Theoretical investigation of solvent effects on the selective hydrogenation of furfural over Pt(111)

It was well known that solvent effect plays a very important role in the catalytic reaction. There are many theoretical studies on the solvent effect in homogeneous catalysis while there are few theoretical studies on the solvent effect in the heterogeneous catalytic reaction and there has been no work to investigate the solvent effect on furfural transformation in heterogeneous catalysis. In the present work, both the density functional calculations and the microkinetic analysis were performed to study the selective hydrogenation of furfural over Pt(111) in the presence of methanol as well as toluene and compared with that in the gas condition. The present results indicated that the methanol can enhance the adsorption strength of furfural and other oxygen-containing reaction species due to its relatively strong polarity properties and this can be a main reason for solvent-induced high activity and selectivity. Another reason is that reaction paths study showed that the presence of methanol solvent makes the dehydrogenation of furfural less thermochemical due to the fact that furfural is more stabilized than that of dehydrogenation species, and methanol also has an inhibition effect on the dehydrogenation of furfural in the kinetic aspect, and further energetic span theory proves highest activity and selectivity for hydrogenation in methanol solvent of vapor, methanol and toluene. Moreover, microkinetic model simulation demonstrated that the activity and selectivity of hydrogenation in methanol is both higher than that in vapor and toluene. The much higher activity in methanol is due to the stabilized adsorbed reactants in the surface, which leads to a higher surface coverage of furfural. It might be proposed based on the present work that a solvent with relatively strong polarity may be favorable for the high selective hydrogenation of furfural.     

Preliminary Studies on Furfural Production from Lignocellulosics

This study focused on the production of furfural from agricultural and industrial biomass residues by a hydrodistillation process. Corncobs, sugarcane bagasse, and eucalypt wood were treated with sulfuric, hydrochloric, and phosphoric acids as catalysts, with different acid concentrations (1.5 to 5.2 mol.L ^?1). In addition, the eucalypt liquor from the auto-hydrolysis, kraft-dissolving pulp production process was also investigated as a source of furfural, using sulfuric and hydrochloric acids as a catalyst (0.9 and 3.9 mol.L ^?1) . Furfural yields of 30.2, 25.8, and 13.9% were achieved for corncob, sugarcane bagasse, and eucalypt wood, respectively, on the basis of biomass dry weight. The efficiency of conversion from pentose to furfural using eucalypt liquor from the auto-hydrolysis kraft process was 71.5% using HCl 3.9 mol.L ^?1 . Due to the presence of a high amount of pentose, corncob produced the highest amount of furfural, followed by sugarcane bagasse and then eucalypt wood.     

Furfural steam reforming over Ni-based catalysts. Influence of Ni incorporation method

Catalytic steam reforming of biomass-derived compounds as furfural could be a promising option to produce renewable hydrogen; however efficient catalysts are still under study. Different commercial supports (SiO₂, Al₂O₃, ASA, MgO, MgAl₂O₃, ZnO, TiO₂, Natural Sepiolite) incorporating Ni by incipient wetness impregnation have been initially tested in the Steam Reforming of Furfural (SRF). Among them, Ni supported in natural sepiolite exhibited the best catalytic activity. In order to improve the catalytic performance of this sepiolite-based catalyst an alternative method for the incorporation of Ni was explored (precipitation). Precipitation method led to a Ni-based catalyst highly active and selective in the production of hydrogen. In addition, the production of undesired products (CO and acetone) decreased significantly. Characterization by BET area, XRD, TEM and TPR shows that precipitation method allows to synthesize a Ni-based catalyst with higher BET surface area and smaller metallic nickel particles. These particular physico-chemical properties seem to be the major responsible of the better catalytic performance exhibited by the material prepared by precipitation.     

