C_(6)/C_(6+)糖基碳水化合物选择性转化为糠醛的研究

糠醛是一种广泛应用在食品、医药、农药和化工等领域的重要的精细化工品。通常,半纤维素解聚到五碳糖后进一步脱水可转化为糠醛,而纤维素解聚后生成的六碳糖难于转化为糠醛。基于此,实验研究了葡萄糖(C_(6))选择性转化糠醛的影响因素,提出了可能的反应路径;比较了几种典型的C_(6)/C_(6+)糖基碳水合物转化为糠醛的差异。结果表明葡萄糖在硫酸-环丁砜体系中可转化收率为32.6%的糠醛,且糠醛在硫酸-环丁砜体系中保持6.0 h后的浓度依然较为稳定,损失率仅为4.6%。以果糖、蔗糖与纤维素为原料时,可分别得到收率为32.4%、46.5%和43.5%的糠醛。上述结果说明溶剂的性质及其对糠醛的稳定作用,糖基碳水化合物的碳链长度和结构是影响糠醛选择性生成的重要因素。

柠檬酸络合溶解铁粉绿色合成费托催化剂

柠檬酸是目前世界上产量最大的生物质有机酸之一,应用十分广泛。文章以还原铁粉为铁源,柠檬酸为多齿络合剂和碳源,采用氨水强化柠檬酸络合溶解能力的策略,使其能较快溶解铁粉形成均相的溶胶-凝胶络合物,再经过原位炭化直接获得碳包覆核壳型铁基费托催化剂。在催化剂的费托合成反应性能测试中,使用柠檬酸直接溶解铁粉制备得到的催化剂表现出了优异的催化活性和稳定性,CO转化率达到99.2%,C_(5+)烃类选择性为53%,经过168 h的稳定性测试后,CO转化率仍稳定保持在97.3%以上。柠檬酸络合法可以避免硝酸铁等铁盐的使用,以及铁盐还原过程中易爆和有害气体的产生,具有更加绿色安全的特点,该合成方法为催化剂的绿色安全生产提供了一种新思路。

山梨醇水相芳构化转化为航空燃料范围内的碳氢化合物

文章利用具有微、介孔双孔结构的机械混合分子筛催化剂(Ni/HZSM-5/SBA-15),在较温和的反应条件下,将山梨醇一步水相芳构化转化为航空燃料范围内的芳烃和环烷烃类碳氢化合物。采用X射线衍射(XRD)、透射电子显微镜(TEM)、N_2吸脱附实验、NH_3程序升温解吸(NH3-TPD)等技术对催化剂的结构、形貌和酸性质进行了表征分析。催化剂反应性能测试结果表明:反应温度为320℃时,油相产率达到42.0%,芳烃含量为69.7%;当反应温度升高到360℃时,油相产率增加到61.3%。油相产物主要由环烷烃、支链烷烃和芳烃组成,通过后续加氢脱氧提质,可以转化为高品质的生物航空燃油添加剂。

乙二醇促进制备高分散的Co/SiO_2催化剂及其催化乳酸乙酯转化为1,2-丙二醇的气相加氢活性（英文）

研究了利用乙二醇共浸渍方法制备高分散的二氧化硅负载钴催化剂,该催化剂有效地提高了乳酸乙酯的气相加氢反应活性。系统地考察了钴金属负载量、乙二醇与硝酸钴摩尔比、醇种类和焙烧温度等制备参数对四氧化三钴纳米粒子物性的影响。乙二醇与硝酸钴摩尔比和醇种类对二氧化硅负载的四氧化三钴纳米粒子大小有显著影响。与常规的浸渍方法相比较,共浸渍过程中的乙二醇增强了二价钴粒子和载体二氧化硅之间的相互作用力,从而引起金属钴分散度的提高以及四氧化三钴纳米粒子粒径从16 nm降到5 nm以下;金属钴的高分散与无定型硅酸钴的形成密切相关;同时显著地提高了乳酸乙酯的加氢活性,在反应条件下(2.5MPa、160°C和10%(w,质量分数)Co/SiO_2)乳酸乙酯的转化率从69.5%提高到98.6%,1,2-丙二醇的选择性达到98.0%。利用X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、N_2吸脱附实验、H_2程序升温还原(H_2-TPR)等表征手段对共浸渍制备的Co/SiO_2催化剂结构和形貌进行了表征分析。

