生物质在高频耦合等离子体中的热解气化研究

采用高频电容耦合等离子体热解技术对生物质原料进行了热解气化试验，研究气体产物产率、成分随反应条件的变化规律。反应在3000-8000Pa的真空范围内进行，热解温度为1000～2000K。该技术可大幅度提高生物质气的热值及产率，本试验中产气率达到了66％以上，并且还有提高的潜力。     

废轮胎中试回转窑热解气特性及能耗分析

在无氧气氛下用中试回转窑热解系统对废轮胎进行了热解试验,热解气用气相色谱仪进行分析,轮胎热解气体主要包含CO、CO2、CH4、C2H4、C2H6、C3H8、C4H8,以及它们派生的不饱和烃。热解温度的不同,回转窑微负压运行时,挥发分在窑内的停留时间不同,气体的成分有所变化。OH4在500℃达到最高,C2H4则在550℃产量最大,虽然温度的提高有利于大分子烃类二次裂解,但由于在窑内停留时间较短,产量反而在较高的热解温度65℃达到最大值,超过10％计算表明,热解气可以作为轮胎热解的热源。     

活化和热解气氛对半焦基活性炭性能的影响

以煤炭分级转化半焦为原料，采用廉价烟气活化法制备适用于小分子污染物吸附脱除的活性炭，分别从活化工况、活化气氛、热解气氛三方面探究并对比了其物化性质和吸附性能。结果表明：分级转化半焦经烟气活化，在最优工况下可以得到比表面积为798.27 m²/g的活性炭，其微孔体积为0.327 cm³/g，碘值可达1056.84 mg/g。当固定烟气气氛中两种组分的浓度时，活性炭的碘值、比表面积和微孔结构随第三种组分浓度的增加呈现先升后降趋势。对比氮气热解半焦和模拟煤炭分级转化多联产系统的煤气热解半焦所制的活性炭，煤气半焦活性炭比表面积、微孔体积和碘值均有所提高，同时可以显著降低能耗，最优活化时间降低50%，经济性较好。     

生物质热解气重整试验平台设计与试验

针对热解气焦油含量高、热值低的问题,文章基于焦油催化裂解和热解气气化重整原理,提出了生物质热解气重整工艺路线,并设计、搭建了生物质热解气重整试验平台,该试验平台主要由热解、催化重整、产品收集、控制系统等组成。以玉米秸秆为原料,在该试验平台上开展了热解气重整试验,试验结果表明:在以石英砂作为惰性材料的条件(高温裂解)下,热解气产率为33.8%,焦油转化率为64.3%;在玉米秸秆炭催化裂解条件下,热解气产率为37.8%,焦油转化率72.6%;高温裂解和催化裂解条件下生成的热解气的热值均达到了17MJ/m3以上。热解气重整试验平台达到了设计目的,为热解气重整研究提供了理论支持和技术支撑。     

污泥热解气/氨旋流火焰燃烧特性

污泥热解气因难以被有效利用导致了大量的能源浪费,而其中所含的氢气、甲烷等可燃组分可有效提升氨燃料的燃烧性能。对污泥热解气掺氨旋流火焰的结构及燃烧特性进行分析,基于化学发光法,通过实验考察当量比、掺氨比对火焰结构的影响。结果表明,旋流燃烧火焰中的OH^*在化学当量条件(φ=1.0)下辐射强度最大,CH^*在富燃条件(φ=1.2)下辐射强度最大,OH^*可以对火焰稳定性进行更好地表征;污泥热解气/氨气混合燃料中,随着氨气比例增大,旋流火焰稳定性下降。     

