Kinetics of acetic acid esterification over ion exchange catalysts

Computer simulation showed that catalytic distillation is an attractive process for the removal of dilute acetic acid from wastewater. Selection of catalysts and kinetic data have been obtained for the design of the catalytic distillation column. Kinetic measurements were conducted in a batch reactor. Methanol was added to the dilute acetic acid solutions and reacted with the acid in water to form methyl acetate and water. The reaction can be catalyzed by solid acid catalysts. It was found that Amberlyst 15 was an effective catalyst for this reaction. The effects of stirrer speed, reaction temperature, reactant concentration and catalyst loading on reaction rate were investigated. A complete kinetic equation for describing the reaction catalyzed by Amberlyst 15 was developed. This equation can be used in the simulation and design of the catalytic distillation column for removing acetic acid from wastewater.     

Acylation of Benzene over Clay and Mesoporous Si-MCM-41 Supported InCl3, GaCl3 and ZnCl2 Catalysts

Liquid phase acylation of benzene by acyl chloride (e.g., benzoyl chloride, butyryl chloride or phenyl acetyl chloride) over InCl₃, GaCl₃ and ZnCl₂ supported on commercial clays (viz. montmorillonite-K10, montmorillonite-KSF and kaolin) or high silica mesoporous MCM-41 at 80°C has been investigated. The Mont.-K10 and Si-MCM-41 supported InCl₃ and GaCl₃ catalysts showed high activity in the acyation of benzene by benzoyl chloride even in the presence of moisture in the reaction mixture. The redox function of the supported InCl₃, GaCl₃ or ZnCl₂ catalysts seems to play a very important role in the acylation process.     

负载型离子液体催化酯化法合成三醋酸甘油酯

研究了以磺酸咪唑基离子液体催化甘油和醋酸通过直接酯化法合成三醋酸甘油酯反应,结果表明,[(n-Bu-SO_3H)MIm][HSO_4]离子液体催化性能最好。采用浸渍法将其固载在SiO_2的表面,利用FT-IR对催化剂结构进行了表征,考察反应工艺条件对甘油转化率和三醋酸甘油酯选择性的影响,结果表明,在催化剂用量8%,醋酸与甘油物质的量比6∶1,110℃条件下反应8.0 h,甘油转化率可达到97.2%,对应的三醋酸甘油酯选择性可达21.2%。回收的催化剂经重复使用4次,反应体系中甘油转化率和三醋酸甘油酯选择性无明显下降。     

The partial oxidation of C4–C6 alkanes to maleic anhydride, 2-methyl maleic anhydride, and acetic acid over MoVO catalysts

Alkanes such as iso-butane, n-pentane, and cyclohexane have been converted effectively to maleic anhydride, 2-methyl maleic anhydride, and acetic acid over MoVO catalysts below 330 °C. In order to explore the possible reaction pathways, the oxidation of iso-butene, cyclohexene, 2-methyl-1-propanol, tert-butanol, and 2-methylacrylic acid were examined over the catalysts. In iso-butene oxidation, acetic acid and 2-methyl maleic anhydride were detected but not maleic anhydride. In cyclohexene oxidation, benzene and phenol were detected as major products but it was not the case in cyclohexane oxidation. The results of our investigation indicate that the oxidation pathway of iso-butane is different from that of iso-butene, 2-methyl-1-propanol, tert-butanol, and 2-methylacrylic acid, whereas the oxidation pathway of cyclohexane is different from that of cyclohexene.     

树脂负载FeCl3固体酸催化甲基丙烯酸酯的研究

以自制的 Ｆｅ Ｃｌ３ 负载在树脂上制备的固体酸催化剂对甲基丙烯酸催化酯化反应进行了研究。结果表明,该催化剂具有较高的催化活性,部分酯收率可达８５％ 以上。     

负载型WO3/SiO2-Al2O3催化剂用于合成乙酸乙酯反应研究

考察了SiO2、γ-Al2O3和SiO2-Al2O3载体负载氧化钨作为催化剂用于乙酸乙酯合成反应研究,并通过XRD、氮气物理吸附、Raman和NH3-TPD对催化剂进行表征。结果表明,氧化钨负载在SiO2-Al2O3载体上,具有更强的酸性和更高的酸量,有利于促进乙酸乙酯合成反应进行。当W在SiO2-Al2O3载体表面的负载量为8%(质量分数,下同)时,乙酸转化率最高可以达到69.7%,载体表面WO3晶体颗粒不利于提高酯化反应活性。     

醋酸、醋酐的生产工艺

介绍了醋酸、醋酐工业化生产工艺及最新进展.通过比较各种醋酸、醋酐的生产工艺,确定了目前最佳的生产工艺.大力发展甲醇羰基化联产醋酸、醋酐,同时也要加快对醋酸、醋酐新工艺的研发和完善.     

