生物质热解液化技术研究与发展趋势

介绍了生物质热解液化技术,总结了该项技术在原料预处理、热解工艺和生物油分离精制3个方面的最新研究成果。在原料预处理方面,介绍了微波干燥、烘焙和酸洗3种方法;在热解工艺方面,介绍了催化热解和混合热解两种新工艺;在生物油分离精制方面,介绍了催化加氢、催化裂解、催化酯化、乳化燃油和分离提纯5种新技术,并分析展望了生物质热解液化技术的产业化发展趋势。     

生物油改性及催化热解技术研究进展

生物质快速热解制取生物油是一种生物质能源热转化的重要方式,是目前可再生能源利用研究的热点。文中介绍了快速热解技术的发展现状,详细讨论了生物质油的特性以及生物质油精制和改性方法,包括催化加氢、催化裂解、添加溶剂与乳化技术,以及近年来倍受关注的生物质催化热解技术。     

生物质裂解油催化裂解精制机理研究(Ⅱ)——生物质油沥青质的分子模型

测定生物质裂解油和催化裂解精制油沥青质的平均分子质量和元素含量,计算两种沥青质基本结构单元的平均分子式。通过1H-NMR,13C-NMR波谱计算得到一系列平均结构参数,建立生物质裂解油和催化裂解精制油沥青质的分子模型,并用傅里叶变换红外光谱进行验证。分析结果表明:精制后的催化裂解精制油的沥青质含量减少,分子量降低,含氧官能团明显少于生物质裂解油沥青质,而芳环数目增加。由此可见,经过精制反应后的催化裂解精制油沥青质的分子量变小,氧含量降低,芳香度增加,从而会影响生物质油的品质。     

生物质裂解油催化裂解精制机理研究(Ⅲ)——生物质裂解油模拟物的催化裂解机理

分析生物质油6种模拟物在裂解温度500℃,不同质量空速条件下的催化裂解产物。不含芳环的生物质油模拟物(乙酸、甲醇、环戊酮和糠醛)经过HZSM-5分子筛催化剂催化裂解后的产物中,均含有苯、萘、茚和多环芳烃及其衍生物,而苯酚和间甲酚经过HZSM-5分子筛催化裂解后,产物中主要是酚类化合物。根据模拟物催化裂解产物,推测不同类型化合物的催化裂解反应途径,说明生物质裂解油催化裂解精制反应过程主要发生脱氧和芳烃化反应,为生物质油催化裂解精制机理研究提供了理论依据。     

生物质油精制中催化剂的应用及进展

回顾了20世纪80年代以来，生物质油精制中各种催化剂的应用，并对各种催化剂的性能进行了比较，尤其是对催化裂解中催化剂的选择、制备、使用、再生和催化效果进行了详细的综述和比较。探讨了生物质油的精制机理，并对催化剂的选择进行了预测和展望。     

生物质裂解油催化裂解精制机理研究(Ⅰ)——生物质裂解油及其催化裂解精制油的物性及组成

通过生物质裂解油和催化裂解精制油的物性和化学分析显示催化裂解精制油的密度、粘度、水含量较生物质裂解油明显降低,而pH值和热值明显提高。催化裂解精制油的碳含量较生物裂解油增加,氧含量降低。催化裂解精制油中的酸、醛、酮、糖和醇含量明显降低,酚和芳烃含量明显增加。说明经过催化裂解精制后的精制油的品质较精制前的生物裂解油明显提高。     

生物质高压液化制生物油研究进展

以生物质为原料进行高压液化制备生物油是目前生物质能领域研究的一个热点。纤维素在水中的降解是复杂的竞争和连串反应机理;在180℃以上,半纤维素就很容易水解,而且不管是酸还是碱都能催化半纤维素的水解反应;在水热条件下木质素会发生分解,生成多种苯酚、甲氧基苯酚等,这些产物可进一步被水解成甲氧基化合物。影响生物质液化产率及生物油组成的主要因素是温度、生物质类型和溶剂种类;次要因素包括停留时间、催化剂、还原性气体和供氢溶剂、加热速率、生物质颗粒大小、反应压力等。纤维素类生物质通过高压液化可以生产生物油,生物油经物理精制及化学加工可以制取车用燃料、生物气及化工产品等。生物油有轻油和重油之分,都是通过对生物质液化产物的分离精制而得到的。目前用来分析生物油的主要方法包括GC-MS(色-质联用)、EA(元素分析)、FTIR(傅里叶变换红外光谱)、HPLC(高效液相色谱)、NMR(核磁共振)、TOC(总有机碳测定)等。人们对生物质高压液化研究已经进行多年,并建立了几套工业试验示范装置。不过因为操作条件太苛刻,到目前为止还没有建立商业化装置。     