不同热转化条件下秸秆灰的熔融特性研究

生物质灰熔融特性的影响因素众多,为了系统地研究生物质灰在不同热转化条件下的熔融特性,以小麦秸秆为例,系统研究了反应温度、热解气氛、O₂体积分数等变量对麦秆灰熔融特征温度的影响规律,探究了麦秆灰的熔融特性。结果表明：随着热解温度升高,灰熔融特征温度升高,这是因为温度升高,碱金属随之挥发,而碱金属含量越低,熔融温度越高;随着气化温度升高,软化温度、半球温度、流动温度变化都不明显,但变形温度明显升高。温度的改变会造成麦秆灰残余矿物质的变化,低温物质转变为高温物质,熔融特征温度进而发生变化。反应气氛改变,麦秆灰的熔融特征温度也会发生变化。在O₂体积分数为6%～18%时,灰熔融特征温度并无明显变化。     

中药渣循环流化床热解气化试验

对含水率为20%的六味地黄丸药渣进行气化试验研究,采用空气预热装置将气化剂空气由常温加热为约200℃的热空气,研究了在两种不同温度的气化剂条件下,空气当量比ER对气化特性的影响,并讨论了水蒸气配比S/B对气化特性的影响。结果表明:随着空气当量比的增加,循环流化床炉内气化温度逐渐升高,燃气热值和燃气中焦油含量均逐渐降低,气化效率则先增大后减小。当气化剂为常温冷空气时,理想空气当量比为0.26~0.30,燃气热值为4 400~5 000 kJ/m3,气化效率为67%~70%;气化剂为200℃热空气时,理想空气当量比为0.24~0.29,燃气热值为4 700~5 700 kJ/m3,气化效率为73%~75%;随着水蒸气配比的增加,炉内温度逐渐降低,焦油含量逐渐升高,燃气热值先增加后减小,当S/B为0.4时,燃气热值可达6 100 kJ/m3。研究结果可为中药渣的资源化处理与利用提供参考。     

生物质水蒸气气化利用过程数学模型的建立

分析了甘蔗渣的水蒸气气化过程,基于气化过程的物料平衡和化学平衡关系,建立了一种生物质气化过程的数学模型。用该模型模拟计算甘蔗渣在水蒸气氛围下气化后的气体成分,计算结果与试验数据基本相符,尤其在温度950℃之后,计算值和测量值更接近。以甘蔗渣和木薯渣为例,研究该气化模型的特性。甘蔗渣和木薯渣水蒸气气化的最佳水蒸气/燃料值(S/B)分别为0.3和0.2。气化气组分和气化效果随温度和S/B变化的结果表明:提高温度有利于气化反应的进行,提高S/B,可以增加气体产率,气体热值有所降低。     

Oxidative catalytic steam gasification of sugarcane bagasse for hydrogen rich syngas production

Reactive Flash Volatilization (RFV) is an emerging thermochemical method to produce tar free hydrogen rich syngas from waste biomass at relatively lower temperature (<900 °C) in a single stage catalytic reactor within a millisecond residence time. Here, we show catalytic RFV of bagasse using Ru, Rh, Pd, or Re promoted Ni/Al₂O₃ catalysts under steam rich and oxygen deficient environment. The optimum reaction conditions were found to be 800 °C, steam to carbon ratio = 1.7 and carbon to oxygen ratio = 0.6. Rh–Ni/Al₂O₃ performed the best, resulting in highest hydrogen concentration in the synthesis gas at 54.8%, with a corresponding yield of 106.4 g-H₂/kg bagasse. A carbon conversion efficiency of 99.96% was achieved using Rh–Ni, followed by Ru–Ni, Pd–Ni, Re–Ni and mono metallic Ni catalyst in that order. Alkali and Alkaline Earth Metal species present in the bagasse ash and char, that deposited on the catalyst, was found to enhance its activity and stability. The hydrogen yield from bagasse was higher than previously reported woody biomass and comparable to the microalgae.     

