生物质催化转化制取芳香化合物

利用分子筛催化剂(NaZSM-5、HZSM-5、ReY和HY)研究了木屑上催化裂解制取芳香物(苯、甲苯、二甲苯)的反应过程,发现HZSM-5催化剂具有最高的生物质裂解制备芳香化合物的活性. 在450 oC、 载气流速为300 mL/min和催化剂/木屑比为2的优化反应条件下,芳香化合物的产率和选择性分别达到26.5%和62.5C-mol%.     

Ru/C催化5-羟甲基糠醛选择氧化高效合成2,5-呋喃二甲醛

在活性炭负载金属钌(Ru/C)催化剂上实现了5-羟甲基糠醛的高效选择氧化.以甲苯为反应溶剂,在383 K和2.0 MPa O₂的反应条件下,2,5-呋喃二甲醛(DFF)收率高达95.8%.与活性炭负载的具有相似粒径的Pt,Rh,Pd,Au等其它贵金属催化剂相比,Ru/C具有更加优良的活性和DFF选择性.同时Ru/C催化剂结构稳定,具有良好的重复使用性能.在相似的反应条件下,采用水代替甲苯作为溶剂,同时添加少量水滑石固体碱,可便捷地将主要产物从DFF调变为5-甲酰基-2-呋喃甲酸或2,5-呋喃二甲酸,显示出Ru/C催化剂在控制5-羟甲基糠醛选择氧化反应产物方面的优异性能.     

Al2O3基Ni-Cu双金属催化剂上乙酰丙酸氢解（英）

Inexpensive γ-alumina-based nickel-copper bimetallic catalysts were studied for the hydrogenolysis of levulinic acid,a key platform molecule for biomass conversion to biofuels and other valued chemicals,into γ-valerolactone as a first step towards the production of 2-methyltetrahydrofurane.The activities of both monometallic and bimetallic catalysts were tested.Their textural and chemical characteristics were determined by nitrogen physisorption,elemental analysis,temperature-programmed ammonia desorption,and temperature-programmed reduction.The monometallic nickel catalyst showed high activity but the highest bγ-product production and significant amounts of carbon deposited on the catalyst surface.The copper monometallic catalyst showed the lowest activity but the lowest carbon deposition.The incorporation of the two metals generated a bimetallic catalyst that displayed a similar activity to that of the Ni monometallic catalyst and significantly low bγ-product and carbon contents,indicating the occurrence of important synergetic effects.The influence of the preparation method was also examined by studying impregnated- and sol-gel-derived bimetallic catalysts.A strong dependency on the preparation procedure and calcination temperature was observed.The highest activity per metal atom was achieved using the sol-gel-derived catalyst that was calcined at 450 ℃.High reaction rates were achieved;the total levulinic acid conversion was obtained in less than 2 h of reaction time,yielding up to 96%γ-valerolactone,at operating temperature and pressure of 250 ℃ and 6.5 MPa hydrogen,respectively.     

TS-1/H2O2碱溶液中低温氧化愈创木酚制备马来酸（英）

可再生生物质资源的开发与利用能够缓解化石燃料产生的温室气体对环境的负面影响.在生物质燃料制备过程中联产高附加值化学品能大幅提高生物质炼制的经济性.愈创木酚是常见的木质纤维素快速热解产物.本文研究了低温液相氧化愈创木酚制备马来酸,并重点考察了催化剂添加量、pH值、反应时间和反应温度等反应条件的影响.研究发现,在钛硅沸石-过氧化氢碱溶液氧化反应体系中（80℃,pH=13.3）,20₃0mol%的愈创木酚可以选择性转化为马来酸.同时初步探讨了愈创木酚氧化开环转化为马来酸的反应机理.     

NOx and N2O precursors (NH3 and HCN) from biomass pyrolysis: Co-pyrolysis of amino acids and cellulose, hemicellulose and lignin

Nitrogen in biomass is mainly in forms of proteins (amino acids). Glycine, glutamic acid, aspartic acid, leucine, phenylalanine and proline are the major amino acids in agricultural straw. The six amino acids were pyrolyzed individually at 800 °C in a tubular reactor in an argon atmosphere. Each amino acid sample was then pyrolyzed individually with cellulose, hemicellulose or lignin with 1:1 mixing ratio by weight under the same condition. The emissions of HCN and NH₃ were detected with a Fourier transform infrared (FTIR) spectrometer. The extent of interaction between the amino acids with cellulose, hemicellulose or lignin was determined by comparing the yields of HCN and NH₃ from co-pyrolysis with those from single amino acid pyrolysis under the same condition. The results indicate that the structure of the amino acid has a significant effect on the nitrogen transformation during pyrolysis. The mixtures undergo solid-state decomposition reactions during co-pyrolysis. The extent of interaction between the amino acids with cellulose, hemicellulose or lignin depends on the amino acid types and the components in biomass. Although single proline and leucine form no char, they give a significant amount of nitrogen-containing char when co-pyrolyzed with cellulose, hemicellulose and lignin. HCN and NH₃ yields and nitrogen conversion pathway from amino acid pyrolysis are influenced by cellulose, hemicellulose and lignin.     