Selective methanation of CO over supported Ru catalysts

The catalytic performance of supported ruthenium catalysts for the selective methanation of CO in the presence of excess CO₂ has been investigated with respect to the loading (0.5–5.0 wt.%) and mean crystallite size (1.3–13.6 nm) of the metallic phase as well as with respect to the nature of the support (Al₂O₃, TiO₂, YSZ, CeO₂ and SiO₂). Experiments were conducted in the temperature range of 170–470 °C using a feed composition consisting of 1%CO, 50% H₂ 15% CO₂ and 0–30% H₂O (balance He). It has been found that, for all catalysts investigated, conversion of CO₂ is completely suppressed until conversion of CO reaches its maximum value. Selectivity toward methane, which is typically higher than 70%, increases with increasing temperature and becomes 100% when the CO₂ methanation reaction is initiated. Increasing metal loading results in a significant shift of the CO conversion curve toward lower temperatures, where the undesired reverse water–gas shift reaction becomes less significant. Results of kinetic measurements show that CO/CO₂ hydrogenation reactions over Ru catalysts are structure sensitive, i.e., the reaction rate per surface metal atom (turnover frequency, TOF) depends on metal crystallite size. In particular, for Ru/TiO₂ catalysts, TOFs of both CO (at 215 °C) and CO₂ (at 330 °C) increase by a factor of 40 and 25, respectively, with increasing mean crystallite size of Ru from 2.1 to 4.5 nm, which is accompanied by an increase of selectivity to methane. Qualitatively similar results were obtained from Ru catalysts supported on Al₂O₃. Experiments conducted with the use of Ru catalyst of the same metal loading (5 wt.%) and comparable crystallite size show that the nature of the metal oxide support affects significantly catalytic performance. In particular, the turnover frequency of CO is 1–2 orders of magnitude higher when Ru is supported on TiO₂, compared to YSZ or SiO₂, whereas CeO₂- and Al₂O₃-supported catalysts exhibit intermediate performance. Optimal results were obtained over the 5%Ru/TiO₂ catalyst, which is able to completely and selectively convert CO at temperatures around 230 °C. Addition of water vapor in the feed does not affect CO hydrogenation but shifts the CO₂ conversion curve toward higher temperatures, thereby further improving the performance of this catalyst for the title reaction. In addition, long-term stability tests conducted under realistic reaction conditions show that the 5%Ru/TiO₂ catalyst is very stable and, therefore, is a promising candidate for use in the selective methanation of CO for fuel cell applications.     

Selective hydrogenation of cyclopentadiene over supported metal catalysts

The selective hydrogenation of cyclopentadiene to cyclopentene has been studied in the liquid phase using Pd and Pd Me/Al₂O₃ bimetallic catalysts (Me = Mn, Ni, Co, W). The highest activity was obtained with Pd Co and Pd W/Al₂O₃. For these catalysts, no hydrogen or CO chemisorption was detected although Pd could be seen by XPS at 335·8 eV; it is considered that new species, more active for the selective hydrogenation of cyclopentadiene, appeared at the catalyst surface. The sulfur resistance towards thiophene has also been studied. It was observed that the highest sulfur resistance is coincident with the highest activity. XPS analysis shows that the poisoning species is thiophene adsorbed on the catalyst surface.     

Selective oxidation of methylamine over zirconia supported Pt-Ru,Pt and Ru catalysts

Pt–Ru, Pt and Ru catalysts supported on zirconia were prepared by impregnation method and were tested in se-lective oxidation of methylamine (MA) in aqueous media. Among three catalysts, Ru/ZrO2 was more active than Pt/ZrO2 while Pt–Ru/ZrO2 demonstrated the best catalytic activity due to the fact that Pt addition efficiently pro-moted the dispersion of active species in bimetallic catalyst. Therefore, the~100%TOC conversion and N2 selec-tivity were achieved over Pt–Ru/ZrO2, Pt/ZrO2 and Ru/ZrO2 catalysts at 190, 220 and 250 °C, respectively.     

