察了磁性固体超强酸的催化性能及催化剂的寿命、回收率和磁性.结果表明,引入Co_0.5Fe_2.5O₄磁性基质不但赋予催化剂以磁性,而且在固体超强酸形成过程中延迟了ZrO₂由四方晶相向单斜晶相的转变,有助于稳定样品表面的含硫物种,磁性固体超强酸对酯化反应具有较高的催化活性,可活化再生,并保持磁性.     

Trimerization of aldehydes with one α-hydrogen catalyzed by sodium hydroxide

Trimerization of 2-methylpropanal (isobutyraldehyde) is a simple and effective method to synthesize 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and 2,2,4-trimethyl-1,3-pentanediol-3-monoisobutyrate which are often used as film forming auxiliaries in paints. The use of solid sodium hydroxide as a catalyst provides an excellent yield of above 85 % after the optimization of the reaction time and the catalyst dosage. Furthermore, trimerization of four other aldehydes with one α-hydrogen catalyzed by solid sodium hydroxide can also take place and the yield of 1,3-diol monoesters reaches 50–70 %. Trimerization of aldehydes with one α-hydrogen can be explained by a three-step reaction mechanism: (i) aldol condensation of aldehyde; (ii) crossed Cannizzaro reaction; and (iii) esterification of carboxylic acid and alcohol.     

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.     

Mg–Al layered double hydroxide intercalated with manganese(III) 5,10,15,20‐tetrakis(4‐benzoate)porphyrinacetate as a highly reusable catalyst for epoxidation

The preparation and characterization are presented of a new catalytic material comprising Mg–Al layered double hydroxide and intercalated manganese(III) 5,10,15,20‐tetrakis(4‐benzoate)porphyrinacetate. Characterization was realized via various techniques. The prepared composite exhibited excellent catalytic activity in the selective epoxidation of various olefins with tetra‐n‐butylammonium hydrogen monopersulfate as an oxidant under mild reaction conditions. Furthermore, the catalytic system could be reused nine times without significant reduction in conversion percentage and any special care or additional treatment of the catalyst.     

Operando ATR-FTIR analysis of liquid-phase catalytic reactions: can heterogeneous catalysts be observed?

The applicability of a React-IR™ system, containing a diamond attenuated total reflection (ATR) crystal, in heterogeneous liquid-phase catalytic reactions was evaluated by analysis of the catalytic esterification of 1-octanol and hexanoic acid over a Nafion/silica catalyst in an open reflux configuration at atmospheric pressure. The reaction was performed in either cumene (at 427 K) or n-decane (at 447 K). The concentration profiles of the esterification reaction, as determined by this real-time in situ IR spectroscopic technique, are in qualitative and quantitative agreement with those determined by conventional off-line GC analysis.Interestingly, besides the bands assigned to the ester, alcohol, and acid, an additional strong and broad absorption band was observed at around 1100 cm⁻¹ in the spectra during the esterification reaction in cumene (at 427 K). It was assessed by variation of the reaction mixture that this band is a result of the reaction of silica with octanol, yielding Si–O–R functionalities. The relevance of this reaction for the kinetics of the studied catalytic esterification, is discussed. More importantly, the contribution of solid particles and leached species to the 1100 cm⁻¹ band is evaluated. Strong indications exist that solid catalyst particles are contributing to the spectra, implying that on-line analysis of intermediate species adsorbed on heterogeneous catalysts is in specific cases possible using the React-IR™ technique.     

