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.     

抽提物对生物质热裂解机理的影响研究

利用惰性溶剂从生物质中提取得到相应抽提物,在热重红外联用仪上研究了抽提物的热裂解行为,并探讨了其对生物质热裂解的影响。结果表明,因不同种类生物质中木质素结构单元中紫丁香基和愈创木基数量不同,从而导致抽提物成分存在差异,相应的热裂解产物分布也不一致。水曲柳抽提物因含有较多的酚类物质而在热解高温段生成了甲醇和甲烷。相比于原样,抽提残渣反应活化能增加,且主要产物析出时间提前,同时酸类物质和直链烷烃析出量减少,而水、CO2、CO和醛类物质的产量则有所增加。     

升温速率对生物质热解的影响

稻壳、稻秆及麦秆是中国主要的农业废弃物,如何综合、有效地利用这些农业废弃物进行资源化研究显得十分必要。热解是热化学转化中最为基本的过程,是气化、液化及燃烧过程的初始和伴生反应,对热解的分析有助于热化学转化过程控制及高效转化工艺的开发。目前,国内外对生物质及其组分的热解已有大量的研究,但对中国主要的农业废弃物稻壳、稻秆及麦秆的研究较少。本研究利用热重和红外联用技术深入研究了升温速率对三种典型生物质热解气体产物的影响,并对生物质的热解动力学及热解气体产物的析出规律进行实时在线分析。     

无机矿物质盐对生物质热解特性的影响

生物质灰中碱金属盐的存在对生物质热解行为起着重要的催化作用。选取典型的农业废弃物花生壳作为实验的研究对象,首先分析了不同脱灰方法（水洗和酸洗（5%盐酸和5%硫酸））对生物质热解特性的影响,并采用ICP-AES测试分析不同洗涤方法的脱灰效果;为了进一步考察碱金属盐对生物质热解的影响,采用添加金属盐（K2CO3和CaCO3.M gCO3）分析了脱灰样的热解特性。结果表明,酸洗明显减少了生物质样内的碱金属含量,加快了生物质的热解速度,热解温度升高,少量金属盐的增加有利于生物质的热解。     

热解温度对生物质焦理化特性的影响

利用SEM、BET及TGA对在873、1 073和1 273 K下制得的麦秆焦的理化特性进行分析,进行了用制得的麦秆焦还原NO的实验,同时考虑了焦样及NO初始浓度对该反应的影响,得出了热解温度对麦秆焦的各种物理化学特性及其与NO反应活性的影响。结果表明,1 073 K焦样的孔隙特征最为发达,燃烧活性最高,并对应最高的NO还原效率。焦作用下NO的还原率随着焦样浓度的增大线性升高,而随着初始NO浓度的增大呈幂函数的规律下降。不同热解温度下麦秆焦样与NO的反应均在1 173 K附近存在动力学控制和扩散控制的转折温度;在动力学控制的反应温度范围内,热解温度对麦秆焦与NO反应活化能的影响不大(89.78~95.41 kJ/mol),其中,NO浓度项和焦浓度项的反应级数分别为0.89和1.00。     

城市生活垃圾典型有机组分混合热解特性的研究

利用自行设计的较大物量(约10 g)的热重分析装置对城市生活垃圾典型有机组分（纸屑、木屑、织物、塑料、橡胶、厨余）的混合热解特性进行了实验研究,并用最小二乘法计算得到由若干平行反应组成的热解反应动力学模型,实验结果与模型计算结果吻合较好。在此基础上对城市生活垃圾典型有机组分混合热解中的交互影响和非线性规律进行了分析。结果表明,城市生活垃圾典型有机组分混合热解动力学模型由2个～4个平行反应组成;混合热解中有反应发生合并的现象;热效应和组分比例对混合物综合热解特性有显著影响。     

热解压力对生物质焦结构及气化反应性能的影响

利用加压固定床反应器、吸附仪、X射线衍射仪、元素分析仪、电感耦合等离子原子发射光谱仪等考察了热解压力对生物质半焦(以下简称半焦)产率、物化结构、元素组成的影响规律。同时,利用热天平对不同热解压力下所制半焦的气化行为进行了考察。结果表明,随热解压力升高,半焦产率增大,当压力升至1.0 MPa后,半焦产率基本不变;半焦中C元素含量随热解压力的升高而增加,而H元素含量和BET比表面积则减小;此外,随热解压力升高,玉米秸秆焦和锯末焦的石墨化程度增强,而稻壳焦的石墨化程度则基本不受热解压力影响。气化反应的研究表明,玉米秸秆焦及锯末焦的平均气化反应速率随热解压力的提高而减小,而稻壳焦的平均气化反应速率基本不受热解压力的影响。热解压力对半焦BET比表面积及碳微晶结构的影响规律与气化反应速率变化规律的对比研究表明,热解压力引起半焦微晶结构的变化是造成热解压力对半焦气化反应速率影响的主要原因。     

