酸预处理对生物质热裂解规律影响的实验研究

在自制的热裂解机理实验台上进行了不同酸处理对稻壳以及白松的热裂解影响实验研究。经过盐酸浸泡后,稻壳中的金属离子含量明显降低;经盐酸洗涤后的稻壳热裂解焦油产量升高,由原始物料时的41.74%增加到7%盐酸洗涤后的52.88%,而气体和焦炭产量相应降低,并且随着盐酸浓度的增加,对应的趋势更加明显。酸洗涤后稻壳热裂解气体产物主要由CO和CO₂组成,其产量相比原样都有所降低;不同种类的酸对生物质热裂解规律的影响存在差异,盐酸因其去离子效果最好而对生物质热裂解产物分布影响最强;对白松原样以及酸洗后白松的微观结构进行了电镜分析,结果发现,硫酸对白松的微观结构产生了明显的影响。     

酸洗预处理对纤维素热裂解的影响研究

为获得液体产量的最大化和提高产物中糖类的质量分数,采用盐酸（3%、5%、7%）、磷酸（7%）和硫酸（7%）对纤维素进行酸洗预处理。不同酸洗预处理下纤维素的微观结构和聚合度变化表明,酸处理损坏了纤维素的物理结构,并使聚合度大幅度降低。在“┣”形石英玻璃反应器的快速热裂解试验装置上进行了不同酸处理前后的纤维素热裂解试验,发现酸浸泡处理后,生物油产率下降,相应的气体和焦炭产率提高,并且随着酸浓度的提高,该趋势逐渐增强。与盐酸和磷酸相比,硫酸对生物油的生成具有更强的抑制作用,这表明,酸对纤维素交联和脱水反应的催化效果。通过GC-MS色质联机分析技术对生物油成分进行分析,发现酸的存在并没有改变生物油成分的种类,但使化合物之间的相对质量分数发生了变化。左旋葡聚糖的质量分数随稀酸溶液浓度的增加呈下降趋势,原因是残留在物料中的微量酸以催化脱水和交联反应的方式,对其生成起抑制作用。     

钾元素对生物质主要组分热解特性的影响

采用热重-红外联用仪对松木及生物质主要化学组分半纤维素、纤维素、木质素的热解特性及钾元素对其热解特性的影响进行了研究.结果表明,半纤维素、纤维素、木质素发生热解的主要温度分别为200~350 ℃、300~365 ℃和200~600 ℃;半纤维热解产物中CO、CO₂较多;纤维素热解产物中LG和醛酮类化合物最多;木质素热解主要形成固体产物,气体中CH₄相对含量较高.三种组分共热解过程中发生相互作用使热解温度提高、固体产物增加,气体中CO增加而CH₄减少.添加K₂CO₃后半纤维素和纤维素热解温度区间向低温方向移动,固体产率提高.K对纤维素作用最明显,CO、CO₂气体与固体产物产率明显增加,醛酮类和酸类物质的产率降低;木质素受K影响相对较小,热解固体产物略有增加,挥发分中H₂O和羰基物质增加;三组分共热解减弱了钾元素的催化作用.     

Plasma-Assisted Pretreatment of Wheat Straw for Ethanol Production

The potential of wheat straw for ethanol production after pretreatment with O(3) generated in a plasma at atmospheric pressure and room temperature followed by fermentation was investigated. We found that cellulose and hemicellulose remained unaltered after ozonisation and a subsequent washing step, while lignin was degraded up to 95% by O(3). The loss of biomass after washing could be explained by the amount of lignin degraded. The washing water of pretreated samples (0-7 h) was analyzed for potential fermentation inhibitors. Approximately 30 lignin degradation products and a number of simple carboxylic acids and phenolic compounds were found, e.g., vanillic acid, acetic acid, and formic acid. Some components had the highest concentration at the beginning of the ozonisation process (0.5, 1 h), e.g., 4-hydroxybenzladehyde, while the concentration of others increased during the entire pretreatment (0-7 h), e.g., oxalic acid and acetovanillon. Interestingly, washing had no effect on the ethanol production with pretreatment times up to 1 h. Washing improved the glucose availability with pretreatment times of more than 2 h. One hour of ozonisation was found to be optimal for the use of washed and unwashed wheat straw for ethanol production (maximum ethanol yield, 52%). O(3) cost estimations were made for the production of ethanol at standard conditions.     