Catalytic performance of Brønsted acid sites during esterification of acetic acid with ethyl alcohol over phosphotungestic acid supported on silica

Different ratios of phosphotungestic acid supported on silica gel were prepared by an impregnation method with PWA loadings ranging from 1 to 30% w/w and calcined at 350 and 500 °C for 4 h in a static air atmosphere. The catalysts were characterized by thermogravimety (TG), differential thermal analysis (DTA), X‐ray diffraction, FT‐IR spectroscopy and N₂ adsorption measurements. The surface acidity and basicity of the catalyst were investigated by the dehydration–dehydrogenation of isopropanol and the adsorption of pyridine (PY) and 2,6‐dimethyl pyridine (DMPY). The gas‐phase estrification of acetic acid with ethanol was carried out at 185 °C in a conventional fixed‐bed reactor at 1 atm using air as carrier gas. The results clearly revealed that the catalyst containing 10% w/w PWA/SiO₂ is the most active and delivers reaction selectively to ester with 85% yield. The Brønsted acid site resulting from hydroxylation of tungsten oxide plays the main role in the formation of ester. Copyright © 2007 Society of Chemical Industry     

甲醇热制备四方相ZrO2及其负载镍催化剂的顺酐加氢性能

通过改变甲醇热时间制备了一系列不同晶粒尺寸的四方相 ZrO₂,采用过体积浸渍法制备了Ni 含量（质量分数）为10%的Ni/ZrO₂催化剂,并考察了其催化顺酐液相加氢性能。采用氮气吸附-脱附（BET）、X射线衍射（XRD）、氢气程序升温还原（H₂-TPR）、X射线光电子能谱（XPS）、原位红外光谱（in situ FTIR）等手段对催化剂进行了表征。研究结果表明,分散性好、晶粒尺寸小的Ni物种有利于C=C键加氢生成丁二酸酐;而金属-载体强相互作用的形成则有利于C=O加氢生成 γ-丁内酯。当甲醇热时间为2 h时,制备的Ni/ZrO₂催化剂的C=O加氢活性最高,在反应温度为210℃,反应压力为5 MPa,反应时间为3 h时,其顺酐转化率达100%,γ-丁内酯选择性为44.7%。     

Adiabatic correction for the esterification of acetic anhydride by methanol via accurate kinetics

In the field of adiabatic correction for complex reactions, a simple one-stage kinetic model was used to estimate the real reaction kinetics. However, this assumption simplified the real process, inevitably generated inaccurate or even unsafe results. Therefore, it was necessary to find a new correction method for complex reactions. In this work, esterification of acetic anhydride by methanol was chosen as an object reaction of study. The reaction was studied under different conditions by Reaction Calorimeter (RC1). Then, Thermal Safety Software (TSS) was used to establish the kinetic model and estimate the parameters, where, activation energies for three stages were 67.09, 81.02, 73.77 kJ·mol^-1 respectively, and corresponding frequency factors in logarithmic form were 16.05, 19.59, 15.72 s^-1. In addition, two adiabatic tests were performed by Vent Sizing Package2 (VSP2). For accurate correction of VSP2 tests, a new correction method based on Enhanced Fisher method was proposed. Combined with kinetics, adiabatic correction of esterification reaction was achieved. Through this research, accurate kinetic parameters for a three-step kinetic model of the esterification reaction were acquired. Furthermore, the correlation coefficients between simulated curves and corrected curves were 0.976 and 0.968, which proved the accuracy of proposed new adiabatic correction method. Based on this new method, conservative corrected results were able to be acquired and be applied in safety assessment.     

Nb2O5负载磷钨酸催化酯化反应研究

采用浸渍法制备TPA/Nb2O5催化剂,用于油酸与甲醇的酯化反应,考察了催化剂焙烧温度、甲醇与油酸物质的量比、反应时间、催化剂用量和TPA负载量等因素对油酸转化率的影响。结果显示,低负载量时(ω=5,10,15),TPA杂多阴离子高度均匀地分散在Nb2O5表面,随着负载量的增加,TPA在Nb2O5表面出现聚结。25-TPA/Nb2O5(300)催化剂在油酸与甲醇的酯化反应中具有良好的催化活性,在n(甲醇)/n(油酸)=12,m(催化剂)/m(油酸)=7%,反应时间在6 h的条件下,油酸的转化率高达92.24%。在303～333 K范围内,油酸的转化率随着温度的升高逐渐增大,油酸与甲醇在TPA/Nb2O5催化剂上的酯化反应符合准二级动力学方程,表观活化能为57.62 kJ/mol,指前因子为1.096×109(mol/L)-1.h-1。     

