不同气氛对生物质热解的影响

在下落式管式炉上研究两种惰性气氛(N2和CO2)对生物质热解产率和液体产物的影响,测定不同气氛下的快速热解和催化热解(HZSM-5为催化剂)的产率,并利用气质联用仪(GC/MS)分析热解油的成分。研究表明,改变热解气氛对结果产生明显影响。CO2对快速热解和催化热解均有不利影响,导致液体产率降低而固定碳和结焦产率上升,热解油的成分复杂化,抑制热解过程的芳香环化反应,使产物结构中出现甲氧基支链,同时在催化热解中促进稠环芳烃的生成。     

改性HZSM-5对油茶籽壳催化热解特性的影响

为改善油茶籽壳热解产物分布和油茶籽壳生物油成分特性,制备了金属Co、Mg和Cu改性的HZSM-5并用于油茶籽壳催化热解.对改性后的HZSM-5进行了表征,表征结果显示改性后的HZSM-5微观形貌没有改变,但比表面积有了较大幅度的降低.金属Mg负载改性的HZSM-5有利于油茶籽壳热解产生更多的液相产物,而金属Cu负载改性的HZSM-5则有利于油茶籽壳热解产生更多的气相产物.金属Co和Cu改性的HZSM-5提高了油茶籽壳热解生物油中酚类的相对含量,降低了生物油中酸类物质的相对含量.     

金属改性ZSM-5催化剂对黄丝藻提油后藻渣催化热解的影响

采用固定床反应器对黄丝藻提油后藻渣进行催化热解,以物料与催化剂质量比为1∶2研究不同金属类型(Mo、Ce、Ni)及金属负载量(4%、6%、8%)改性后的ZSM-5催化剂对黄丝藻提油后藻渣热解产物特性的影响。对催化剂进行BET、XRD等表征,对热解气体产物通过气相色谱分析,对液体产物采用气相色谱-质谱联用仪进行定性及半定量分析。结果表明:金属改性后ZSM-5催化剂加剧热解挥发分裂解,导致液体产物收率降低,热解气体产物的收率增加。反应过程中,催化剂的加入使气体产物中CO含量增加,CO_2含量减少。采用6%Ni/ZSM-5催化剂时所获得液体产物中酸类物质降低为0.09%,碳氢化合物组分达34.81%,且含有较低的稠环化合物和最高的烷基苯成分(4.92%)。     

生物质快速热解蒸气的在线催化研究

在固定床上对生物质流化床快速热解产生的蒸气进行了直接催化试验.选用HZSM-5催化剂,探讨了催化温度和催化剂量对催化后产物分布及生物油组分的影响.结果表明:在催化温度为375℃、催化剂量为30 mL时,可获得较高的液相产率(36.4%)、较低的气相产率(20.4%)和焦产率(13.9%).通过分析最佳工况下的生物油组分,发现精制油中含氧量高的有机酸、酯、酮、醛、呋喃等含量明显降低,而含氧量低的小分子酚类及不合氧的烃类含量大幅提高.     

Py-GC/MS技术用于Chaetoceros sp. 硅藻的催化热解研究

采用热裂解−气质联用（Py-GC/MS）技术研究Chaetoceros sp. 硅藻粉末的催化热解特性。以HZSM-5为催化剂,考察了不同Si/Al比的HZSM-5催化剂对硅藻热解产物的影响,并考察了催化剂的使用量、热解升温速率、热解反应时间对产物的影响。结果表明：未加催化剂时,硅藻热解产物以脂肪酸为主,含量为50.05%,苯系物含量仅为0.87%;加入HZSM-5催化剂后,硅藻热解产物中脂肪酸含量减少,芳香类化合物显著增加。热解实验结果发现,Si/Al比为38、硅藻和HZSM-5比例为1∶9、热解速率10 000℃/s、热解时间为10 s时,能得到较理想的热解产品,其中苯系物产率可达57.76%,脂肪酸含量为2.63%。这说明HZSM-5（38）具有较好的脱氧和芳构化功能,有利于硅藻催化热解生成高品质的生物油产品。     