Exergy analysis of sugarcane bagasse gasification

The gasification technology has been object of study of many researchers, especially those involved in promoting large-scale electricity generation in sugarcane mills. This paper presents a simplified model for the gasification process based on chemical equilibrium considerations. The model consists in the minimization of the Gibbs free energy of the produced gas, constrained by mass and energy balances for the system. Despite the simplicity of the model, its results are reliable in identifying the tendencies of the working parameters of the system. A parametric study has been carried aiming the verification of the influence of many variables inherent to the model, such as: gasification temperature, moisture content, and air temperature, among others. The results were compared with those found in literature and real systems. Following this parametric study, an exergy analysis has been performed in order to evaluate irreversibilities associated to the process, and the influence of temperature, moisture, charcoal production, and thermal losses on them. Finally, a first attempt to integrate a gasifier into a sugarcane mill was performed, which showed the potential benefits regarding the use of such technology.     

Parametric gasification process of sugarcane bagasse for syngas production

This research focuses on parametric influence on product distribution and syngas production from conventional gasification. Three experimental parameters at three different levels of temperature (700, 800 and 900 °C), sugarcane bagasse loading (2, 3 and 4 g) and residence time (10, 20 and 30 min) were studied using horizontal axis tubular furnace. Response Surface Methodology supported by central composite design was adopted in order to investigate parameters impact on product distribution (i.e., gas, tar and char) and gaseous products (i.e., H₂, CO, CO₂ and CH₄). The highest H₂ fraction obtained was 42.88 mol% (36.91 g-H₂ kg-biomass⁻¹) at 3 g of sugarcane bagasse loading, 900 °C and 30 min reaction time. The temperature was identified as the most influential parameter followed by reaction time for H₂ production and diminishing the bio-tar and char yields. An increase in sugarcane bagasse loading, on other hand, favored the production of bio-tar, CO₂ and CH₄ production. The statistical analysis verified temperature as most significant (p-value 0.0008) amongst the parameters investigated for sugarcane bagasse biomass gasification.     

Combined slow pyrolysis and steam gasification of biomass for hydrogen generation—a review

Hydrogen, the inevitable fuel of the future, can be generated from biomass through promising thermochemical methods. Modern‐day thermochemical methods of hydrogen generation include fast pyrolysis followed by steam reforming of bio‐oil, supercritical water gasification and steam gasification. Apart from the aforementioned methods, a novice technique of employing combined slow pyrolysis and steam gasification can be also engaged to produce hydrogen of improved yield and quality. This review paper discusses in detail about the existing hydrogen generation through thermochemical methods. It elaborates the merits and demerits of each method and gives insight about the combined slow pyrolysis and steam gasification process for hydrogen generation. The paper also elaborates about the various parameters affecting integrated slow pyrolysis and steam gasification process. Copyright © 2014 John Wiley & Sons, Ltd.     

污泥热解残渣水蒸气气化制取富氢燃气

采用固定床反应器,进行了污泥热解残渣水蒸气气化制取富氢燃气的研究。考察了反应温度、固相停留时间、水蒸气流量及催化剂对气化效果及气体产物组成的影响。结果表明:随着反应温度的升高,气体产率由0.096 7 m3/kg逐渐增加到0.460 0 m3/kg,燃气中H2含量由17.87%逐渐增加到52.44%;在最佳固相停留时间为15min时,气体产率达到0.540 m3/kg;最佳水蒸气流量为1.19 g/min,此时产气量达到最大值0.61 m3/kg,H2含量为64.7%;添加催化剂有利于气体中H2含量的提高。     

Catalytic fast pyrolysis of sugarcane bagasse pith with HZSM-5 catalyst using tandem micro-reactor-GC-MS

Fast pyrolysis of biomass is praised as an efficient and feasible process to selectively convert lignocellulosic biomass into bio-fuels and bio-chemicals. Pith of sugarcane bagasse could be an attractive lignocellulosic waste from depithing process from pulp and paper mill, which can utilize for production of biofuel and added value products. In this study, we employed a tandem micro-reactor coupled with gas chromatography-mass spectroscopy to investigate the products distribution from pith of sugarcane bagasse via catalytic fast pyrolysis. In the operating conditions, pyrolysis temperature and HZSM-5 catalyst had significant effect on products and distributions. An increase in the pyrolysis temperature from 400°C to 550°C led to an increase in the yield of phenolic compounds (6.3%, w/w%), followed decrease at higher temperature. The maximum carboxylic acids (10.6%) and furfural (3.5%) were obtained at lower temperature. At presence of HZSM-5 catalyst, the selectivity of aromatics such as benzene, toluene, indene, and naphthalene were improved.     

