微波热解工艺参数影响气液产物组成的研究

针对生物质微波热解生物油产率低且含水量高,气体产物较为复杂的特点,通过实验对热解参数、堆积程度、传热介质3个方面进行考察研究。实验结果表明,在热解温度为600℃,预热温度为160℃,填充程度为100%的条件下得生物油最大产率为51.12%,生物炭产率为26.56%,合成气产率为22.32%;生物油以酚类化合物和呋喃类化合物为主,合成气以CO,H2,CH4,CO2,C2～C4小分子气体为主。     

内循环串行流化床生物质催化热解试验研究

在处理量为0.2 kg/h的新型内循环串行流化床(IIFB)上进行了生物质催化热解制油的试验研究.以木屑为原料、石英砂为热载体,研究了在没有催化剂条件下反应温度对热解产物分布的影响;以HZSM-5催化剂与石英砂混合物为床料进行了催化热解试验,并对热解产物和反应后的催化剂进行了表征分析.结果表明:反应温度为515℃时,液体产物的收率最高.HZSM-5催化剂的加入促进了气体以及焦炭的生成,使液体产物的收率降低,且催化剂体积分数越大,影响越显著.催化荆表面的积炭经燃烧反应后被除去,催化剂的稳定性得到改善.热解不可冷凝气体的主要成分为CO和CO2,随着热解温度的升高,CO2产量下降,CO和CH4的产量增加.经HZSM-5催化热解后,生物油中的酸、醛和酮类物质含量明显减少,而小分子的烃类与酚类物质含量明显增加,表明催化剂具有明显的脱氧效果.     

稻壳连续热解特性研究

在自行研制的生物质连续热解反应装置上进行稻壳连续热解和二次裂解实验研究。随着稻壳热解温度的提高,炭产率降低,气体产率增加,液体产率先增加后减少;随着滞留时间的减少,炭产率、液体产率增加,气体产率减少。稻壳热解气以CO2和CO为主,且二者为竞争关系,热解温度提高,CO2产量降低,CH4、H2、C2H4、C2H6产量增加,CO的产率变化不大;滞留时间对热解气组分影响不大。二次裂解温度提高,裂解气中的H2、CH4、C2H4含量明显增加,二次裂解温度为800℃时,H2产率达到12%。稻壳500℃热解挥发物600℃二次裂解木醋液中醋酸含量高达49.44%,焦油中检测到的物质主要为丙酮和异丙醇。     

高温移动床废轮胎与生物质直接热解制气性能研究

对以不同比例组成的废轮胎与生物质均匀混合物在移动床内高温直接热解的制气性能进行了研究,考察了温度和废轮胎含量对产物产率、气体组分以及热值等影响。结果表明,温度对直接热解气产率和热值影响较大,温度越高,气体产率越大而热值越小;混合物中废轮胎含量增大,热解气中碳氢气体含量增多而含氧气体减少,气体产率逐渐减小而热值增大。温度升高,合成气(H2+CO)含量和H2/CO比值均增大;废轮胎含量增大,合成气(H2+CO)含量和H2/CO比值先增大后减小。当热解温度为1 000℃,废轮胎含量为35%时,热解产物中(H2+CO)含量最高为61%,且H2/CO的比值达到最大值为1.53,有利于作为工业合成气原料。同一温度下,混合物直接热解气热值远远高于生物质单独热解,说明废轮胎的掺入有助于优化热解气组成,提升燃气品质。     

生物油部分供氧气化试验研究与数值模拟

采用小型实验装置和计算机数值模拟研究当量比和反应温度对生物油气化产物的产率、组成及碳转化率的影响,获得在O2和N2两种氛围下气化反应器内速度场和温度场的分布情况。结果表明:在相同气化温度下,CO2产率随O2当量比的增大而增加,最高可达447.72 m L/g;可燃气体产率随当量比的增大而减少并趋于稳定;碳转化率随当量比的增大先减少后增加,最高可达93.92%;生物油气化气体的产率随气化温度的升高而增加,且模拟值与实验值吻合较好,其中CO2含量及产率的实验值与模拟值的平均相对误差达到最小值,分别为24.74%和33.72%。     

