基于等转化率法的生物焦CO_2气化反应动力学参数研究

利用热重分析仪在800~950℃对稻秆焦和木屑焦CO2等温气化过程进行了研究。分别采用等转化率法和随机孔模型求解了稻秆焦和木屑焦气化反应的动力学参数。通过等转化率法发现,随着碳转化率的增加,反应活化能随着碳转化率的升高而增大,稻秆焦和木屑焦在碳转化率为0.02时刻(即接近初始时刻)的活化能分别为157.2 k J/mol和166.4 k J/mol;采用随机孔模型计算得到稻秆焦和木屑焦的活化能分别为155.1 k J/mol和165.5 k J/mol,与等转化率法求得的碳转化率为0.02时刻的活化能接近,表明随机孔模型可以准确地描述稻秆焦和木屑焦的气化特性。同时发现,同一气化温度下,稻秆焦的结构参数大于木屑焦的结构参数;不同温度下的同一焦炭的结构参数f与对应的气化温度存在良好的指数关系。最后结合结构参数f与气化温度的指数关系表达式,得出稻秆焦和木屑焦的等温气化反应动力学随机孔模型速率表达式。     

不同种类生物质热解残焦的CO_2气化研究

在常压固定床反应器中,以不同种类生物质热解残焦为原料进行CO_2气化制取CO研究,并与煤焦的CO_2气化效果进行对比。实验在气化温度700~1000℃条件下进行,研究热解残焦制备温度、生物质热解残焦种类、气化温度对气化产气中CO浓度、热解残焦转化率的影响。研究结果表明:制备温度为550℃的生物质热解残焦的气化效果优于600℃时;生物质热解残焦的气化效果明显优于煤焦,且垃圾焦气化效果最佳;污泥焦、垃圾焦、秸秆焦的最佳气化温度为900℃,煤焦的最佳气化温度为1000℃。     

生物质半焦CO2气化反应动力学研究

采用热天平研究生物质半焦CO2气化反应动力学特性。考察半焦粒径、热解制焦温度以及热解制焦气氛对气化反应碳转化率的影响。采用随机孔模型、未反应芯缩核模型和混合模型对生物质半焦气化反应速率随碳转化率变化的趋势进行拟合,并求出半焦气化的动力学参数,结果表明随机孔模型的拟合效果最好。     

生物质半焦气化的反应动力学

利用热重分析仪研究了CO2气氛下的生物质半焦的反应性。研究发现，所研究的4种生物质半焦都表现出了相同的反应性趋势。其反应性随着转化率的增加而增加。这可能是由于生物质焦样中的碱金属含量，尤其是钾的含量较高的原因。对比生物质气化反应动力学参数研究表明，4种焦样的气化行为可以用收缩核模型来描述，并求出了4种生物质焦样的反应动力学参数。在不同的CO2分压下进行了花生壳焦样的反应性实验研究，发现焦样的反应性正比于反应气体浓度，求出了花生壳焦样的反应动力学方程式。     

典型农业生物质催化气化反应动力学特性研究

以CaO、MgO和Fe2O3为催化剂,用程序升温热重法对典型农业生物质催化气化特性及反应动力学进行了研究.利用均相反应模型和缩核反应模型对转化率与温度的关系进行了拟和计算,得到了谷壳样在4种不同二氧化碳气化条件下热解阶段及焦炭气化阶段的活化能和指数前因子.结果表明,在820～1000℃区间内,添加CaO的谷壳样表观活化能比谷壳的大;而添加MgO和Fe2O3的谷壳样表观活化能与谷壳的相比,分别下降了32.6%和17.9%以上,可以看出3种催化剂催化活性大小顺序为MgOFe2O3CaO,活化能区间范围为15.25～123.74kJ/mol.研究表明在低温区间(热解阶段),反应机理更趋向于均相反应模型,而在高温区间(气化阶段),反应机理更趋向于缩核反应模型.最后给出了谷壳在热解阶段及焦炭气化阶段的反应动力学方程.     

制焦条件对稻秆与大同烟煤共气化特性影响的实验研究

在自行设计搭建的气化实验装置上进行不同制焦条件下稻焦-大同烟煤焦的混合焦样气化特性实验。对比不同工况下气化特性曲线发现:在本实验工况下,稻-煤焦样经机械掺混后的气化特性优于相同工况下浸渍混合后的气化特性;混合后制焦所得焦样气化特性优于先制焦后混合处理所得焦样的气化特性;煤和稻焦热解温度对混焦的气化特性影响不同,热解温度对生物质焦以及随后气化特性的影响大于对煤焦的影响;无论是稻焦还是煤焦,热解时间对混焦的气化特性影响均不明显。通过上述热解条件对稻-煤气化特性的影响,为煤与生物质共气化的工业应用提供指导。     

生物质半焦高温水蒸汽气化反应动力学的研究

利用高温定碳炉研究了1000~1300℃条件下水蒸汽与生物质半焦的反应过程以及反应性.研究结果表明:高温条件下有利于缩短反应时间,提高CO产率;3种生物质半焦的反应性表现出相同的趋势,当转化率在0.3~0.4之间时,生物质半焦的反应性达到最大值,随后又降低;含碳量及灰中金属氧化物含量对其反应性存在一定的影响;生物质半焦的水蒸汽气化行为可以用未反应收缩核模型来描述.在水蒸汽分压不变的情况下,求出了3种生物质半焦的动力学参数,并对比了不同转化率时的动力学参数.     