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。     

利用Py-GC/MS研究温度和时间对生物质热解的影响

以稻壳为原料,采用Py-GC/MS装置对其在不同热解条件下进行快速热解,并对热解气进行在线检测分析,考察了热解温度和时间对生物质热解性质的影响.结果表明,低于450 ℃,随着温度的升高,生物质热解产物种类及其产率均增加,但低温条件下产物种类较少,有利于产物的分离提纯;高于450 ℃,生物质热解产物种类基本稳定,仅在产率上有所变化,当550 ℃时,收率最大.随着热解温度的升高,其对应的最佳热解时间缩短,且生物质低温热解时间延长时热解比高温解热时间缩短时热解更充分.     

生物质与废轮胎共热解催化热解油蒸发过程及其动力学研究

采用热重微商(TG-DTG)法考察生物质稻壳与废轮胎共热解经催化与非催化热解油的热失重行为,并同0#柴油的热失重行为进行了比较;同时采用Achar微分法和Coats-Redfern积分法对热解油热失重蒸发过程的蒸发热进行了计算,并结合Satava和Bagchi法确定了热失重蒸发过程的机理函数, 建立了0#柴油和在催化与非催化条件下得到的热解油蒸发过程的动力学方程,得出了在催化与非催化条件下热解油热失重过程的机理函数,其动力学方程为dα/dt=Ae-△vapH/RT(1-TBX〗α)2;而0#柴油的热失重蒸发过程动力学方程为dα/dt=1.5Ae-△vapH/RT(1-α)2/3[1-(1-α)1/3]-1。蒸发热的顺序由大到小依次为,柴油＞非催化热解油＞SBA-15热解油＞MCM-41热解油。结果表明,通过建立的模型函数得到的蒸发热与实验值非常接近。催化剂SBA-15和MCM-41的存在对降低高沸点馏分的物质具有一定作用,而SBA-15催化作用强于MCM-41。     

Investigating morphological and performance deterioration of injection-molded rice husk–polypropylene composites due to various liquid uptakes

Systematic investigations for the tensile strengths, tensile moduli, flexural strengths, flexural moduli, and impact strengths of various reinforced conditions of rice husk–polypropylene composites under the effect of different liquids uptakes were carried out. Three different liquids, i.e., lubricant oil, sea water, and distilled water, were utilized in this work to investigate their effects on the composites’ mechanical performance. Moreover, morphological analysis of the designed composites was also carried out. Various fiber loadings at 35, 40, 45, 50, and 55 wt% have been designed and investigated. The rice husk–polypropylene composites have been prepared by injection molding, and struktol was used as an additive. The composites were immersed in three different liquids—lubricant oil, sea water, and distilled water—for 4 weeks. The water uptake of rice husk–polypropylene composites for distilled water was the highest compared to lubricant oil and sea water. Moreover, results have demonstrated that mechanical properties of composites immersed in sea water were the best, followed by those immersed in lubricant oil, and then those immersed in distilled water. In addition, it was observed that more voids and pull-out existed in composites immersed in lubricant oil, followed by those immersed in distilled water, and then those immersed in sea water. Tensile moduli showed a reduction trend for all composites with increasing filler loading. However, flexural moduli improved as the filler loading increased. Also, results here demonstrated an optimum filler loading condition for each particular mechanical property of rice husk–polypropylene composites.     

Mechanical and morphological properties of injection-molded rice husk polypropylene composites

In this work, the investigation of the physical, mechanical, and morphological properties of the rice husk flour/polypropylene composites was performed utilizing various filler loadings and coupling agent. Five levels of filler loading (35, 40, 45, 50, and 55 wt%) were designed. In addition, to help the interaction between fiber and polypropylene matrix, struktol coupling agent was added to the composites. All of tensile strength, Young's modulus, flexural strength, flexural modulus, and impact strength properties of the composites were carried out. Moreover, the 50 wt% filler-loaded composites had optimum tensile strength, flexural strength, and flexural modulus, whereas the 35 wt% of filler loading case was the best regarding Young's modulus, flexural strength, flexural modulus, and impact strength. Furthermore, the scanning electron microscope results demonstrate that as filler loading increases, more voids and fiber pullout occur.     