我国生物质热解液化技术的现状

文章主要阐述了我国生物质热解液化技术的研究现状，包括现有的热裂解液化装置、反应动力学模型、已检测出的不同原料裂解产生的生物油成分及其物理特性分析，提出了生物油精制的必要性和未来需要研究的问题。     

生物质快速热解制取生物油

生物质能源是可再生能源的重要组成部分,具有资源丰富和低污染的特点,它的开发与利用已成为21世纪研究的重要课题。本文概述了生物质快速热解的过程、设备及其产物,并对热解的重要产物——生物油的组成、性质、精制以及转化利用进行了详细的阐述。     

流化床反应器中生物质的热解研究

以松木锯末、花生壳、大豆秸秆等几种典型生物质为试验原料,在流化床反应器内进行了热解试验,分别考察了热解反应温度、停留时间、进料量对生物质热解产物(油、气、炭)产率的影响,以及这几种生物质原料热解产油率的最佳工艺条件.运用GC/MS方法确认了生物质热解油中的40种化合物,生物质热解油的GC/MS法分析结果为其在化工和能源方面的综合利用提供了有价值的数据.     

催化技术在降低汽油机排放方面的应用

本文介绍了当前催化技术在改善和降低汽油机排放方面的应用情况，指出：催化技术是改善汽油机排放的一种有效措施和重要手段。     

三效催化转化器性能的劣化及其对策

本文详细分析了三效催化转化器的性能劣化机理，并提出了减缓劣化速度的对策。     

Graphene-anchored Ni6MnO8 nanoparticles with steady catalytic action to accelerate the hydrogen storage kinetics of MgH2

Transition metal-based oxides have been proven to have a substantial catalytic influence on boosting the hydrogen sorption performance of MgH₂. Herein, the catalytic action of Ni₆MnO₈@rGO nanocomposite in accelerating the hydrogen sorption properties of MgH₂ was investigated. The MgH₂ + 5 wt% Ni₆MnO₈@rGO composites began delivering H₂ at 218 °C, with about 2.7 wt%, 5.4 wt%, and 6.6 wt% H₂ released within 10 min at 265 °C, 275 °C, and 300 °C, respectively. For isothermal hydrogenation at 75 °C and 100 °C, the dehydrogenated MgH₂ + 5 wt% Ni₆MnO₈@rGO sample could absorb 1.0 wt% and 3.3 wt% H₂ in 30 min, respectively. Moreover, as compared to addition-free MgH₂, the de/rehydrogenation activation energies for doped MgH₂ composites were lowered to 115 ± 11 kJ/mol and 38 ± 7 kJ/mol, and remarkable cyclic stability was reported after 20 cycles. Microstructure analysis revealed that the in-situ formed Mg₂Ni/Mg₂NiH₄, Mn, MnO₂, and reduced graphene oxide synergically enhanced the hydrogen de/absorption properties of the Mg/MgH₂ system.     

A study on the catalytic hydrogenation of N-ethylcarbazole on the mesoporous Pd/MoO3 catalyst

Mesoporous MoO₃ shows an apparent activity in the catalytic hydrogenation of N-ethylcarbazole (NEC), where a significant amount of tetrahydro-N-ethylcarbazole (4H-NEC) and perhydro-N-ethylcarbazole (PNEC) are detected with the hydrogen uptake of 0.97 wt% after 6 h when the temperature rises to 220 °C. 0.5 wt% Pd/MoO₃ catalyst shows a superior catalytic efficiency than the traditional precious metal catalysts 0.5 wt% Ru/Al₂O₃ and 0.5 wt% Pd/Al₂O₃, especially in the conversion of Octahydro-N-ethylcarbazole (8H-NEC) to PNEC. The hydrogenation mechanism of MoO₃ is completely different from the traditional precious metal catalysts. With the presence of a small amount of Pd, the breaking of HH bond is greatly accelerated, result in the promotion of hydrogen spillover rate and the increase of the concentration of hydrogen molybdenum bronze H_xMoO₃, which improves the catalytic efficiency of the MoO₃ catalyst. Rise the temperature also helps increasing the concentration of H in H_xMoO₃.     

