Catalytic dehydration of lactic acid to acrylic acid over sulfate catalysts

The production of acrylates from biomass‐originated lactic acid is of extraordinary importance to overcome the increasing worldwide shortage of petroleum. In this work, the catalytic dehydration of lactic acid to acrylic acid was carried out over calcium sulfate catalyst with cupric sulfate and phosphates as promoters. The mass ratio of m(CaSO₄)/m(CuSO₄)/m(Na₂HPO₄)/m(KH₂PO₄) is 150.0:13.8:2.5:1.2. In the dehydration of lactic acid, effects of carrier gas, calcination temperature for catalyst, concentration of lactic acid as well as contact time are discussed in detail. With carbon dioxide as carrier gas, the highest acrylic acid yield of 63.7% is achieved from 26 wt.% lactic acid at 330°C and 88 s contact time.     

Selective conversion of lactic acid into acrylic acid over hydroxyapatite catalysts

Lactic acid conversion into acrylic acid was carried out over Ca-HAP catalysts at 623 K. Stoichiometric Ca-HAP catalyst gave a high acrylic acid yield of about 60 C-%. Furthermore, non-stoichiometric calcium deficient Ca-HAP catalysts containing the specific amounts of sodium ions, which were prepared under hydrothermal conditions, exhibited remarkably high acrylic acid yields of about 80 C-%. In contrast, non-stoichiometric Ca-HAP catalysts with vacancy sites and Ca-HAP catalysts with excess amounts of sodium species showed relatively low acrylic acid yields and high selectivities into acetaldehyde and 2,3-pentanedione.     

基于BP神经网络的乳酸脱水制丙烯酸仿真模拟

通过生物质发酵产生的乳酸（2-羟基丙酸）在食品和医药领域具有广泛的商业应用价值,作为可再生资源的生物质乳酸已成为备受关注的化学原料。本文采用BP神经网络对乳酸脱水制丙烯酸的催化过程进行了仿真研究。采用正交实验设计确定实验点,主要考察原料液pH、原料液流速、载气流量和温度4个因素对丙烯酸产率的影响。针对正交实验的缺陷,将正交实验设计和神经网络结合起来,采用基于DOS界面并能方便调节BP神经网络计算的程序包对正交实验结果进行训练,用训练好的网络模拟催化反应体系的动态过程。结果表明,由神经网络仿真模拟出的三维图可以直观地体现各个反应条件对丙烯酸产率的影响,并用穷举法求出最佳反应条件,在该条件下的神经网络模拟产率为27.45%,与实验结果较吻合,相对误差约为－0.4391%。     

Catalytic dehydration of methanol to dimethyl ether over mordenite catalysts

The conversion of methanol to dimethyl ether was carried out over various commercial mordenite and ion-exchanged catalysts to evaluate the catalytic performance of mordenite catalysts with different pore structures and acidities. These catalysts were compared for their catalytic properties in a fixed-bed reactor at 1 atm, 573 K and LHSV of 2.84 h^− 1. The catalysts were characterized by BET, ICP, NH₃-TPD, XRD, TGA and FT-IR techniques. The ion-exchanged mordenite showed higher activity, selectivity and good stability in dehydration of methanol due to the addition of medium acid sites. Also, the effect of water on catalyst deactivation was investigated over two selected catalysts in order to develop a suitable catalyst for synthesis of dimethyl ether. It was found that the H-mordenite catalyst supplied by Süd-chemie Co., (MCDH-1) was more active and less deactivated than another one in a feed containing 20 wt.% water.     

