导向喷动流化床生物质快速热解技术

综述了生物质在导向喷动流化床反应器中快速热解的理论基础与过程特征,分别从反应机理、流体动力学特性与传热传质、二次裂解、气相和固相停留时间、操作相图、热解产物的收集与处理等方面进行阐述。比较了喷动流化床与其它流化床在快速热解上的异同,概述了导向喷动流化床生物质热解特性, 并提出了导向喷动流化床生物质快速热解技术的发展方向。     

生物质快速热解制油试验及流程模拟

使用自主研发的流化床热解反应器对生物质热解制油进行实验研究,通过对不同实验温度450、500、525、550、580、610℃下得到的目标产物进行分析,得到了反应温度对生物油产率的影响规律。实验表明：550℃时,最大液体产率为42.5%（质量）;实验得到的不可冷凝气体的组分以CO、CO₂、CH₄和H₂为主,气相产物产率约为37.7%（质量）。在实验基础上,利用Aspen Plus流程模拟软件,建立了生物质热解制油工艺模拟流程,模拟分析了热解温度对生物油产率的影响,结果表明该模型能准确模拟实际热解过程,具有较好的适用性和可靠性。     

生物质快速热解技术现状

生物质能源是可再生能源的重要组成部分,有丰富的资源和低污染的特点,它的开发与利用已成为21世纪研究的重要课题。本文概述了生物质转化利用的方法,并重点阐述了生物质热化学转化法中的快速热解技术,同时综述了国内外快速热解反应器的现状,以及其产物———生物油的收集与特征分析,并提出了我国在快速热解研究方面应采取的有关措施。     

Preparation of Hydrogen through Catalytic Steam Reforming of Bio-oil

Hydrogen was prepared via catalytic steam reforming of bio-oil which was obtained from fast pyrolysis of biomass in a fluidized bed reactor. Influential factors including temperature, weight hourly space velocity (WHSV) of bio-oil, mass ratio of steam to bio-oil (S/B) as well as catalyst type on hydrogen selectivity and other desirable gas products were investigated. Based on hydrogen in stoichiometric potential and carbon balance in gaseous phase and feed, hydrogen yield and carbon selectivity were examined. The experimental results show that higher temperature favors the hydrogen selectivity by H2 mole fraction in gaseous products stream and it plays an important role in hydrogen yield and carbon selectivity. Higher hydrogen selectivity and yield, and carbon selectivity were obtained at lower bio-oil WHSV. In catalytic steam reforming system a maximum steam concentration value exists, at which hydrogen selectivity and yield, and carbon selectivity keep constant. Through experiments, preferential operation conditions were obtained as follows: temperature 800~850℃, bio-oil WHSV below 3.0 h-1, and mass ratio of steam to bio-oil 10~12. The performance tests indicate that Ni-based catalysts are optional, especially Ni/a-Al2O3 effective in the steam reforming process.     

生物质快速热解液化工艺研究进展

对近期国内外快速热解液化工艺研究进展进行了回顾。分别对生物质原料、反应器类型、生物质炭与灰分的分离、热解产物收集以及生物油产品特性等方面的研究进行了论述和分析,指出了生物质快速热解液化的研究方向。     

碱土金属氧化物基催化剂催化热解生物质研究进展

快速热解是生物质高效转化利用的重要方法之一,然而其目标产物生物油因含氧量高、组分复杂等不足而难以直接利用。通过在热解体系中引入碱土金属氧化物基催化剂,可以将热解产物中的氧元素以CO₂和H₂O等方式脱除,从而实现生物油品质的提升。总结了典型碱土金属氧化物基催化剂对生物质催化热解过程中发生的酮基化、羟醛缩合、开环和侧链断裂反应及机理,讨论了催化剂类型（CaO、MgO、基于碱土金属氧化物的分子筛和活性炭等）、生物质原料、温度、催化剂用量、停留时间、催化方式、催化剂失活等因素对生物油产率与品质的影响,并对生物质催化热解制备高品质生物油及其应用进行了展望。     

10 kWth级串行流化床中木屑化学链燃烧试验

设计并建立了10 kW_th级串行流化床化学链燃烧反应器系统,以NiO/Al₂O₃为载氧体,在该系统上进行生物质（松木木屑）化学链燃烧分离CO₂的试验研究,探讨了燃料反应器温度T、水蒸气/生物质比率S/B对两个反应器（空气反应器和燃料反应器）气体产物组成以及燃烧效率的影响。试验结果表明,燃料反应器温度是影响生物质化学链燃烧过程的重要因素,随着温度的升高,燃料反应器气体产物中CO₂浓度不断上升,CH4浓度显著降低,CO浓度先升高而后迅速下降;较高的反应器温度有助于燃烧效率的提高。随着S/B的增加,燃料反应器气体产物中CO和CH₄浓度均会增大,CO₂浓度以及燃烧效率有所降低。在100 h的连续试验过程中,采用共沉淀法制备的NiO/Al₂O₃载氧体展现出良好的氧化-还原性能和较强的持续循环能力,是生物质化学链燃烧理想的载氧体。     