Effect of sample preparation on the thermal degradation of metal-added biomass

The present study investigates the effect of different sample preparation methods on the pyrolysis behaviour of metal-added biomass; Willow samples were compared in the presence of two salts of zinc and lead containing sulphate and nitrate anions which were added to the wood samples with three different techniques as dry-mixing, impregnation and ion-exchange. The effect of acid and water wash as common demineralisation pre-treatments were also analysed to evaluate their roles in the thermal degradation of the biomass. Results from thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR) and pyrolysis-mass spectrometry (Py-MS) measurements indicated that these pre-treatments change the matrix and the physical–chemical properties of wood. Results suggested that these structural changes increase the thermal stability of cellulose during pyrolysis. Sample preparation was also found to be a crucial factor during pyrolysis; different anions of metal salts changed the weight loss rate curves of wood material, which indicates changes in the primary degradation process of the biomass. Results also showed that dry-mixing, impregnation or ion-exchange influence the thermal behaviour of wood in different ways when a chosen metal salt was and added to the wood material.     

A comparative study on the pyrolysis of metal- and ash-enriched wood and the combustion properties of the gained char

This study aims to investigate the pyrolysis behaviour of metal-contaminated wood and the combustion properties of char derived from wood pyrolysis. Seven metals (Na, Mg, Ca, Zn, Cd, Pb and Fe(III)) were introduced to willow in cation form by ion-exchange and the thermal behaviour of demineralised samples and samples with additional ash were also investigated.The results show that the char yield increased from 21% to 24–28% and levoglucosan yield in vapour phase decreased from 88% to 62–29% after the addition of inorganic compounds, even though the metal binding capacity of wood varied from one metal ion to another. While char yield seems to be effected mainly by the concentration of the metal ions, levoglucosan yield was more dependent on the ionic species especially when sodium ions were present. When combustion experiments were carried out with char made of the metal enriched wood, two consecutive steps were observed, both effected by the presence of inorganic compounds. The first step was identified as the release and combustion of volatiles, while the second peak of the burning profile is the actual combustion of the fixed carbon. The burnout temperatures, estimated ignition indices and the conversion indicate that the type and not the amount of metal ions were the determining factors during the second step of combustion.     

钾对松木热解特性影响实验研究

采用管式炉热解实验装置对浸渍K2CO3松木进行直接热解,并将松木热解气通过含钾石英砂层、含钾焦层以模拟钾对热解气体反应的影响。结果表明,松木中浸渍K后会促进热解固体焦生成,提高H2/CO比,低温下K会降低液相产率、提高气相产率,而热解温度较高时则使气体产率下降、液体产率提高。松木热解气经过含K石英砂后发生催化裂解,液体产率降低,CO、CO2和H2产量上升。松木焦也可以催化裂解焦油,使气体产物增加,H2和CO2产量提高,CO、CH4和C2产量降低。K与松木焦共同作用,不仅使焦油发生裂解而且促进更多焦参与气固反应。钾对松木热解作用是通过对松木的直接热解、对气体中间产物再反应的均相催化及对固体焦气化的非均相催化等复杂过程实现的。     

Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels

Lignocellulosic biomass is the most abundant and bio-renewable resource with great potential for sustainable production of chemicals and fuels. This critical review provides insights into the state-of the-art accomplishments in the chemocatalytic technologies to generate fuels and value-added chemicals from lignocellulosic biomass, with an emphasis on its major component, cellulose. Catalytic hydrolysis, solvolysis, liquefaction, pyrolysis, gasification, hydrogenolysis and hydrogenation are the major processes presently studied. Regarding catalytic hydrolysis, the acid catalysts cover inorganic or organic acids and various solid acids such as sulfonated carbon, zeolites, heteropolyacids and oxides. Liquefaction and fast pyrolysis of cellulose are primarily conducted over catalysts with proper acidity/basicity. Gasification is typically conducted over supported noble metal catalysts. Reaction conditions, solvents and catalysts are the prime factors that affect the yield and composition of the target products. Most of processes yield a complex mixture, leading to problematic upgrading and separation. An emerging technique is to integrate hydrolysis, liquefaction or pyrolysis with hydrogenation over multifunctional solid catalysts to convert lignocellulosic biomass to value-added fine chemicals and bio-hydrocarbon fuels. And the promising catalysts might be supported transition metal catalysts and zeolite-related materials. There still exist technological barriers that need to be overcome (229 references).     