乳酸生产丙烯酸研究进展

随着石油资源的日渐短缺,丙烯酸的生产受到了较大影响,如何利用可再生资源生产丙烯酸显得尤为重要。发酵法生产乳酸工艺已经比较成熟,以发酵乳酸为原料脱水转化为丙烯酸成为生产丙烯酸的一种有效途径。本文综述了丙烯酸的主要生产途径,重点是乳酸脱水制备丙烯酸的研究现状,并指出了乳酸制备丙烯酸的发展前景。     

Catalytic dehydration of glycerol to acrolein over sulfuric acid-activated montmorillonite catalysts

For the development of efficient solid acid catalysts for the catalytic dehydration of glycerol to acrolein, catalysts made from montmorillonitic clay activated by sulfuric acid were investigated. Montmorillonite was activated in diluted sulfuric acid in the concentration range of 5–40 wt.%. The effects of sulfuric acid treatment on the structure of the montmorillonite were characterized by X-ray diffraction, measurements of acidity, N₂ adsorption–desorption isotherms, and Fourier transform infrared spectroscopy. The catalytic behavior of sulfuric acid-activated montmorillonite catalysts in the gas-phase dehydration of glycerol were investigated under varying conditions, including the reaction temperature, the feed rate, and the concentration of glycerol. After montmorillonitic clay was activated by sulfuric acid, the layered structural features of montmorillonite remained nearly intact. Ca^2 +-montmorillonite was changed to H⁺-montmorillonite by ion exchange reaction during activation. The optimal catalytic glycerol dehydration reaction conditions were found to be: temperature at 320 °C, liquid hourly space velocity (LHSV) = 18.5 h^− 1, concentration of glycerol solution = 10 wt.%, and the flow rate of N₂ carrier gas = 10 mL/min. A conversion of 54.2% of glycerol and a yield of 44.9 wt.% acrolein were achieved over the montmorillonite catalyst activated by an aqueous 10 wt.% sulfuric acid solution. The H⁺ in the interlayer space of acid-activated montmorillonite catalysts played a critical role in the catalytic dehydration of glycerol. The temperature, the LHSV, and the concentration of glycerol affected the performance of the catalysts through their influence on the reaction mechanism, the contact time, and the reaction equilibrium.     

碱改性介-微孔HZSM-5分子筛催化乙醇脱水制乙烯性能

对两种不同硅铝比的HZSM-5分子筛进行碱处理,制备介-微孔复合HZSM-5分子筛,研究乙醇脱水制乙烯的催化性能,并考察碱溶液浓度和处理温度对HZSM-5分子筛孔结构和表面酸性的影响。结果表明,适宜的碱处理条件有利于分子筛发生骨架脱硅和脱铝,从而形成介孔。碱处理对硅铝比低的HZSM-5分子筛酸性质影响明显,而硅铝比高的HZSM-5分子筛在碱处理过程中酸性质变化不明显,更易发生脱硅和脱铝而形成更多介孔。碱改性介-微孔HZSM-5分子筛催化剂使乙醇脱水制乙烯催化性能得到改善,尤其低温催化活性提高,这主要归功于碱处理中介孔的形成和表面酸性的调变。     

镍改性HZSM-5催化乙醇脱水制备乙烯

在前期研究工作的基础上,通过正交实验对离子交换法制备Ni-HZSM-5的离子交换液浓度、交换温度和交换次数3个因素进行了考察。结果表明:硝酸镍溶液浓度为0.4 mol/L,交换温度为80℃,交换次数为2次时,制备的Ni-HZSM-5催化乙醇脱水制乙烯的效果最好。其中硝酸镍浓度对乙醇转化率和乙烯选择性的影响都最大。选取了3个催化剂和未改性的HZSM-5分别进行了XRD、BET和Py-TPD表征。最后对最佳条件下制备的Ni-HZSM-5进行了稳定性测试,15 h内乙醇转化率和乙烯选择性保持大于95%,催化性能得到显著提高。     

Dehydration of lactic acid to acrylic acid in high temperature water at high pressures

Reaction of lactic acid was investigated with a flow apparatus in water at high temperatures (450 °C) and high pressures (40–100 MPa). The major products obtained from the reaction of lactic acid were acrylic acid, acetaldehyde, and the minor products were acetic acid and propionic acid. The maximum selectivity of acrylic acid was 44% at 23% lactic acid conversion that was obtained at 450 °C, 100 MPa and a residence time of 0.8 s. The reaction kinetics could be modeled by considering two pathways defined as a dehydration pathway to acrylic acid and a combined reaction pathway that consisted of decarboxylation and decarbonylation to acetaldehyde. The data and the kinetic analysis consistently show that both dehydration and the combined decarboxylation and decarbonylation reactions continue to be promoted in supercritical water as pressure (water density) increases. However, high water densities increase the selectivity of the dehydration reaction.     