Gas phase esterification of acetic acid with ethanol over MoO3 supported on AlPO4 and the effect of modification with phosphomolybdic acid and Ce4+ ions

A series of AIPO₄–MoO₃ (APM) systems with various molybdena loadings (5–50) mol %, same modified with phosphomolybdic acid (PMA) and cerium ions, were prepared by an impregnation method and calcined at 400 °C, except for the samples modified with PMA which were calcined at 350 °C for 4 h. The catalysts were characterized by TG/DTG, XRD, IR spectroscopy, N₂ adsorption and electrical conductivity measurements. The surface acidity and basicity of the catalysts were determined by adsorption of pyridine and the dehydration–dehydrogenation of isopropyl alcohol. The catalytic esterification of acetic acid with ethanol was carried out in a convention fixed bed reactor. The results clearly revealed that the catalyst with a composition of 10 mol % MoO₃ (APM10) was the most active and selective catalyst for the production of ethyl acetate. Moreover, the yield of ethyl acetate increases on addition of PMA into APM10 while it decreases on the addition of Ce⁴⁺ ions. These results were correlated with structure, semiconductivity and the acid–base properties of the prepared catalysts. Copyright © 2003 Society of Chemical Industry     

羰基合成醋酐联产醋酸工艺研究

在确定选用均相铑系催化剂后,为了进一步研究中试放大,需对羰基合成小试工艺进行研究。实验采用贵金属铑为主催化剂,碘甲烷为助催化剂,以醋酸甲酯、甲醇和一氧化碳为原料,选用锆材高压釜,均相羰基化合成醋酐并联产醋酸。在温度180—200℃下,压力3.0—6.0MPa,催化剂质量分数700×10-6—1000×10-6,碘甲烷质量分数10%—15%和停留时间70—90min的工艺条件下,按一氧化碳计醋酐选择性为95.4%,CO转化率为97.4%,羰基产物醋酐收率为92.9%;催化剂的时空收率(按醋酐计)为38671.28g/(mol.h)。此工艺参数的提出可以初步指导中试放大并为工业化生产提供基础数据。     

Vanadium-molybdenum phosphates supported by TiO2-anatase as new catalysts for selective oxidation of ethane to acetic acid

Dispersion of vanadium and molybdenum phosphates on titanium oxide (anatase) below the monolayer gives good catalysts for direct oxidation of ethane to acetic acid. By comparison with the dispersion of only vanadium phosphate, the higher selectivity to acetic acid for vanadium and molybdenum phosphates has been explained by an interaction between molybdenum and vanadium as it can be deduced from electron spin resonance and laser Raman spectroscopy studies.     

PtAu/ZrO_2催化甘油选择性制备乳酸

采用溶胶-沉积法制备了Pt Au/ZrO_2系列催化剂,在惰性气体气氛下用于催化甘油选择性制备乳酸。研究不同反应温度下,不同单金属负载和不同比例Pt Au双金属负载催化剂的催化活性以及不同气氛下催化剂重复使用性能,对催化剂进行BET、AAS和TEM等表征。结果表明,在浓度1.1 mol·L-1甘油水溶液10 m L、(1∶1)Pt Au/ZrO_2催化剂用量0.132 g、反应温度160℃、氮气压力1.4 MPa和反应时间6 h条件下,甘油转化率90%,乳酸选择性93.7%。催化剂重复使用性能实验验证了氧气气氛下催化剂活性保持良好。     

Liquid phase selective hydrogenation of phthalic anhydride to phthalide over titania supported gold catalysts

Au/TiO₂ catalysts with different gold loadings were prepared by deposition–precipitation method and used for the liquid phase hydrogenation of phthalic anhydride. All the studied Au/TiO₂ catalysts exhibited excellent activity with high selectivity (>92%) to phthalide under mild reaction conditions (180 °C and 3.0 MPa H₂). Specially, catalysts with 2–3 wt.% gold loading were highly active and selective for the formation of phthalide. When reused, the catalyst showed a certain deactivation, but still was highly selective to phthalide. The deactivation was attributed to the leaching of gold, collapse of the pore structure and accumulation of organic species on the surface.