Production of Mixed Alcohols from Bio-syngas over Mo-based Catalyst

A series of Mo-based catalysts prepared by sol-gel method using citric acid as complexant were successfully applied in the high efficient production of mixed alcohols from bio-syngas, derived from the biomass gasification. The Cu1Co1Fe1MO1Zn0.5-6%K catalyst exhibited a higher activity on the space-time yield of mixed alcohols, compared with the other Mobased catalysts. The carbon conversion significantly increases with rising temperature below 340 ℃, but the alcohol selectivity has an opposite trend. The maximum mixed alcohols yield derived from biomass gasification is 494.8 g/（kg catal·h） with the C2＋ （C2-C6 higher alcohols） alcohols of 80.4% under the tested conditions. The alcohol distributions are consistent with the Schulz-Flory plots, except methanol. In the alcohols products, the C2＋ alcohols （higher alcohols） dominate with a weight ratio of 70%-85%. The Mo-based cata- lysts have been characterized by X-ray diffraction and N2 adsorption/desorption. The clean bio-fules of mixed alcohols derived from bio-syngas with higher octane values could be used as transportation fuels or petrol additives.

Highly Efficient Synthesis of Clean Biofuels from Biomass Using FeCuZnAIK Catalyst

Highly efficient synthesis of clean biofuels using the bio-syngas obtained from biomass gasi- fication was performed over Fel.5CulZnlAllK0.117 catalyst. The maximum biofuel yield from the bio-syngas reaches about 1.59 kg biofuels/（kgcat·rh） with a contribution of 0.57 kg alcohols/（kgcat·rh） and 1.02 kg liquid hydrocarbons/（kgcat·rh）. The alcohol products in the resulting biofuels were dominated by the C2＋ alcohols （mainly C2-C6 alcohols） with a content of 73.55%-89.98%. The selectivity .of the liquid hydrocarbons （C5＋） in the hydrocarbon products ranges from 60.37% to 70.94%. The synthesis biofuels also possess a higher heat value of 40.53-41.49 MJ/kg. The effects of the synthesis conditions, including temperature, pressure, and gas hourly space velocity, on the biofuel synthesis were investigated in detail. The catalyst features were characterized by inductively coupled plasma and atomic emission spectroscopy, X-ray diffraction, temperature programmed reduction, and the N2 adsorption-desorption isotherms measurements. The present biofuel synthesis with a higher biofuel yield and a higher selectivity of liquid hydrocarbons and C2＋ alcohols may be a potentially useful route to produce clean biofuels and chemicals from biomass.

Hydrogen Production by Low-temperature Steam Reforming of Bio-oil over Ni/HZSM-5 Catalyst

We investigated high catalytic activity of Ni/HZSM-5 catalysts synthesized by the impregnation method, which was successfully applied for low-temperature steam reforming of bio-oil. The influences of the catalyst composition, reforming temperature and the molar ratio of steam to carbon fed on the stream reforming process of bio-oil over the Ni/HZSM-5 catalysts were investigated in the reforming reactor. The promoting effects of current passing through the catalyst on the bio-oil reforming were also studied using the electrochemical catalytic reforming approach. By comparing Ni/HZSM-5 with commonly used Ni/Al2O3 catalysts, the Ni2O/ZSM catalyst with Ni-loading content of about 20% on the HZSM-5 support showed the highest catalytic activity. Even at 450 ℃, the hydrogen yield of about 90% with a near complete conversion of bio-oil was obtained using the Ni2O/ZSM catalyst. It was found that the performance of the bio-oil reforming was remarkably enhanced by the HZSM-5 supporter and the current through the catalyst. The features of the Ni/HZSM-5 catalysts were also investigated via X-ray diffraction, inductively coupled plasma and atomic emission spectroscopy, hydrogen temperature-programmed reduction, and Brunauer-Emmett-Teller methods.