Thermal analysis of the rice and by-products

The thermogravimetry (TG) is a technique used in the quality control of foods. In this work the moisture and ash contents in the rice and by-products (bran and husk), the thermal stability and the gelatinization process by conventional, thermogravimetric and calorimetric methods were studied. The moisture and ash contents obtained by TG and conventional methods did not present significant differences. The rice presented higher starch content, while the bran presented higher protein content. The thermogravimetric data presented the following thermal stability order: rice>bran>husk. The calorimetric curves indicated the gelatinization of the starch. The kinetic parameters were compatible. This revised version was published online in August 2006 with corrections to the Cover Date.     

Production of High Purity Amorphous Silica from Rice Husk

Combustion of the rice husk produces rice husk ash, which consists of mainly silica. High purity silica can be produced by controlled combustion after acid treatment. In this study, leaching of rice husk with hydrochloric acid and sulfuric acid were carried out prior to combustion to obtain purer silica. It was found that pre-treatment of the rice husk with sulfuric acid had accelerated the hydrolysis and decomposition of organic components as revealed by thermogravimetry (TG) and Scanning Electron Microscopy (SEM) analyses. In a systematic study, the combustion of un-leached, hydrochloric acid-leached and sulfuric acid-leached rice husks were performed in a muffle furnace at 500, 600, 700, 800 and 900^oC for 2 h. Results demonstrated that all the samples produced amorphous silica (SiO₂) and the average particle size were in the range of 0.50 to 0.70 μm. The effect of combustion at different temperatures between 500^oC and 900^oC on the silica production is very small, particularly at temperature above 600^oC. Thus, amorphous silica with purity above 99% as confirmed by X-Ray Fluorescence (XRF) analysis can be produced by hydrochloric and sulfuric acids leaching of the rice husk, followed by controlled combustion at 600^oC for 2 h. The BET surface area of the silica produced after leaching the rice husk with hydrochloric acid was higher (218 m²/g) than with sulfuric acid (209 m²/g). The silica obtained has potential application as filler in plastics and rubber compounding.     

再燃温度对稻壳焦理化结构演变的影响

利用高温携带流装置,在再燃条件下获得了不同的稻壳焦。采用元素分析、SEM-EDS分析、N2吸附-脱附、ICP-AES、XRD和FT-IR等手段对稻壳焦的理化结构进行了分析与表征,研究了再燃温度对稻壳再燃过程中灰焦理化结构演化规律的影响。结果表明,在850-1 150℃,反应温度的升高有利于稻壳焦孔隙结构的形成,进而有效提高稻壳焦的比表面积和孔容积。稻壳中碱(土)金属元素的释放顺序为NaCaMgK,且随温度升高,碱(土)金属元素的释放率呈现先略微升高后逐渐趋于稳定的趋势,氯的释放率逐渐增大。稻壳焦中的碱(土)金属主要以硅酸盐和硫酸盐的形式存在。稻壳焦表面含氧官能团随反应温度的升高逐渐减少。     

聚硫醚型纤维素的合成及其吸附性能

稻壳纤维素;氯甲基硫杂丙环;金属离子;聚硫醚型纤维素的合成及其吸附性能     

Separation of Pt(IV) from Industrial Wastewater Using Rice Husk Adsorbent and Its Derivatives

Some novel adsorbents were prepared by rice husk (RH). The esterified rice husk (RHS) was prepared by treating RH with anhydride of succinic acid to introduce carboxylic function to rice husk. This RHS was used to anchor various polyamines, viz., ethylenediamine (ED) and diethylenetriamine (DT) to prepare new adsorbents. These adsorbents were used to separate Pt(IV) from synthetic as well as industrial wastewaters. Adsorbents were characterized by Fourier transform infrared spectra, elemental analysis, scanning electron microscopy, and energy dispersive x-ray spectrometry. The selectivity order for Pt(IV) removal found was: RHS-DT > RHS-ED > RH > RHS. The Freundlich isotherm provided the high correlation (0.9750–0.9938) for the adsorption with low SSE (0.00215–0.00785) value of Pt(IV) for all the adsorbents. Among the kinetic models, pseudo-second order kinetic model was found to best fit with high correlation for all the adsorbents. The results of thermodynamic parameters suggest that the Pt(IV) adsorption was spontaneous and endothermic in nature. The maximum percentage of desorption of Pt(IV) metal ion was obtained when the reagent HCl–thiourea mixture was used as desorbing agent.