花生壳和松木屑固定床低温热解特性的实验研究

分别以花生壳和松木屑为原料在固定床上进行低温热解实验,探究热解温度对热解产物产率的影响。利用气相色谱-质谱联用仪(GC-MS)对热解所得生物油组分进行定性分析,并对生物油中的愈创木酚进行定量分析。结果表明:花生壳和松木屑热解过程中半焦的产率都随热解温度的升高而降低;生物油的产率都随热解温度的升高先升高后降低,且都在500℃达到最大值,最大产率分别为13.14%和20.41%;热解气体的产率都随热解温度的升高而升高。两种生物质热解生物油中各类组分的含量随热解温度的升高发生不同的变化,其中愈创木酚的含量都随热解温度的升高先升高后降低,并在400℃达到最大值。     

ZnCl_2预处理对玉米芯热解特性的影响

对采用ZnCl_2浸渍法预处理的玉米芯进行实验,考察其预处理前后微观结构的变化;研究ZnCl_2用量和温度对玉米芯热解特性和产物分布及生物油成分的影响。结果表明:ZnCl_2浸渍处理使玉米芯表面结构变疏松,产生片状结构;随着ZnCl_2用量的增加,热解初始温度和最大热解失重速率对应温度向低温方向移动;当温度不变时,随着ZnCl_2浸渍量的增加,生物油产率降低,ZnCl_2质量分数为1.69%时玉米芯在450℃下生物油产率高达47.39%;相同的ZnCl_2浸渍量下糠醛在生物油中相对峰面积随温度的升高而降低,而同温下ZnCl_2浸渍量越大,糠醛相对峰面积越高;在350℃和ZnCl_2质量分数为5.89%的条件下,玉米芯热解获得的生物油中糠醛相对峰面积达到51.61%。     

秸秆类生物质选择性脱灰脱氧预处理耦合 热解制备高品质生物油研究

选取稻秆、玉米秆和麦秆作为原料,经脱灰脱氧联合预处理后在550℃下热解10 min收集液态产物生物油。通过对三种原料进行工业分析、元素分析和热值分析,结合红外光谱和热重曲线的图像分析,发现酸洗脱灰后K和Ca元素含量明显下降,麦秆中的K元素洗除率更是高达99.6%,烘焙脱氧后原料的C/O明显升高,原料热值增大。再经过对三种原料热解产物生物油进行GC/MS分析,发现酸洗脱灰有助于提高生物油收益率,可减少生物油中酸类和酚类物质含量,而糖类物质含量则明显提高。在烘焙脱氧过程中能有效减少纤维素和半纤维素的含量,从而减少其分解形成的酸的含量。因此,文中提出采用脱灰脱氧预处理的方法耦合热解制备高品质生物油,并通过三种原料的综合比较发现玉米秆为制备高品质生物油的最佳原料。     

二次热解对污泥热解产物影响的研究

针对上海市污水污泥,以提高热解气体、抑制热解焦油为目标,利用两段固定床反应器,研究二次热解温度对污泥一次热解挥发分的热解特性的影响。利用气相色谱定量研究不同二次热解温度下热解气中H2、CO、CO2、CH4的含量变化。利用全二维气相色谱-飞行时间质谱联用仪(GC×GC-TOFMS)定性研究不同二次热解温度下热解油化学组分。结果表明:二次热解温度高于600℃时,热解气体产率明显增加,液体产率明显减少。这表明,在仅改变上段固定床二次热解温度的条件下,一部分污泥热解油通过高温二次热解转化为气体。其中CH4是受二次热解影响最大的气体,相比于一次热解,当二次热解温度高达700℃时,CH4的累计释放量增加了7.0倍,这表明热效应明显促进了污泥热解挥发分的脱甲烷反应。为了更好地揭示污泥热解油转化成热解气的机理,运用GC×GC-TOFMS分析污泥热解油中上千种化合物。我们猜测长链脂肪含氮化合物主要通过脱甲烷反应产生CH4。酮类通过脱羧反应生成CO。     