Biomass pyrolysis in pulverized-fuel boilers: Derivation of apparent kinetic parameters for inclusion in CFD codes

Biomass combustion in pulverized-fuel boilers is a growing way to produce electricity from a renewable source of energy. Slagging and fouling limit however the reliability of the units that were initially designed for coal combustion. Computational Fluid Dynamics (CFD) codes aiming at studying those phenomena include simplified models of biomass particle pyrolysis, of which the pertinence has already been questioned for the typical conditions of interest. A comprehensive model has been developed to investigate pyrolysis of particles in pulverized-fuel boilers, with sizes ranging from 17 μm to 2.5 mm. The detailed model accounts for internal heat conduction, internal gaseous convection, moisture evaporation and particle shrinkage. It includes a competitive, multi-component kinetic scheme, improved for high temperatures. The discrepancy between the simplified models integrated in most CFD applications and the detailed simulations is highlighted. The simplified isothermal models underestimate pyrolysis time for the largest particles. Moreover, such models delay and shorten the volatiles release. The flame lengths, the local temperature fields and the pollutant emissions might be importantly impacted in global combustion simulations. Apparent kinetic parameters have been derived from the detailed simulations. Their use in existing simplified models improves the behavior of the biomass particles during pyrolysis, and offers therefore an efficient alternative to the integration of complex pyrolysis models in CFD codes.     

Activated carbon produced from paulownia sawdust for high-performance CO2 sorbents

In this paper, activated carbons （ACs） with high specific surface areas were successfully synthesized by simple one-step carbonization-activation from paulownia sawdust biomass, and the effects of the synthetic conditions on their CO2 capture capacity were investigated as well. The results show that, when the mass ratio between activator and biomass is 4, the activation temperature is 700℃ and the activation time is 1 h, as-made AC provides the most micropores for CO2 adsorption. As a consequence, the maximum CO2 uptake of 8.0 mmol/g is obtained at 0 ℃ and 1 bar.     

常压连续反应性萃取法由预处理生物质制备乙酰丙酸

采用双相联系流反应性萃取技术实现常压下小麦秸秆向乙酰丙酸的转化,其中生物质在水相中完成降解,形成乙酰丙酸,而后比水密度大的有机相作为乙酰丙酸的萃取相,把生成的乙酰丙酸萃取到有机相,并经过虹吸到收集瓶中,有机相经蒸馏可反复使用,实现了预处理生物质到乙酰丙酸的高效转化,乙酰丙酸最大的产率为30.66%.     

Investigation on the geometric and matrix effects and quantitative determination of K, Cl and S atomic fraction for biomass burning particles by Monte Carlo simulation

Using Monte Carlo simulation, the geometric and matrix effects on intensity and intensity ratio measured by EPMA were investigated for both synthetic particles and biomass burning particles. Three particulate standards, KCl, K₂SO₄, KHSO₄, were prepared and measured along with biomass burning particles. The modified CASINO program (University of Sherbrooke, Quebec, Canada) at the University of Antwerp, Belgium was used. The relative intensities obtained by the UA version of the CASINO program appear to be in line with those from experiments.The CASINO program and iterative procedures were applied to quantitatively determinate the atomic fraction of K, Cl and S in particulate standard and real samples. After correcting the geometric and matrix effects, the atomic fraction ratio of K to Cl in KCl sample was found to be 1.007±0.025, 0.996±0.013 and 1.011±0.019 for experiments with high voltages of 15, 20 and 25 keV, respectively. The same procedure was also applied to K₂SO₄ and KHSO₄ standard particle sample. The atomic fraction ratio of K to S was 1.945±0.049 (25 keV) for K₂SO₄ and 1.014±0.072 (20 keV) for KHSO₄. These ratios obtained are close to the theoretic values 1 or 2. Reasonable data were obtained for biomass burning particles, indicating that it is possible to perform chemical speciation.     

Catalytic effects of eight inorganic additives on pyrolysis of pine wood sawdust by microwave heating

In this paper, pyrolysis of pine wood sawdust was carried out by microwave heating at ca. 470 °C under dynamic nitrogen atmosphere. Eight inorganic additives (NaOH, Na₂CO₃, Na₂SiO₃, NaCl, TiO₂, HZSM-5, H₃PO₄, Fe₂(SO₄)₃) were investigated in terms of their catalytic effects on the pyrolysis. All of the eight additives have increased yields of solid products greatly and decreased yields of gaseous products more or less. Yields of liquid products have not subjected to dramatic change. The incondensable gases produced from pyrolysis consist mainly of H₂, CH₄, CO and CO₂. All of the eight additives have made these gases evolve earlier, among which the four sodium additives have the most marked effect. All the additives have made the amount of CH₄ and CO₂ decrease, while all of them except NaCl, TiO₂ and Fe₂(SO₄)₃ have made that of H₂ increase and all of them except Na₂SiO₃ and HZSM-5 have made that of CO decrease. Alkaline sodium compounds NaOH, Na₂CO₃ and Na₂SiO₃ favor H₂ formation most. The most abundant organic component in the liquid products from pyrolysis of untreated sample and samples treated by all the additives except H₃PO₄ and Fe₂(SO₄)₃ is acetol. All the four sodium compounds favor acetol formation reaction and the selection increasing effect follows the order of NaOH > Na₂CO₃ ≈ Na₂SiO₃ > NaCl. TiO₂ goes against the formation of acetol, HZSM-5 has no marked effect on acetol formation. The two dominant organic components identified in the liquid products from pyrolysis of H₃PO₄ and Fe₂(SO₄)₃ treated samples are both fufural and 4-methyl-2-methoxy-phenol. A possible pathway for acetol formation is tentatively proposed.