Effect of mineral matter on the formation of NOX precursors during biomass pyrolysis

Formation of NO_X precursors during pyrolysis of three typical kinds of biomass (wheat straw, rice straw and corn cob) was studied using a thermogravimetric analyzer (TGA) coupled with a Fourier transform infrared (FTIR) spectrometer in argon atmosphere. Two pretreatment methods, including deionized water washing and acid washing were utilized to investigate the effect of included minerals on the distribution of nitrogen containing species during wheat straw pyrolysis. KOH and CaO were loaded onto the demineralized (dem) wheat straw to study the effect of excluded minerals on nitrogen release. The residues of the samples after pyrolysis were characterized by X-ray diffraction (XRD) analysis. The results show that different kinds of biomass have distinctive formation characteristics of N-containing species. HCN and HNCO are the main N-containing species for rice straw, while NH₃ and HCN are the main N-containing species for wheat straw and corn cob.The existence of minerals influences the formation of N-containing species during biomass pyrolysis. Both the included potassium and excluded potassium promote N-conversion to NH₃, HCN, NO and HNCO at lower temperature, but decrease the total yields of N-containing species. The included calcium decreases N-conversion to HCN, NH₃ and HNCO at lower temperature (<about 330 °C), while favors the total yields of N-containing species. However, the presence of added calcium restrains N-conversion to HCN, NH₃, NO and HNCO.     

硝酸钙对内蒙古褐煤热解和气化特性的影响

在小型固定床反应装置上开展了内蒙古褐煤原煤(RC)和脱灰煤(DC)以及分别负载钙盐的煤样的热解实验,并对热解所得焦样开展了焦样与水蒸气气化反应的实验研究。结果表明,硝酸钙的添加对煤的热解和气化阶段均有影响。在热解阶段,硝酸钙的存在能显著改变主要气相产物H₂、CO₂和CO等组分的逸出规律和累积生成量;在气化阶段,作为催化剂的碱土金属,降低了焦样的气化反应活化能,更有利于气化反应的进行。     

钾和一氧化碳对松木屑快速热解半焦特性的影响

利用固定床反应器、红外光谱仪、吸附仪、X射线衍射仪、电感耦合等离子原子发射光谱仪、偏光显微镜等对比研究了原生生物质(原生物质)及水洗脱钾生物质(脱钾生物质)在N_2及富一氧化碳(CO)气氛下所得半焦的产率、官能团及其他物化结构的变化规律。研究表明,与脱钾生物质相比,热解温度低于750℃时,原生物质的半焦产率降低、比表面积增大、芳环结构减少而烷基、脂肪族结构等增加;与N_2相比,富CO气氛下所得半焦产率降低、比表面积增大,芳香结构、脂肪族结构、烷基减小。而热解温度高于750℃时,生物质中的钾和热解气氛中的CO均使生物质半焦产率增加、官能团数量和比表面积减少。利用偏光显微镜对生物质半焦表面矿物质的研究表明,热解温度低于750℃时,所得半焦表面矿物组分较少且高度分散;热解温度高于750℃时,所得半焦表面矿物组分较多,分布密集且熔融团聚现象随温度升高而增多。而对于半焦石墨化程度的研究表明,半焦石墨化程度随温度升高而增加,但低热解温度所得半焦的石墨化程度较差。温度高于750℃时,CO气氛使石墨化程度增加,而钾使石墨化程度降低。     

Palladium cluster catalysts supported on chelate resin-metal complexes

The dry beads of chelate resin-metal complexes have been prepared from metal ions and the chelate resin containing iminodiacetic acid moieties. The surface area of the chelate resin can be increased both by washing with an organic solvent miscible with water and by complexing with multi-valent cations. Palladium clusters are supported on the chelate resin-metal complexes by two methods, in which the order is reversed between “complexing of metal ions” and “supporting of palladium clusters”. The supported palladium clusters catalyze the hydrogenation of C=C bonds, and the catalytic activity greatly depends on the metal ions used for the complexation. In the case of typical metal ions, the complexing of metal ions after supporting of palladium clusters makes the surface area of the resin increase, but makes the catalytic activity decrease compared with the reverse order. In the case of lanthanoid ions, on the other hand, the same order makes both the surface area and the catalytic activity increase.     