Promotion of Ni/MCM-41 Catalyst for Hydrogenation of Naphthalene by co-Impregnation with Polyols

The activities of nickel supported on MCM-41 catalysts, prepared by co-impregnation with polyols （ethylene glycol, glycerol, xylitol, sorbitol and glucose）, were investigated by hydrogenation of naphthalene. Compared with the conventional wetness impregnation, addition of moderate polyols into the metal nitrate support surface, resulting in formation of persion of the active phase and significant aqueous solution could enhance interaction with very small NiO particle size （〈5 nm）, high discatalytic activity. Particle size of Ni^0 decreased from 36.1 nm to below 5 nm; meanwhile the complete hydrogenation of naphthalene was dependent on the Ni^0 particle size. The hydrogenation activities of the catalysts prepared by co-impregnation with polyols were very high with 100% conversion even at iow temperature of 55 ℃.

C12A7-MgO催化剂上的生物油裂解制氢

Catalytic steam reforming of condensable vapors, i.e. bio-oil, derived from pyrolysis of biomass is an important process for hydrogen production, which is expected to form renewable and clean energy. The generation of hydrogen from bio-oil was investigated from 250 to 750 ℃ by a MgO mixed C12A7-O^-(C12A7-MgO) catalyst in a fixed-bed micro-reactor. The hydrogen yield on C12A7-MgO was about 44% at 750 ℃. It is found that both the catalytic activity and catalysis life are improved by doping MgO. The XRD results show that the C12A7 structure of the positively charged lattice framework remains in the C12A7-MgO catalyst.

Synthesis of Methyl Acetate by Dimethyl Ether Carbonylation over Cu/HMOR： Effect of Catalyst Preparation Method

Dimethyl ether carbonylation to methyl acetate was comparatively investigated over mor- denite supported copper （Cu/HMOR） catalysts prepared by different methods including evaporation, urea hydrolysis, incipient wetness impregnation and ion-exchange. The results showed that Cu/HMOR prepared via iron-exchange method exhibited the highest catalytic activity due to the synergistic effect of active-site metal and acidic molecular sieve support. Conversion of 95.3% and methyl acetate selectivity of 94.9% were achieved under conditions of 210℃, 1.5 MPa, and GSHV of 4883 h-1. The catalysts were characterized by nitrogen absorption, X-ray diffraction, NH3 temperature program desorption, and CO temperature program desorption techniques. It was found that Cu/HMOR prepared by ion-exchange method possessed high surface area, moderate strong acid centers, and CO adsorption centers, which improved catalytic performance for the reaction of CO insertion to dimethyl ether.

Effect of Calcination Temperature on Catalytic Activity and Textual Property of Cu/HMOR Catalysts in Dimethyl Ether Carbonylation Reaction

The effect of calcination temperature on the catalytic activity for the dimethyl ether （DME） carbonylation into methyl acetate （MA） was investigated over mordenite supported copper （Cu/HMOR） prepared by ion-exchange process. The results showed that the catalytic activity was obviously affected by the calcination temperature. The maximal DME conversion of 97.2% and the MA selectivity of 97.9% were obtained over the Cu/HMOR calcined at 430 ℃ under conditions of 210 ℃, 1.5 MPa, and GSHV of 4883 h^-1. The obtained Cu/HMOR catalysts were characterized by powder X-ray diffraction, N2 absorption, NH3 temperature program desorption, CO temperature program desorption, and Raman techniques. Proper calcination temperature was effective to promote copper ions migration and diffusion, and led the support HMOR to possess more acid activity sites, which exhibited the complete decomposing of copper nitrate, large surface area and optimum micropore structure, more amount of CO adsorption site and proper amount of weak acid centers.