碱脱硅改性的HZSM-5分子筛催化裂解小球藻的研究

用NaOH水溶液对HZSM-5分子筛进行脱硅改性。通过XRD、N_2物理吸附、NH_3-TPD对脱硅前后的HZSM-5分子筛进行表征,并研究脱硅改性前后分子筛对小球藻催化裂解的影响规律。结果表明:在适宜的温度和相同的碱处理时间下,改变NaOH水溶液的浓度,能调节分子筛晶体中产生的介孔比例并改变分子筛酸性能;以0.3 mol/L NaOH溶液在80℃下处理2 h改性制备的HZSM-5分子筛催化剂,其表面酸量增加、酸强度降低,有利于反应;小球藻催化热解产物中的氧大部分以CO和CO_2的形式脱除,可有效降低生物油的含氧量;裂解液体产率和生物油热值分别为46.83%、32.851 MJ/kg,生物油中烃类物质总量达到40.34%(质量分数),羰基化合物和醇类物质明显减少。     

核桃壳热解分级冷凝产物分布特性研究

为研究热解温度、载气流量和冷凝温度对核桃壳热解产物分布的影响,在实验室研制的生物质热解与分级冷凝装置上对核桃壳热解进行实验研究,结果表明:液体产物收率随着热解温度的升高而增加,但增加速率逐步降低;载气流量对液体产物总收率及各级液体产物收率影响较小;冷凝温度对液体产物总收率影响较小,但对各级生物油的收率影响较大。GC/MS分析表明:热解温度为450~500℃时,酚类物质含量达到最大值;随着二级冷凝器温度的升高,二级生物油中酚类物质富集程度逐渐提高,酸类物质的富集程度逐渐降低,二级生物油的收率逐渐下降。     

负载型HZSM-5对紫茎泽兰微波催化热解产物的影响

随着化石能源的消耗及环境条件的恶化,寻找新的可替代能源已经成为整个社会面临的重大难题.文中试验以世界性恶性杂草紫茎泽兰为原料,讨论了天然催化剂以及负载型HZSM-5催化剂对生物质微波催化热解的产物的影响.结果表明:凹凸棒土对酸类加氢还原反应具有较强的催化作用,使产物中羰基类物质含量增加.而HZSM-5催化剂能够促进芳香...     

分级孔HZSM-5催化烘焙预处理杨木快速热解制取芳烃

采用NaOH溶液对HZSM-5进行处理,通过XRD,BET,NH3-TPD方法对改性前后的HZSM-5进行表征。在管式炉中对杨木进行烘焙预处理,利用改性前后的HZSM-5在催化剂评价装置中进行烘焙预处理杨木的催化热解实验,探究杨木烘焙预处理温度和HZSM-5碱处理浓度对芳烃产物的影响。研究结果表明,碱处理后的HZSM-5形成了含有微-介孔的分级孔道结构,酸分布有所变化;随着NaOH浓度的增加,生物油中多环芳烃的含量逐渐降低,单环芳烃的含量呈现先增加后降低的趋势,在0.3-HZSM-5催化下达到最高产率58.12%;随着烘焙温度的升高,生物油中单环芳烃的含量先增加后降低,含氧化合物的含量先减小后增加,260℃烘焙预处理杨木催化热解效果最佳,芳烃化合物总收率达到82.01%,其中单环芳烃选择性达到70.87%。     

烘焙对生物质催化热解产物特性的影响研究

为了探究烘焙对生物质快速催化热解产物的影响,首先对棉秆在管式炉上进行不同温度(200、250、300℃)烘焙,然后在550℃下进行快速热解试验。随着烘焙温度的升高,气体产物中CO含量由51%逐渐减少到34%;烘焙后,热解油中酮类含量大幅减少,其中主要产物为芳香烃,其含量随烘焙温度的升高先增大后减少;烘焙可缓解催化热解过程中积碳的生成,300℃烘焙后的积碳量最少,仅为原样的46%。     