生物质热解和气化过程Cl及碱金属逸出行为的化学热力学平衡分析

减少生物质在热转化反应器中Cl与碱金属K和Na以气态组元逸出可有效遏制积灰、腐蚀等现象和减少污染气体排放。采用化学热力学平衡分析方法,在400K~1600K研究了秸秆、树皮、木屑、废木和橄榄渣五种生物质在过剩空气系数分别为0、0.4、0.8的热解和气化过程中Cl与碱金属K和Na的赋存形态变化及逸出特性。结果表明,Cl在热解和气化过程中主要是以KCl(s)、HCl(g)、KCl(g)、(KCl)2(g)和NaCl(g)化合物赋存并相互转化;在800K~1000K时,含Cl固态组元逐渐转化为气态组元;K和Na在900K时开始以气态组元逸出,且热解过程有少量KCN(g)和NaCN(g)逸出,而气化过程,温度大于1000K随过剩空气系数的增加,KCl(g)、K(g)和Na(g)等气态组元量逐渐减少,逐渐转化为NaCl(g)、KOH(g)和NaOH(g);减少Cl和碱金属K和Na逸出的理论最佳热解和气化温度分别为800K和900K。     

生物质气化过程中碱金属和碱土金属的析出特性研究

研究了固定床上生物质及热解焦CO2气化过程中碱金属及碱土金属(AAEMs)的析出特性。利用原子吸收光谱仪,考察了不同生物质种类、不同热解制焦温度对AAEMs析出的影响。不同生物质由于其挥发分含量不同引起气化失重率的差异,焦气化活性随制焦温度升高而降低。生物质及焦气化过程中Na析出率最大,其次是K,碱土金属析出率低于碱金属,这与元素在生物质中的存在形式、金属价态有关。低温段K的析出率随热解制焦温度的提高而增加,而Na在热解与气化段总的析出率与制焦温度关系不大。生物质的种类尤其是灰中的Si含量对Ca和Mg的析出影响较大,气化效率高的生物质AAEMs析出较多。热力学计算结果显示,气化过程中Na、K多以氯化物的形式存在并析出,Ca、Mg则更倾向于形成硅酸化合物而不易析出。     

TG-MS analysis for studying the effects of fire retardants on the pyrolysis of pine-needles and their components

Thermogravimetry-mass spectrometry (TG-MS) was used to study the effect of the inorganic salts (NH₄)₂SO₄ and (NH₄)₂HPO₄, active substances of many commercial forest fire retardants, on the pyrolysis of Pinus halepensis needles and their main components (cellulose, lignin and extractives). These salts seemed to affect the pyrolysis of cellulose by increasing significantly the char residue, decreasing the pyrolysis temperature and changing the composition of the evolved gases, that is, increasing levoglucosenone and decreasing oxygen containing volatile products. (NH₄)₂SO₄ seemed to have negligible effect on the pyrolysis of lignin, while (NH₄)₂HPO₄ increased the char residue and decrease the relative contribution of guaiacols in the evolved gases. No effects of the inorganic salts on the extractives were observed. Finally, the inorganic salts seemed to affect the pyrolysis of pine-needles, mainly the cellulose component, but the effects were not as intense as in the pyrolysis of cellulose.     

Thermogravimetry/mass spectrometry study of woody residues and an herbaceous biomass crop using PCA techniques

The devolatilization behaviour of pine and beech wood from carpentry residuals and an herbaceous product from an energy plantation (artichoke thistle) was investigated by thermogravimetry/mass spectrometry (TG/MS). The effect of three pre-treatments, hot-water washing, ethanol extraction and their combination, was also studied. Principal component analysis (PCA) was employed to help in the evaluation of the large data set of results. The characteristics of the thermal decomposition of the herbaceous crop are considerably different from that of the woody biomass samples. The evolution profiles of some characteristic pyrolysis products revealed that the thermal behaviour of wood and thistle is still considerably different after the elimination of some of the inorganic ions and extractive compounds, although the macromolecular components of the samples decompose at similar temperatures. With the help of the PCA calculations, the effect of the different pre-treatments on the production of the main pyrolysis products was evidenced.     