生物质快速裂解液化技术的研究进展

综述了生物质能转化的技术途径,生物质热裂解的４种方式,着重介绍了生物质快速裂解直接液化的各种著名工艺和生物质燃料油的特点及其开发和利用。指出了目前生物质裂解技术以及生物质油深加工的难点和发展方向。     

响应面法优化竹材热裂解制备生物油的工艺研究

为了提高竹材生物质流化床快速热裂解制备生物油产率,利用响应面法优化其最佳工艺条件.试验选择热裂解温度(450～550℃)、气相停留时间(1.5～2.5 s)和物料粒径(0.18 ～0.22 mm)三因素作为独立变量,采用中心组合设计建立模型和考察上述因素对生物油收率的影响.结果表明三因素对生物油收率具有显著影响而它们之间的交互作用均不显著.依据所得到的模型,在各因素设定范围内获得的最佳工艺条件为:热裂解温度519.0℃、气相停留时间2.1s、物料粒径0.18mm,生物油理论收率为58.17％.在该条件下进行的三次重复试验,竹材生物油的实际平均收率为57.85％,与模型预测值58.17％无显著差异.响应面法简便、高效,优化结果能给生物质流化床快速热裂解制备生物油制备工艺提供一定的参考.     

生物质微波热解产生物油的影响因素研究进展

生物质作为可再生资源具有低成本、分布广泛且易得等优点,生物质能的开发利用可有效缓解能源压力,减少环境污染。微波热解技术是生产燃料油和高附加值化学品的有效方法之一,与传统的热解相比,微波热解具有加热速率快、均匀性好、选择性加热、节能与易于控制等优点。在简单分析微波热解产物分布的基础上,详细综述了近年来微波热解生物油产率的影响因素,主要包括热解温度、功率、吸波剂、催化剂、原料预处理、加热时间、原料性质和物料尺寸等因素;最后,总结和展望了微波技术在生物质催化热解制备生物油领域应用中存在的问题、解决途径和发展前景。     

生物质裂解油催化裂解精制

在HZSM-5催化剂存在的条件下，生物质裂解油在固定床反应器内进行了催化裂解. 实验研究了精制生物油的产率受温度、催化剂粒度、质量空速、溶剂诸因素的影响程度. 在较佳的反应条件下，即质量空速3.7 h-1、温度380℃时，获得了较高的精制生物油产率(44.68%). 产物分析表明，精制油中的含氧化合物如有机酸、酯、醇、酮、醛的含量大大降低，而不含氧的芳香族碳氢化合物和多环芳香碳氢化合物含量有所增加.     

生物质油改性方法研究进展

生物质快速裂解液体产物生物油(简称生物质油),具有水含量高、氧含量高、热值低、粘度大、热不稳定和化学不稳定等特性,在一定程度上影响了其广泛应用,因此必须通过精制改善其品质.按生物质快速裂解的反应过程,将提高生物质油品质的方法归纳为三类:第一类(反应前),快速裂解反应前,原料脱水和脱碱金属处理;第二类(反应中),快速裂解反应过程中,生物质油蒸汽不经冷凝直接改质;第三类(反应后),快速裂解反应完成后,采用对收集到的生物质油催化加氢、催化裂解、催化酯化、乳化、添加溶剂或添加抗氧化剂等方法进行改质.     

Hydrodynamics of a Novel Biomass Autothermal Fast Pyrolysis Reactor: Flow Pattern and Pressure Drop

A novel biomass, autothermal, fast pyrolysis reactor with a draft tube and an internal dipleg dividing the reactor into two interconnected beds is proposed. This internally interconnected fluidized beds (IIFB) reactor is designed to produce high‐quality bio‐oil using catalysts. Meanwhile, the pyrolysis by‐products, i.e., char, coke and non‐condensable gases, are expected to burn in the combustion bed to provide the heat for the pyrolysis. On the other hand, the catalysts can be regenerated simultaneously. In this study, experiments on the hydrodynamics of a cold model IIFB reactor are reported. Geldart group B and D sand particles were used as the bed materials. The effects of spouting and fluidizing gas velocities, particle size, static bed height and the total pressure loss coefficient of the pyrolysis bed exit, on the flow patterns and pressure drops of the two interconnected beds are studied. Six distinct flow patterns, i.e., fixed bed (F), periodic spouted/bubbling bed (PS/B), spouted bed with aeration (SA), spout‐fluidized bed (SF), spout‐fluidized bed with slugging (SFS) and spouted bed with backward jet (SBJ) are identified. The investigations on the pressure drops of the two beds show that both of them are seen to increase at first (mainly in the F flow pattern), then to decrease (mainly in the PS/B and SA flow patterns) and finally to increase again (mainly in the SA and SF flow patterns), with the increase of the spouting gas velocity. It is observed that a larger particle size and lower static bed height lead to lower pressure drops of the two beds.     