反应气体对松木生物质催化热解产物的影响

使用双颗粒流化床反应装置,对松木生物质进行了连续催化反应,选用CoMo-B和硅砂这2种流化介质,调查了氦气、氢气以及甲烷不同反应气体分别在不同流化介质作用下以及混合气体中氢气分压对热解产物的分布及其收率的影响。实验结果表明:在硅砂条件下,热解产物主要受温度的影响,在氦气和1173K高温下,IOG的分布主要以一氧化碳为主,其收率到达37.78wt%,daf,轻质芳烃HCL为3.10wt%,daf。但在催化剂CoMo-B作用下,适度的催化加氢有利于反应产物的控制,在863K下,轻质芳烃HCL和碳氢化合物气体HCG可达到6.29wt%,daf和15.43wt%,daf。采用工业用炼焦煤气作为加氢气体,在催化剂的作用下可以实现生物质中温连续催化加氢制取化学品的新过程。     

生物质炭催化裂解焦油的性能研究

采用管式反应器研究了生物质炭作为焦油裂解催化剂的性能,选用白云石和石英砂作对比试验。通过对焦油转换率、裂解产物、裂解气气体组分和动力学参数的分析对比可知:在所选用的3种材料中,生物质炭作为催化剂的焦油转化率最高,裂解产物中气体所占比重最大,且可燃气体的组分较高,反应动力学参数最小。生物质炭的催化性能显著高于石英砂,稍好于白云石,是一种高效的焦油裂解催化剂。     

Steam gasification of coal cokes in an internally circulating fluidized bed of thermal storage material for solar thermochemical processes

A laboratory-scale prototype windowed internally circulating fluidized-bed reactor made of quartz sand and coal coke particles was investigated for steam gasification using concentrated Xe-light radiation as the energy source. The quartz sand was used as a chemically inert bed material for the fluidized bed, while the coal coke particles functioned as the reacting particles for the endothermic gasification reaction. The advantages of using quartz sand as the bed material for the directly irradiated gasification reactor are as follows: (1) The bed height is maintained at a constant level during the gasification. (2) The quartz sand functions as a thermal transfer/storage medium inside the reactor. The gasification performances such as the production rates of CO, H₂, and CO₂; carbon conversion; and light-to-chemical energy conversion were evaluated for the fluidized-bed reactor with a thermal transfer/storage medium (quartz sand). The effects of using the bed material (quartz sand) on the gasification performance are described in this paper.     

床料对流化床颗粒层过滤器过滤元件的压降的影响

介绍了在三维流化床颗粒层过滤器冷态试验台上采用黄砂和石英砂两种床料进行试验的初步结果，为新型流化床颗粒层过滤器过虑颗粒的优化选择提供参考依据。     

Comparison of catalytic and noncatalytic pyrolysis and product yields of some waste biomass species

The products obtained by fast pyrolysis of biomass can be used as an energy source or chemical raw material. In this study, samples of hazelnut shells, tea bush, and hazelnut knot selected as waste biomass were from the cities of Trabzon and Rize in the Eastern Black Sea Region. Firstly, the waste biomass samples were granulated into four different particle sizes by milling and sieving operations. Fast pyrolysis of the samples with specific mixing rates was carried out in a fixed bed reactor. Additionally, 2 wt% vanadium (V) oxide (V₂O₅) was used as catalyst to maximize the yield of pyrolysis liquid products. The influence of temperature, heating rate, and particle size on fast pyrolysis yields under both catalytic and noncatalytic conditions were investigated and compared. While the amount of liquid product increased with the addition of catalyst, the amount of solid products decreased. It has been found that the temperature and heating rate parameters are very effective in liquid product yield. In all experiments, the maximum liquid yield was acquired at the same heating rate of 450°C min^?1 and the temperature of 450°C with particle size of 0.5 to 1.0 mm. The maximum pyrolysis liquid (bio‐oil) was obtained with catalytic pyrolysis, and this value was 60.58 wt%.     