Catalytic dehydration of methanol to dimethyl ether (DME) over Al-HMS catalysts

A series of Al-HMS with different Si/Al ratio was used as a solid acid catalyst for methanol dehydration to dimethyl ether (DME). The effect of temperature, feed composition, space velocity, and the catalyst Si/Al ratio on the catalytic dehydration of methanol was investigated. By decreasing Si/Al, the temperature required to reach equilibrium conversion of methanol decreased due to the increased number of acidic sites. Compared to commercial γ-Al₂O₃, Al-HMS-5 and Al-HMS-10, catalysts exhibited a high yield of DME. Among all Al-HMS catalysts, Al-HMS-10 exhibited an optimum yield of 89% with 100% selectivity and excellent stability for methanol dehydration to DME.     

Catalytic dehydration of glycerol to acrolein over mesoporous MCM-41 supported heteropolyacid catalysts

Journal of Porous Materials - A series of vanadium substituted phosphomolybdic acid (VPMA) supported on mesoporous MCM-41 catalysts with varying VPMA content ranging from 10 to 50 wt% were...     

Catalytic dehydration of bioethanol to ethylene

This review presents an up-to-date analysis of the scientific and patent literature concerning ethanol dehydration catalysts and ethylene synthesis processes, taking into consideration the specific features of utilizing biological raw materials.     

氯化铁催化乳酸的酯化作用

报道了氯化铁水合物催化乳酸和醇的酯化作用制备了１５种乳酯。     

复合金属氧化物催化丙烷选择氧化制丙烯酸

采用溶液法制备Mo-V-Te-Nb-O催化剂,研究了焙烧次数对催化剂性能的影响,考察催化剂在普通密封条件下储存时间和连续反应过程中的稳定性。结果表明,二次焙烧制备的催化剂中M1和M2相增强,对丙烯酸生成有利,且晶相形态不随焙烧次数的增加而改变,而烧结现象逐渐增加。催化剂可在普通密封条件下储存24个月,性能不发生变化,催化剂活性和选择性随反应进行不断震荡升高,丙烯酸初期收率为24.7%,反应180 h左右达31.8%,随后催化剂迅速失活。XRD、BET表征及催化剂再生实验表明,其失活的主要原因是Te流失。     

Oxidative conversion of propane to acrylic acid and acetic acid over mixed oxide catalysts

The oxidative conversion of propane to acrylic acid and acetic acid over Mo? V? Sb? R? O (R?La, Ce, Nd and Sm) catalysts at different reaction conditions (viz. temperature, C₃H₈/O₂ ratio, H₂O/C₃H₈ ratio, space velocity, etc.) was investigated. The catalytic activity and selectivity of the Mo? V? Sb catalyst are strongly influenced by the addition of rare earth metals to the catalyst. The addition of water vapour to the feed of propane and oxygen enhances greatly the formation of oxygenated products, particularly acrylic acid and acetic acid. The ratio of selectivities of acrylic acid to acetic acid was found to depend on the rare earth metal used in the catalyst's preparation and the reaction conditions. High contact times, i.e. high degrees of propane conversion, are detrimental to the formation of acrylic acid but beneficial for acetic acid formation. Copyright © 2005 Society of Chemical Industry     