Ru助剂对Co/SiO_2/HZSM-5催化剂合成航空燃油类烃的影响

以中孔硅胶和微孔HZSM-5分子筛为复合载体,添加Ru制备了钴基催化剂,考察了Ru添加量（1%-4%,质量分数）对催化剂结构和固定床费托合成航空燃油类烃的影响。实验结果表明,制备的复合载体催化剂有一定的微孔和中孔结构,Ru的添加有利于Co分散,Ru促进的催化剂低温还原过程提高了催化剂在150-750℃的还原度和CO转化率,复合载体中HZSM-5分子筛利用其微孔结构,提高了异构烃的收率。当Ru负载量为1%时,CO转化率达到62.8%,航空燃油类烃的收率达到37.7%,包括约10.9%的异构烃。 Ru负载量超过2%时,增强的催化剂CO加氢活性和CH4选择性,导致合成产物向低碳烃方向偏移。

Urchin-like CoCu Bimetallic Nanocomposites for Catalytic Hydrogenolysis of Glycerol to Propanediols

Bimetallic CoCu nanocomposites were synthesized in polyol by using Ru as heterogeneous nucleation agent and stearic acid as surfactant, and their catalytic properties were investi- gated by hydrogenolysis of glycerol to propanediols. It was found that the surfactant could induce Co nanocrystals to form nanowires as structure-directing agent, while it＇s ineffective for Cu because only spherical Cu particles were produced under the same condition. When Co2＋ and Cu2＋ coexist in polyol, Cu2＋ is firstly reduced and forms the spherical particles, and then the Cu particles afford surface for the subsequential reduction of Co2＋ and growth of Co nanocrystals to form the nanorods, obtaining the urchin-like CoCu nanocomposites. The catalytic performance in selective hydrogenolysis of glycerol to propanediols proposed that the CoCu urchin-like nanocomposites was superior to the Co nanowires possibly due to that the synergistic effect between Co and Cu component promoted conversion of glyc- erol and obtained the higher propanediol yields based on the specific surface areas of the catalysts.

Bio-methanol from Bio-oil Reforming Syngas Using Dual-reactor

A dual-reactor, assembled with the on-line syngas conditioning and methanol synthesis, was successfully applied for high efficient conversion of rich CO2 bio-oil derived syngas to bio-methanol. In the forepart catalyst bed reactor, the catalytic conversion can effectively adjust the rich-CO2 crude bio-syngas into the CO-containing bio-syngas using the CuZnA1Zr catalyst. After the on-line syngas conditioning at 450℃, the CO2/CO ratio in the blo- syngas significantly decreased from 6.3 to 1.2. In the rearward catalyst bed reactor, the conversion of the conditioned bio-syngas to bio-methanol shows the maximum yield about 1.21 kg/（kgcatarh） MeOH with a methanol selectivity of 97.9% at 260 ~C and 5.05 MPa using conventional CuZnA1 catalyst, which is close to the level typically obtained in the conventional methanol synthesis process using natural gas. The influences of temperature, pressure and space velocity on the bio-methanol synthesis were also investigated in detail.

生物质催化转化制备1,5-戊二醇和1,6-己二醇研究进展

1,5-戊二醇和1,6-己二醇是具有高附加值的精细化工产品,广泛应用于增塑剂、高级油墨、化妆品、医药、光固化(UV)涂料等领域。该文综述了生物质基1,5-戊二醇和1,6-己二醇制备技术的研究现状,与石油基路径相比,生物质基路径具有原料可再生、资源丰富、转化路线短(2～3步转化)、产物选择性高(大于90%)及水相反应体系绿色无污染等优点,但还存在铂、铑、铼、铱等贵金属催化剂昂贵、转化率偏低和碳氧键断裂机理研究不足等问题。进一步开发非贵金属替代贵金属催化剂和提高贵金属利用率、新的高效制备路径和明晰碳氧键选择性断裂机理具有非常重要的意义。

Facile Green Synthesis of Magnetic Fe3C@C Nanocomposite using Natural Magnetite

One simple and environmental friendly synthesis strategy for preparing low-cost magnetic Fe3C@C materials has been facilely developed using a modified sol-gel approach,wherein natural magnetite acted as the iron source.A chelating polycarboxylic acid such as citric acid(CA)was employed as the carbon source,and it dissolved Fe very effectively,Fe3O4 and natural magnetite to composite an iron-citrate complex with the assistance of ammonium hydroxide.The core-shell structure of the as-prepared nanocomposites was formed directly by high-temperature pyrolysis.The Fe3C@C materials exhibited superparamagnetic properties(38.09 emu/mg),suggesting potential applications in biomedicine,environment,absorption,catalysis,etc.