稻壳快速热解制取生物质油的试验研究

目前生物质快速热解高温热解气主要利用间壁式冷却器进行冷凝,容易造成冷却管道的结焦堵塞问题,本试验根据流化床稀相输送特点、生物质的热解特性以及生物质油的冷凝收集特点,设计了生物质快速热解反应装置,改进生物质物快速冷凝系统,以稻壳为原料进行快速热解制取生物质油的试验研究,分别考察单因素反应温度、流化气量以及进料速度对生物质油产率的影响。试验表明:稻壳热解气能够快速顺利地得到冷凝,反应系统能够连续顺利运行,随着反应温度、流化气量、进料速度的增大,生物质油的产率都呈现先增大后减小的趋势。另外对产出的生物质油用气质联用设备进行了成分分析,得出了生物质油的主要成分,其中酸类、酮类、脂类以及酚类的含量相对较高。     

Hydrogen from biomass-production by steam reforming of biomass pyrolysis oil

Thermo-conversion of biomass is one of the leading near-term options for renewable production of hydrogen and has the potential to provide a significant fraction of transportation fuel required in the future. We propose a two-step process that starts with fast pyrolysis of biomass, which generates high yields of a liquid product, bio-oil, followed by catalytic steam reforming of bio-oil to produce hydrogen. A major advantage of such a concept results from the fact that bio-oil is much easier and less expensive to transport than either biomass or hydrogen. Therefore, the processing of biomass and the production of hydrogen can be performed at separate locations, optimized with respect to feedstock supply and to hydrogen distribution infrastructure. This approach makes the process very well suited for both centralized and distributed hydrogen production. This work demonstrates reforming of bio-oil in a bench-scale fluidized bed system and provides hydrogen yields obtained using several commercial and custom-made catalysts.     

矿物质对生物质热解的影响及其解决方案

通过对一年生和多年生的生物质及其热解油组成的分析,探讨了影响生物质热解油组成及其酸度的重要因素是生物质中的金属盐矿物质,金属盐舍量增加,致使热解油收率降低、酸含量增加。对现有的生物质热解工艺进行了比较和评述,提出了消除金属矿物质影响和含酸少的新型生物质热解工艺。     

Hydro-pyrolysis of lignocellulosic biomass over alumina supported Platinum,Mo<Subscript>2</Subscript>C and WC catalysts

In-line hydro-treatment of bio-oil vapor from fast pyrolysis of lignocellulosic biomass (hydro-pyrolysis of biomass) is studied as a method of upgrading the liquefied bio-oil for a possible precursor to green fuels. The nobel metal (Pt) and non-noble metal catalysts (Mo₂C and WC) were compared at 500 °C and atmospheric pressure which are same as the reaction conditions for fast pyrolysis of biomass. Results indicated that under the pyrolysis conditions, the major components, such as acids and carbonyls, of the fast pyrolysis bio-oil can be completely and partially hydrogenated to form hydrocarbons, an ideal fossil fuel blend, in the hydro-treated bio-oil. The carbide catalysts perform equally well as the Pt catalyst regarding to the aliphatic and aromatic hydrocarbon formation (ca. 60%), showing the feasibility of using the cheap non-noble catalysts for hydro-pyrolysis of biomass.

Open image in new window

     

Flash co-pyrolysis of biomass with polylactic acid. Part 1: Influence on bio-oil yield and heating value

High amounts of water present in bio-oil are one of the major drawbacks for its utilisation as a fuel. One technology that shows the potential to satisfy the demand for bio-oil with a reduced water content is the flash co-pyrolysis of biomass with polylactic acid, PLA. The influence of PLA on the pyrolysis of willow is investigated with a semi-continuous home-built pyrolysis reactor. Flash co-pyrolysis of willow/PLA blends (10:1, 3:1, 1:1 and 1:2) show synergetic interaction. A higher bio-oil yield and a lower water content as a function of the willow/PLA ratios are obtained. Among the tested blends, the 1:2 willow/PLA blend shows the most pronounced synergy: a reduction in the production of pyrolytic water of almost 28%, accompanied by an increase of more than 37% in the production of water-free bio-oil. Additionally, PLA shows to have a positive influence on the energetic value of the bio-oil produced and on the resulting energy recuperation.     

Model development and validation: Co-combustion of residual char, gases and volatile fuels in the fast fluidized combustion chamber of a dual fluidized bed biomass gasifier

A one-dimensional steady state model has been developed for the combustion reactor of a dual fluidized bed biomass steam gasification system. The combustion reactor is operated as fast fluidized bed (riser) with staged air introduction (bottom, primary and secondary air). The main fuel i.e., residual biomass char (from the gasifier), is introduced together with the circulating bed material at the bottom of the riser. The riser is divided into two zones: bottom zone (modelled according to modified two phase theory) and upper zone (modelled with core-annulus approach). The model consists of sub-model for bed hydrodynamic, conversion and conservation. Biomass char is assumed to be a homogeneous matrix of C, H and O and is modelled as partially volatile fuel. The exit gas composition and the temperature profile predicted by the model are in good agreement with the measured value.     

生物质快速热解与生物油精制研究进展

本文综述了生物质快速热解与生物油精制工艺。阐述了快速热解的机理、工艺以及影响因素;介绍了生物油的组分与特性;概括了目前生物油精制的3种工艺:催化加氢、催化裂化以及乳化技术,评价了这3种工艺的机理、效果以及优缺点,并从3个方面预测了该课题未来的研究方向。