磺酸型阳离子交换树脂催化合成肉桂酸甲酯

以磺酸型阳离子交换树脂为催化剂，由肉桂酸和甲醇合成了肉桂酸甲酯。考察了反应条件对酯化反应的影响和树脂的催化稳定性。结果表明，肉桂酸的转化率可达９５．５％，且催化剂的性能稳定。     

Characterization and catalytic performance of basaltic dust as an efficient catalyst in the liquid‐phase esterification of acetic acid with n‐butanol

Three natural basaltic samples were collected and used as efficient catalysts for the liquid‐phase synthesis of n‐butyl acetate. The samples were characterized by X‐ray fluorescence analysis (XRF), X‐ray diffraction (XRD), thermogravimetry (TG), differential thermal analysis (DTA), Fourier transform infrared (FT‐IR), scanning electron microscopy (SEM), and N₂ sorption. The acidity of the samples was determined using isopropanol dehydration, and the strength of the acid sites was measured using chemisorption of basic probes. The catalytic activity of the samples towards the esterification of acetic acid with n‐butanol was extensively examined. The influence of different parameters, such as the reaction refluxing time, molar ratio, catalyst loading, reusability, and calcination temperature, on the esterification reaction was studied in detail. The results revealed that all samples had high catalytic activity with a selectivity of 100% to n‐butyl acetate formation. In addition, the sample obtained from the top hill of Volcano had the highest activity with a 80% yield of n‐butyl acetate. Moreover, the significant catalytic performances were well correlated with the acidity of the samples and to the reaction rate constants.     

Sulfonated porous biomass-derived carbon with superior recyclability for synthesizing ethyl levulinate biofuel

The synthesis of ethyl levulinate (EL) via esterification of levulinic acid (LA) with ethanol, which can be derived from biomass, has become an attractive topic since EL can be applied in many fields, such as fuel additives for petroleum and biodiesel, food additives and fragrance. Herein, the sulfonated porous carbon catalysts derived from the rinds of corn stalk biomass wastes were prepared by using sulfuric acid and phosphoric acid as the sulfonating agent and activator, respectively. The preparation parameters were optimized based on the catalytic activity for LA esterification with ethanol and the acid density of the corresponding catalysts. Also, various reaction factors were optimized to improve the catalytic efficiency over the optimal sulfonated corn stalk-derived carbon (s-CSC). Under the conditions of reaction temperature 80 °C, catalyst dosage 5 wt%, ethanol-to-LA molar ratio 5.0:1 and reaction time 8 h, the LA conversion reached 94% and 93% catalyzed by s-CSC and the optimal porous catalyst (s-p-CSC), respectively. Noticeably, benefitting from the hierarchical porous structure with large surface area, s-p-CSC exhibited much better recyclability than s-CSC. This work offers a highly effective solid acid catalyst for the synthesis of biofuel.

     

Modulation of Self-Separating Molecular Catalysts for Highly Efficient Biomass Transformations

The energetically viable fabrication of stable and highly efficient solid acid catalysts is one of the key steps in large-scale transformation processes of biomass resources. Herein, the covalent modification of the classical Dawson polyoxometalate (POMs) with sulfonic acids (-SO₃H) is reported by grafting sulfonic acid groups on the POM's surface followed by oxidation of (3-mercaptopropyl)trimethoxysilane. The acidity of TBA₆-P₂W₁₇-SO₃H (TBA=tetrabutyl ammonium) has been demonstrated by using ³¹P NMR spectroscopy, clearly indicating the presence of strong Brønsted acid sites. The presence of TBA counterions renders the solid acid catalyst as a promising candidate for phase transfer catalytic processes. The TBA₆-P₂W₁₇-SO₃H shows remarkable activity and selectivity, excellent stability, and great substrate compatibility for the esterification of free fatty acids (FFA) with methanol and conversion into biodiesel at 70 °C with >98 % conversion of oleic acid in 20 min. The excellent catalytic performance can be attributed to the formation of a catalytically active emulsion, which results in a uniform catalytic behavior during the reaction, leading to efficient interaction between the substrate and the active sites of the catalyst. Most importantly, the catalyst can be easily recovered and reused without any loss of its catalytic activity owing to its excellent phase transfer properties. This work offers an efficient and cost-effective strategy for large-scale biomass conversion applications.