掺混生物质焦和煤焦共气化的热重分析

采用热重分析法对煤焦和几种生物质焦及其混合物的气化过程及动力学规律进行了分析,分析结果表明煤焦的失重与生物质焦相比差别明显,混合物中的生物质焦所占比重越大、发生失重的温度越低。进一步采用Coats—Redfern方法对样品气化过程进行了动力学分析,得到了生物质焦、煤焦及其混合物表观活化能。     

基于ASPEN PLUS模拟生物质气流床气化工艺过程

基于ASPEN PLUS模拟平台,对热解后半焦气化与生物质原料直接气化分别进行了模拟计算,得出如下结论:热解方法作为生物质气流床气化工艺的前处理手段是可行的。热解终温为300℃时对气流床气化是最合适的;O/C摩尔比在0.9～1.1之间比较合适;气化温度和碳转化率随着O/C摩尔比的增加而升高;对于300℃半焦进行气化,空气温度预热到550℃比较合适,气化温度可达到1056℃,煤气热值可达到5958kJ/Nm~3,碳转化率也可达到99.59%。     

制备温度对芒草热解焦CO2气化反应动力学的影响

利用热重分析仪进行了芒草热解焦与CO_2气化反应实验研究,选取均相反应模型、颗粒反应模型和随机孔模型计算了芒草热解焦的CO_2气化反应动力学参数,探讨了3种动力学模型的适用性.为进一步探讨制备温度对热解焦CO_2气化反应的影响机理,利用扫描电镜(SEM)和Brunauer-Emmett-Teller(BET)分析了芒草热解焦的孔隙结构和表面形态.研究表明,随着制备温度的升高,热解焦表面结构被逐渐加深,表面粗糙度提高,比表面积相对增大,制备温度为600℃的热解焦具有最大的微孔容积与总孔容积之比,使得其更容易发生气化反应;制备温度为400℃时,芒草热解焦在3种模型下具有最小的平均活化能,随机孔模型对芒草热解焦实验数据拟合效果最好,其模拟的相关性系数R2均大于0.97.     

Mechanisms of Thermochemical Biomass Conversion Processes. Part 2: Reactions of Gasification

Abstract

Gasification as a thermochemical process is defined and limited to combustion and pyrolysis. The gasification of biomass is a thermal treatment which results in a high proportion of gaseous products and small quantities of char (solid product) and ash. Biomass gasification technologies have historically been based upon partial oxidation or partial combustion principles, resulting in the production of a hot, dirty, low Btu gas that must be directly ducted into boilers or dryers. In addition to limiting applications and often compounding environmental problems, these technologies are an inefficient source of usable energy. The main objective of the present study is to investigate gasification mechanisms of biomass structural constituents. Complete gasification of biomass involves several sequential and parallel reactions. Most of these reactions are endothermic and must be balanced by partial combustion of gas or an external heat source.     

浑源煤焦CO_2气化反应的影响因素及动力学特性分析

研究了热解温度、热解时间以及气化温度对浑源煤焦CO2气化反应的影响,并获得了气化反应的动力学模型.结果表明：浑源煤焦的气化活性随热解温度的提高而降低;每个热解温度都对应着一个最佳热解时间,且存在最佳热解时间随温度升高而缩短的趋势;提高气化温度能够显著提高煤焦的气化反应性能,气化温度对气化反应的影响大于热解温度的影响;低温度煤焦的气化活性随气化温度的提高而增加更为剧烈;900℃及以上的高温使活性点数增加,从而使煤焦间的活性差距分布均匀;浑源煤焦的气化反应适宜用体积模型来描述,所求取的动力学参数之间存在补偿效应,其等动力学温度约为1 199.6℃.     