Catalytic effects of V and V2O5 on hydrogen storage property of Mg17Al12 alloy

A Mg₁₇Al₁₂ alloy was synthesized via sintering, and the catalytic effects of V and V₂O₅ on the hydrogen (H₂)-storage properties of this alloy were investigated. The results revealed that the hydrogenation/dehydrogenation temperature of Mg₁₇Al₁₂ decreased markedly and the reversible hydrogen storage properties improved with the addition of V or V₂O₅. For example, at 250 °C, the Mg₁₇Al₁₂ alloy underwent hydrogenation only and a hydrogen absorption capacity of 2.22 wt.% was realized. However, with the addition of V and V₂O₅, (i) reversible hydrogen absorption/desorption occurred, (ii) the hydrogen absorption capacity increased to 2.95 wt.% and 3.35 wt.%, and (iii) the hydrogenation/dehydrogenation enthalpy of the Mg₁₇Al₁₂alloy decreased from 65.7/83.1 kJ·mol^?1 to 62.6/69.3 kJ·mol^?1 and 59.9/68.1 kJ·mol^?1, respectively.     

Transient effect on a catalytic reactor

At time t < 0, a steady motion of a chemically reacting dilute binary mixture of a gas exists in a long cylindrical porous pipe, such that the steady-state velocity component and the gas concentration are given by (u_s, v_s, O) and c_s in cylindrical polar co-ordinates (r, ø, z). When t = O, a constant pressure gradient is applied at one end of the tube. If the inertia terms are neglected, a Laplace transform and a finite-difference scheme are employed to solve for the transient flow (u, v. w) and c. The time required to achieve a steady state is different for w on one hand, and for u, v and c on the other hand.     

Numerical studies of heterogeneous reaction in stagnation flows using one-dimensional and two-dimensional Cartesian models

Flow over a thin strip is one of the major experimental configurations in the study of catalytic combustion. 1D laminar stagnation-flow models are generally employed to investigate the catalytic combustion characteristics in this experimental configuration. In this study, a 2D Cartesian model is developed to examine the conditions under which 1D models are applicable. The results show that the 1D model is only appropriate in the experimental configurations with a length-to-width ratio less than 1 to 3 (depending on the flow conditions). The 1D model failed because of the neglecting of transverse diffusive mass transfer (at Re < 30) and of the oversimplified convective mass transfer (at Re > 60). The calculations of the 1D and 2D models are also compared against the OH measurements performed in a typical stagnation-flow reactor with a length-to-width ratio of 16. The results show that the computations of the 2D model are in better agreement with the experimental data.     

Improvement of dehydrogenation performance by adding CeO2 to α-AlH3

The α-AlH₃ + nCeO₂ (n = 0.5, 1 and 2, mol%) composite materials were prepared by ball milling, and the phase composition and dehydrogenation performance of the composites were investigated. The results revealed that α-AlH₃ doped with CeO₂ could effectively decrease the dehydrogenation temperature. The dehydrogenation onset temperature of α-AlH₃ + 2 mol% CeO₂ dropped to 106 °C, which was significantly reduced by 24.3% compared with pure α-AlH₃. At 100 °C, the α-AlH₃ + 2 mol% CeO₂ composite released 3.8 wt% hydrogen within 100 min, while the pure α-AlH₃ released only 0.12 wt% hydrogen in the same duration. Kissinger analysis indicated that apparent activation energy for hydrogen desorption of α-AlH₃ was significantly decreased with CeO₂ doping. The improvement of dehydrogenation performance was due to the finely dispersed CeH_2+x, which was formed by the reaction between CeO₂ and α-AlH₃.     

Linear analysis of an aerothermal instability occurring in diffusion-controlled premixed catalytic combustion

The onset of the unstable temperature distribution which may appear in plane axisymmetric catalytic burner is studied. The instability mechanism is assumed to be related with the temperature dependence of the viscosity, thus with the pressure drop in the porous combustor, governed by Darcy’s law. An area e.g., of lower temperature (dark zone) characterised by a smaller value of the kinetic viscosity gives rise to a locally increased gas flow mass velocity, the pressure drop remaining constant over the burner cross-section. The locally increased mass velocity produces an enhanced cooling of the area, whereby heat conduction from the hotter surrounding area tends to restore a homogeneous temperature distribution. A linear analysis of this thermal instability mechanism is carried out and yields a simple analytic solution for the state of neutral stability.     

Investigation into a catalytically controlled reaction gasifier (CCRG) for coal to hydrogen

Energy demands will increase as industrialized nations strive to maintain progress and productivity gains and as developing nations increase their consumption and productivity. One direction that is evolving to satisfy the demand while minimizing environmental impacts is to move toward a hydrogen economy. For the foreseeable future, the majority of these demands will be met through the increased usage of fossil fuels. One of the most abundant and readily available fuels is coal. This realization has raised some questions about the responsible use of such a fuel and as such it is critical that a Greenhouse Gas Management strategy/technology be developed to forestall projected global warming and its impacts.