Hydrocarbon gases and oils from the recycling of polystyrene waste by catalytic pyrolysis

The yield and composition of oils and gases derived from the pyrolysis and catalytic pyrolysis of polystyrene has been investigated. The pyrolysis and catalytic pyrolysis was carried out in a fixed bed reactor. Two catalysts were used, zeolite ZSM‐5 and Y‐zeolite and the influence of the temperature of the catalyst, the amount of catalyst loading and the use of a mixture of the two catalysts was investigated. The main product from the uncatalysed pyrolysis of polystyrene was an oil consisting mostly of styrene and other aromatic hydrocarbons. The gases were found to consist of methane, ethane, ethene, propane, propene, butane and butene. In the presence of either catalyst an increase in the yield of gas and decrease in the amount of oil produced was found, but there was significant formation of carbonaceous coke on the catalyst. Increasing the temperature of the Y‐zeolite catalyst and also the amount of catalyst in the catalyst bed resulted in a decrease in the yield of oil and increase in the yield of gas. Copyright © 2004 John Wiley & Sons, Ltd.     

The effect of online catalytic pyrolysis on the yield of light liquid products

Hydro-catalytic pyrolysis on Yunnan lignite were studied in a fixed bed to determine their effects on high-value raw materials, such as BTX, PCX and lower naphthalene, in liquid products. Ni and Mo were chosen as active pyrolysis centers through thermogravimetry, after which their catalytic effects were analyzed in a fixed bed. The results showed that different concentrations of impregnated Ni and Mo solution can significantly increase the yield of high-value products and enable catalyst separating and recycling with this method of online catalytic pyrolysis.     

The flash pyrolysis of cellulosic materials using concentrated visible light

The radiant flash pyrolysis of Avicel cellulose and kraft paper particles using concentrated visible light is described. The particles circulate in a clear quartz spouted bed reactor while undergoing pyrolysis in an incident radiant flux of up to 200 W/cm². This flux is supplied by an arc image furnace which uses a 5 kW Xenon bulb as its light source. The volatile pyrolysis products are quenched by the steam flow used to spout the bed and are entrained out of the reactor before secondary reactions can occur, ensuring a high sirup yield (63 per cent from cellulose). The major sirup component is levoglucosan.     

酒糟在流化床中燃烧特性的试验研究

利用X射线荧光光谱仪、灰熔点仪和热重分析仪等对酒糟的灰成分、灰熔点及着火温度进行了测试,并在小型流化床试验台上进行了酒糟燃烧试验,对不同含水率酒糟的着火特性、烧结特性和NOx排放质量浓度进行了研究.结果表明:酒糟灰中K2O和Na2O的含量很低,只有4.936%;酒糟灰的软化温度较高,高于1 290℃;干燥酒糟的挥发分较高,高于250℃就能够着火燃烧;当石英砂的平均粒径为300μm、流化床内的流化速度大于0.36m/s时,流化状况良好;在900℃下,酒糟在石英砂流化床中燃烧不会出现烧结现象;在不同的燃烧温度下,NOx排放质量浓度均较大,且随着燃烧温度的升高而增大;酒糟可以在石英砂流化床中燃烧,且燃尽效果良好.     

Short contact time catalytic partial oxidation of biogas – A comprehensive study on CO2 and N2 dilution

The short contact time catalytic partial oxidation of methane diluted with nitrogen and/or carbon dioxide to act as a surrogate for biogas conversion was carried out. Experiments were carried out under varying operating conditions to determine the possible use of the products in pyrolysis.Carbon dioxide has a larger effect on the product selectivities and back face temperature of the catalyst compared to nitrogen for equal dilutions. Carbon dioxide is consumed in the reactor whereas nitrogen is not. Since carbon dioxide likely takes part in endothermic reactions, the temperature of the catalyst is lower as is the conversion of methane and selectivity to carbon monoxide and hydrogen.The product stream is at an appropriate composition and temperature for subsequent use in a pyrolysis reactor. The presence of hydrogen and carbon monoxide will result in the removal of oxygen from bio-oils that are produced in the pyrolysis reactor.