Two-step steam pyrolysis of biomass for hydrogen production

In this study, different char based catalysts were evaluated in order to increase hydrogen production from the steam pyrolysis of olive pomace in two stage fixed bed reactor system. Biomass char, nickel loaded biomass char, coal char and nickel or iron loaded coal chars were used as catalyst. Acid washed biomass char was also tested to investigate the effect of inorganics in char on catalytic activity for hydrogen production. Catalysts were characterized by using Brunauer–Emmet–Teller (BET) method, X-ray diffraction (XRD) analyzer, X-ray fluorescence (XRF) and thermogravimetric analyzer (TGA). The results showed that the steam in absence of catalyst had no influence on hydrogen production. Increase in catalytic bed temperature (from 500 °C to 700 °C) enhanced hydrogen production in presence of Ni-impregnated and non-impregnated biomass char. Inherent inorganic content of char had great effect on hydrogen production. Ni based biomass char exhibited the highest catalytic activity in terms of hydrogen production. Besides, Ni and Fe based coal char had catalytic activity on H₂ production. On the other hand, the results showed that biomass char was not thermally stable under steam pyrolysis conditions. Weight loss of catalyst during steam pyrolysis could be attributed to steam gasification of biomass char itself. In contrast, properties of coal char based catalysts after steam pyrolysis process remained nearly unchanged, leading to better thermal stability than biomass char.     

生物质气化气中焦油非催化裂解实验研究

生物质气化是一种环境友好的新能源利用技术,焦油作为生物质气化的副产物,是限制气化技术发展的主要因素.试验针对生物质气化产出气中焦油在700～1 000℃裂解温度区间的裂解特性进行了分析,并提出了焦油裂解产气率的概念.试验表明,焦油裂解气可以成为生物质气化气的有效的能量补充,而且随着裂解温度的升高,焦油裂解产气率增加,焦...     

Effect of pore structure on CO2 gasification reactivity of biomass chars under high-temperature pyrolysis

The CO₂ gasification reactivity of pine sawdust chars (PS char) obtained from the different high-temperature pyrolysis is studied based on non-isothermal thermogravimetric method. Results show that the order of gasification reactivity is PS char-1073 > PS char-1273 > PS char-1473. Under the effect of high-temperature pyrolysis, the surface structure of biomass char is gradually destroyed and the pore structure parameters of specific surface area, total pore volume and average pore diameter increase. By means of the N₂ adsorption-desorption isotherms, it is seen that biomass char has more micro- and mesoporous at higher pyrolysis temperature. Besides, the PS char-1073 mostly has rich closed cylinder pores and parallel plate pores, and the PS char-1273 and PS char-1473 have plentiful open cylinder pores and parallel plate pores. An increase of pyrolysis temperature contributes to the development of porosity and improves diffusion path, which promotes the gasification reactivity. But, its effect on the decline of active site hinders the gasification reactivity. What's more, the kinetic model of distributed activation energy model (DAEM) is applied to calculate activation energy and pre-exponential factor with the integral and differential methods. The calculation results of integral method is more accurate and precise because the differential method is more sensitive than integral method for experimental noise. There is a compensation effect in the CO₂ gasification process.     

加压喷动流化床煤气化数值模拟

建立了基于CFD的三维非稳态喷动流化床煤气化动力学模型.此模型包含气固流动模型,煤的挥发分析出模型,焦炭气化反应模型和气相间的均相反应模型等子模型.焦炭的非均相反应速率由气体扩散和化学反应动力学共同控制.气体均相反应可以作为二级反应来处理.将试验结果和模拟的计算结果进行了对比,结果表明,入口中心喷动区的温度最高,温度场沿床高方向逐渐降低.煤气质量在加压后有了明显提高.验证的结果表明此CFD模型可以用来预测煤气化的反应过程.     

煤气化过程的神经网络直接辨识

煤在水蒸汽环境中气化时,煤的热解和焦的气化同时发生,两个过程有一些相同的产物,因此无法通过测量确定两个过程各自的进行情况。如果用煤的热解模型和焦的气化模型共同描述煤在水蒸汽中的气化过程,由于缺乏必要的数据,难以保证模型参数的合理性。要直接描述煤热解和焦气化形成的综合过程,传统的数学回归方法又难以胜任。本文用神经网络方法对煤在水蒸汽中气化的综合过程进行了直接辨识,取得了较好的模拟效果,并对煤在水蒸汽中的气化过程有了更深入的了解,为煤气化过程的“活性焦比”模型提供了支持。     

Kinetic model of biomass gasification

A kinetic model for biomass gasification is developed based on the mechanism of surface reactions. The apparent rate constants are computed by minimizing the differences between experimental data and theoretical results for different residence times and different temperatures. The kinetic model is validated by comparing experimental data with the theoretical results for different equivalence ratios; the simulations agree well with the experimental data. Simulations modeling the influence of char particle size on the time required to achieve 90% carbon conversion agree with the results of tests performed by other investigators. Simulations are performed to evaluate the effects of the following parameters on biomass gasification: (a) type of oxidant, (b) residence time, (c) char particle size, (d) temperature, (e) pressure, (f) equivalence ratio, and (g) moisture.