生物质组分及温度对闪速热解挥发分的影响

生物质是一种可再生、污染小的自然资源，它可以直接燃烧产生热能，也可以转化为气体、液体燃料或化工原料。生物质热转化技术近年来受到国内外学者的广泛重视。而热转化过程中，热解是第一步，与生物质组分、热解温度、滞留时间等因素有关。热重仪（TGA）是一种研究热解机理常用的方法，它适用于慢速程序升温的热解研究。研究发现，热解条件及生物质种类对反应表观活化能与表观频率因子等动力学参数有很大影响。层流炉闪速加热设备，已经用于煤的热解研究。本文利用自己设计的以热等离子体为热源的层流炉系统，对椰子壳、棉花秆和稻壳粉末进行了闪速热解实验研究及模型理论分析，探讨了生物质化学组分、热解温度和滞留时间对挥发分的影响，为生物质闪速热解提供了一定的基础数据。     

Kinetic study of wood chips decomposition by TGA

Pyrolysis of a wood chips mixture and main wood compounds such as hemicellulose, cellulose and lignin was investigated by thermogravimetry. The investigation was carried out in inert nitrogen atmosphere with temperatures ranging from 20°C to 900°C for four heating rates: 2 K min⁻¹, 5 K min⁻¹, 10 K min⁻¹, and 15 K min⁻¹. Hemicellulose, cellulose, and lignin were used as the main compounds of biomass. TGA and DTG temperature dependencies were evaluated. Decomposition processes proceed in three main stages: water evaporation, and active and passive pyrolysis. The decomposition of hemicellulose and cellulose takes place in the temperature range of 200–380°C and 250–380°C, while lignin decomposition seems to be ranging from 180°C up to 900°C. The isoconversional method was used to determine kinetic parameters such as activation energy and pre-exponential factor mainly in the stage of active pyrolysis and partially in the passive stage. It was found that, at the end of the decomposition process, the value of activation energy decreases. Reaction order does not have a significant influence on the process because of the high value of the pre-exponential factor. Obtained kinetic parameters were used to calculate simulated decompositions at different heating rates. Experimental data compared with the simulation ones were in good accordance at all heating rates. From the pyrolysis of hemicellulose, cellulose, and lignin it is clear that the decomposition process of wood is dependent on the composition and concentration of the main compounds.     

Metal ion extraction using newly-synthesized bipyridine derivative as a chelating reagent in supercritical CO(2).

4,4'-Bis(dihexylaminocarbonyl)-2,2'-bipyridine (BDC-Bipy) was synthesized and studied systematically as a chelating reagent for metal ions extraction in supercritical CO(2). The compound showed high extraction efficiency for Co(2+) (100%), Cu(2+) (100%), Cd(2+) (98.2%), and Zn(2+) (100%) ions and good extraction efficiency for Sr(2+) (79.4%) and Pb(2+) (89.8%) when the extraction was performed in supercritical CO(2) at 313 K and 25 MPa with the system of BDC-Bipy, deionized water and perfluoro-1-octanesulfonic acid tetraethylammonium salt. The recoveries of mixed metal ions were also measured; unfortunately, the system of extraction has no selectivity for the metal ions.     

Pyrolysis of sorghum bagasse biomass into bio-char and bio-oil products

The transformation of renewable biomass into valuable products as alternatives to fossil fuels is essential for sustainable energy in sustainable society. This work systematically investigates the pyrolysis of sorghum bagasse biomass into bio-char and bio-oil products and studies the effect of temperature (623–823 K) on the conversion of sorghum bagasse and products yields. The physicochemical properties of bio-char were thoroughly studied using powder X-ray diffraction, elemental analysis (CHNSO), scanning electronic microscope, calorific value (CV), and Fourier transform infrared (FTIR) spectroscopy techniques. Also, gas chromatography–mass spectrometry (GC–MS), CV, and FTIR were used to understand the properties of bio-oil. The results obtained indicate that an increase in the pyrolysis temperature from 623 to 823 K leads to a decrease in the bio-char yield from 42.55 to 30.38%. On the other hand, the maximum bio-oil yield of 15.94% was obtained at 723 K. The bio-char obtained at 673 and 773 K was found by FTIR analysis to be composed of a highly ordered aromatic carbon structure. The calorific value of bio-oil, which contains a greater amount of acidic compounds, was found to be 6740 kcal/kg. The GC–MS analyses revealed the presence of octadecenoic acid, p-cresol, 2,6-dimethoxy phenol, 4-ethyl 2-methoxy phenol, phenol, o-guaiacol, and octadecanoic acid in the bio-oil obtained from the pyrolysis of sorghum bagasse biomass. The present study provides useful information for understanding the quality of bio-oil and bio-char obtained from high biomass sorghum bagasse.