糠醛精制装置水溶液系统腐蚀问题分析和解决措施

分析了克拉玛依石化公司二套糠醛装置水溶液系统管道及设备的腐蚀原因,并提出控制了原料脱气塔脱气效果和加注KQ-1缓蚀剂来控制水溶液的PH值解决方法,实施后水溶液系统腐蚀得到了有效控制。     

Effect of activation temperature on the surface copper particles and catalytic properties of Cu–Ni–Mg–Al oxides from hydrotalcite-like precursors

The Cu–Ni–Mg–Al oxides catalysts for furfural hydrogenation were prepared from the hydrotalcite-like precursors, and the effect of activation temperature on the Cu⁰ particles and catalytic properties of the catalyst was thoroughly investigated. The catalyst activated by H₂ at 300 °C was found to exhibit the best catalytic activity, due to the presence of the smallest Cu⁰ particles with a high dispersion. Moreover, the bigger Cu⁰ particles were active for furfuralcohol hydrogenolysis to 2-methylfuran in the liquid-phase (ethanolic solution), and the hydrogenation of the furan ring of furfuralcohol and 2-methylfuran on Cu⁰ particles was easily achieved in the vapour-phase.     

Production of hydrogen through the coupling of dehydrogenation and hydrogenation for the synthesis of cyclohexanone and furfuryl alcohol over different promoters supported on Cu-MgO catalysts

Cu-MgO is found to be an efficient catalyst for the coupling reaction of furfural (FAL) hydrogenation and cyclohexanol (CyOH) dehydrogenation. This process is not only efficient in compensating the thermodynamic equilibrium constraints in the cyclohexanol dehydrogenation and improving the yields towards cyclohexanone but also is a economical route for the synthesis of furfuryl alcohol (FFA) and cyclohexanone (Cyone) as the process do not need any external pumping of hydrogen. The effect of incorporation of various promoters viz., Co, Zn, Fe, Cr, Pd and Ni in Cu-MgO over its activity towards this coupling reaction has been studied. Incorporation of Cr in Cu-MgO catalyst is found be an advantageous in enhancing the yields of both FFA and Cyone. All other promoters though found to show higher activity for the individual reactions of FAL hydrogenation and CyOH dehydrogenation, failed to do the same in their coupling reaction. The stabilization of active species (Cu⁺/Cu⁰) by Cr which also seem to increase the synergetic interaction between Cu and MgO as observed from higher dispersion of copper (from XRD results) and easier reducibility of copper oxide (from TPR results) seem to be the factors behind its higher activity over other promoted catalysts.     

Hydrothermal decomposition of xylan as a model substance for plant biomass waste – Hydrothermolysis in subcritical water

Beech wood xylan, as a model substance for hemicellulose contained in plant biomass waste, was subjected to thermohydrolysis in subcritical water. The composition of the product fractions obtained as a result of its hydrothermal decomposition was studied: the water fraction, the oil fraction and the solid fraction of charred post-reaction residue. An increase in temperature favors xylan thermohydrolysis, leading to the production of saccharides – the products of its hydrolytic depolymerization. The yield of the saccharides contained in the water-soluble product fraction reaches it maximum value at 220 °C and 235 °C, with the retention time of 0 min. Both extending reaction time up to 30 min and further increasing the temperature favor the occurring of secondary reactions – saccharide decomposition – leading to the production, among others, of carboxylic acids, furfurals and aldehydes, and their further carbonization and gasification.     

Au/SBA-15催化糠醛选择性加氢制糠醇

通过后修饰法制备出高分散的金属纳米催化剂Au/SBA-15,并运用XRD对制备的催化剂进行表征。以糠醛加氢制糠醇的反应为例,考察反应温度、反应压力及反应时间等对催化剂催化性能的影响。结果表明,含金质量分数为1%、反应温度220℃、反应压力5MPa、反应时间4h、催化剂质量分数2%的条件下,糠醛的转化率为92.1%,选择性97.8%。经过6次重复实验,催化剂的性能没有明显下降。     

α—呋喃丙酸酯香料的合成研究

以糠醛为原料 ,通过三步反应合成了α-呋喃丙酸甲酯、乙酯、正丙酯、异丙酯、正丁酯、正戊酯等六种呋喃丙酸酯香料。此外 ,通过正交实验对呋喃丙酸甲酯的合成条件进行了优化。