稀土元素(Y、Nd、Ce、La)改性NaY分子筛催化乳酸脱水制丙烯酸

采用浸渍法以稀土元素(Y、Nd、Ce、La)对NaY分子筛进行改性,并以改性后的分子筛为催化剂,考察催化乳酸脱水制丙烯酸反应活性。通过NH₃-TPD、CO₂-TPD和XRD等对催化剂进行表征,结果表明,稀土元素进入NaY分子筛骨架,其中,La对分子筛晶体结构影响最小;随着负载稀土元素离子半径的增大(Y³⁺＜Nd³⁺＜Ce³⁺＜La³⁺） ,总酸性位数量减少,除了重稀土元素Y,弱酸性位比例和中等强度碱性位数量增多,La改性最有利于丙烯酸的生成。稀土元素改性的NaY分子筛在一定程度上提高丙烯酸收率,抑制乙醛生成。以质量分数38%的乳酸为原料,在空速3 h^-1、反应温度325 ℃和2%La/NaY分子筛为催化剂时,丙烯酸收率为54.2%,而未改性NaY分子筛上丙烯酸收率仅为34.7%。     

乳酸酯催化脱水制备丙烯酸酯

以NaY分子筛与Li型蒙脱土复配为催化剂,乳酸酯催化脱水制备丙烯酯,考察催化反应温度和溶剂对乳酸酯类脱水的影响,并对催化脱水机理进行探讨。结果表明,温度升高有利于乳酸酯类的脱水,乳酸甲酯与乳酸乙酯最佳脱水温度分别为320 ℃和290 ℃。溶剂效应显示脱水产物与溶剂相关,乳酸酯催化脱水机理为E2消除机理。     

硼酸改性Hβ沸石分子筛催化2-（4’-乙基苯甲酰基）苯甲酸脱水合成2-乙基蒽醌

采用离子交换法制备由不同浓度硼酸改性的Hβ沸石分子筛,并利用XRD、NH₃-TPD和红外-吡啶对催化剂进行表征。结果表明,硼酸改性后的Hβ沸石分子筛弱酸中心强度有所增加,强酸中心强度略有下降,产生的总酸量增加且以L酸为主,L酸中心有利于反应。研究了改性后的Hβ沸石分子筛对2-（4’-乙基苯甲酰基）苯甲酸脱水合成2-乙基蒽醌反应催化性能的影响。系统考察了反应温度、反应时间和进料速率对2-（4’-乙基苯甲酰基）苯甲酸转化率和2-乙基蒽醌选择性的影响,最佳反应条件为：反应温度240 ℃,催化剂用量1.0 g,进料速率0.5 mL·min-1,反应时间1 h。在此条件下,2-（4’-乙基苯甲酰基）苯甲酸转化率为44.59%,2-乙基蒽醌选择性为77.56%。     

Oxidation of propane to acrylic acid

Partial oxidation of propane was performed over V₂O₅-P₂O₅-based catalysts in the presence of a large excess of oxygen at 350 to 400°C. The main products were acrylic acid, acetic acid, and carbon oxides. Of the V₂O₅- P₂O₅ binary oxides, the best catalyst performances were obtained at a P/V atomic ratio of 1.00; the presence of an excess of phosphorus with respect to the P/V = 1.00 composition induced a large decrease in both the activity and selectivity to form acids. Incorporation of H₃PMo₁₂O₄₀ to a P/V = 1.00 oxide enhanced greatly the formation of acetic acid.     

Catalytic and kinetic study of methanol dehydration to dimethyl ether

Dimethyl ether (DME), as a solution to environmental pollution and diminishing energy supplies, can be synthesized more efficiently, compared to conventional methods, using a catalytic distillation column for methanol dehydration to DME over an active and selective catalyst. In this work, using an autoclave batch reactor, a variety of commercial catalysts are investigated to find a proper catalyst for this reaction at moderate temperature and pressure (110–135 °C and 900 kPa). Among the γ-alumina, zeolites (HY, HZSM-5 and HM) and ion exchange resins (Amberlyst 15, Amberlyst 35, Amberlyst 36 and Amberlyst 70), Amberlysts 35 and 36 demonstrate good activity for the studied reaction at the desired temperature and pressure. Then, the kinetics of the reaction over Amberlyst 35 is determined. The experimental data are described well by Langmuir–Hinshelwood kinetic expression, for which the surface reaction is the rate determining step. The calculated apparent activation energy for this study is 98 kJ/mol.