Assessment of sugarcane bagasse gasification in supercritical water for hydrogen production

Sugarcane bagasse is one of the major resources of agricultural biomass waste in the world. In this work, supercritical water gasification characteristics of sugarcane bagasse were investigated. The effect of temperature (600–750 °C), concentration (3–12 wt%), residence time (5–20 min) and catalysts (Raney-Ni, K₂CO₃ and Na₂CO₃) on bagasse gasification were studied. A kinetic study on the non-catalytic and Na₂CO₃ catalytic bagasse gasification was conducted to describe the kinetic information of the bagasse gasification reaction. The results showed that a higher reaction temperature, a lower bagasse concentration and a longer residence time could favor the gasification of bagasse, leading to a higher hydrogen yield. Bagasse was nearly completely gasified at 750 °C without using any catalyst and the carbon gasification efficiency could reach up to 96.28%. The addition of employed catalysts remarkably promoted the bagasse gasification reactivity. The maximum hydrogen yield (35.3 mol/kg) was achieved at 650 °C with the Na₂CO₃ loading of 20 wt%. The experimental data fitted well with a homogeneous model based on a Pseudo-first-order reaction hypothesis. The kinetic study showed that Na₂CO₃ catalyst could lower the activation energy E_a of bagasse gasification from 117.88 kJ/mol to 78.25 kJ/mol.     

Syngas yield during pyrolysis and steam gasification of paper

Main characteristics of gaseous yield from steam gasification have been investigated experimentally. Results of steam gasification have been compared to that of pyrolysis. The temperature range investigated were 600–1000 °C in steps of 100 °C. Results have been obtained under pyrolysis conditions at same temperatures. For steam gasification runs, steam flow rate was kept constant at 8.0 g/min. Investigated characteristics were evolution of syngas flow rate with time, hydrogen flow rate and chemical composition of syngas, energy yield and apparent thermal efficiency. Residuals from both processes were quantified and compared as well. Material destruction, hydrogen yield and energy yield is better with gasification as compared to pyrolysis. This advantage of the gasification process is attributed mainly to char gasification process. Char gasification is found to be more sensitive to the reactor temperature than pyrolysis. Pyrolysis can start at low temperatures of 400 °C; however char gasification starts at 700 °C. A partial overlap between gasification and pyrolysis exists and is presented here. This partial overlap increases with increase in temperature. As an example, at reactor temperature 800 °C this overlap represents around 27% of the char gasification process and almost 95% at reactor temperature 1000 °C.     

Experimental research for biomass steam gasification in a fluidized bed

A fluidized bed gasification system was built to investigate the biomass steam gasification performance in different conditions. Medium heating value syngas with 34% H₂ content and no more than 20 g/Nm³ tar content could be obtained under 800°C with a S/B (steam vs. biomass ratio) of 0.9 by using olivine as bed material. The results indicated that syngas quality (including H₂ content, gasification efficiency, tar reduction, etc.) is in a positive correlation with temperature and S/B, but has a negative correlation with fluidization number (FN). Compared with quartz sand and dolomite, olivine is more suitable for fluidized bed because of its catalytic ability and good abrasion performance for fluidized bed gasifier. As a result, a set of optimum parameters is recommended with S/B of 0.9~1.0, FN of 1.4, and temperature of 800°C in this study.

Tar is a by-product from the gasification process, which will cause the pipeline congestion, reduce the gasification efficiency, and deteriorate the working condition. According to this experiment, the temperature and S/B both have a negative effect on tar content, while tar content increased with increase in the FN. Dolomite and olivine both have an inhibition function on tar, and the olivine is considered the best choice of bed material because of its good anti-wear properties.