中药渣固废的碳酸钾催化热解特性与产物分布规律

以木本中药渣为原料,采用浸渍法负载不同含量K₂CO₃催化剂;通过热重实验,分析中药渣催化热解特性和热解特征参数,并采用Starink法进行动力学分析,计算催化热解反应的表观活化能;使用固定床热解炉,优化催化热解反应条件,考察不同K₂CO₃负载量对热解产物分布的影响规律。热重结果表明,K₂CO₃能显著降低中药渣的初始热解温度和最大热解温度,从而降低热解快速失重段的反应活化能;且K₂CO₃负载量越大,催化热解效果越好。热解实验证实：K₂CO₃含量为中药渣催化热解反应的最主要影响因素,它可加速生物基大分子的低温解聚和热解中间产物的催化裂解,既可降低热解油产率,又能大幅提升H₂、CO和C₂H₆等小分子低碳烃气体的产率,且有利于提高热解气的H₂/CO比例。     

钙盐催化纤维素快速热裂解机理试验研究

在红外辐射加热实验装置内进行了钙盐催化纤维素快速热裂解机理实验研究。实验发现以生物油产率 的降低为代价,氯化钙促进了焦炭和气体产物的生成,尤其对焦炭的生成体现出明显的催化选择性。检测产物 中金属离子分布证实钙离子的催化作用主要发生在物料的固相空间,结合生物油成分分析认为钙盐在催化过程 中以离子的形式进入有机化合物内部结构,经由大量的脱水过程,促进了分子碎片重整和异构化过程,从而提 高了生物油中杂环类、脱水化合物以及缩醛化合物含量。     

Evaluation of esterified pyrolysis bio-oil as a diesel alternative

Refined pyrolysis bio-oil was produced via the pretreatment and esterification of pyrolysis bio-oil over 732-type ion-exchange resin. The main parameters of fuel property such as components, low calorific value and viscosity of refined pyrolysis bio-oil were analyzed. Different volume fractions of refined pyrolysis bio-oil were added to neat diesel to prepare bio-fuel blends. Combustion performances and emission characteristics of engine fueled with bio-fuel blends were analyzed at various loads. The results show that after esterification, the amount of esters and ketones in the crude pyrolysis bio-oil was significantly increased while the contents of acids, phenols and ethers were reduced. Compared with crude pyrolysis bio-oil, the pH value of refined pyrolysis bio-oil was improved to 5.6, the low calorific value increased by 14.89%, and the kinematic viscosity decreased by 10.13%. At the same load, the equivalent brake specific fuel consumption (BSFC) of bio-fuel blends was increased, the maximum cylinder pressures and the brake thermal efficiency (BTE) were both decreased but the peak of instantaneous heat release was increased slightly, and the exhaust gas temperatures also rose up. With the increase of refined pyrolysis bio-oil in bio-fuel blends, the difference between bio-fuel blends and neat diesel in the above indicators was more obvious. Besides, bio-fuel blends produced more HC, CO and smoke emissions but less NO_x emissions than neat diesel.     

Comparative study on pyrolysis and catalytic pyrolysis upgrading of biomass model compounds: Thermochemical behaviors,kinetics, and aromatic hydrocarbon formation

In order to understand the pyrolysis mechanism, reaction kinetic and product properties of biomass and select suitable agricultural and forestry residues for the generation desired products, the pyrolysis and catalytic pyrolysis characteristics of three main components (hemicellulose, cellulose, and lignin) of biomass were investigated using a thermogravimetric analyzer (TGA) with a fixed-bed reactor. Fourier transform infrared spectroscopy (FTIR) and elemental analysis were used for further characterization. The results showed that: the thermal stability of hemicellulose was the worst, while that of cellulose was higher with a narrow range of pyrolysis temperatures. Lignin decomposed over a wider range of temperatures and generated a higher char yield. After catalytic pyrolysis over HZSM-5 catalyst, the conversion ratio increased. The ratio for the three components was in the following order: lignincellulose < biomass < xylan. The Starink method was introduced to analyze the thermal reaction kinetics, activation energy (Ea), and the pre-exponential factor (A). The addition of HZSM-5 improved the reactivity and decreased the activation energy in the following order: xylan (30.54%) > biomass(15.41%) > lignin (14.75%) > cellulose (6.73%). The pyrolysis of cellulose gave the highest yield of bio-oil rich in levoglucosan and other anhydrosugars with minimal coke formation. Xylan gave a high gas yield and moderate yield of bio-oil rich in furfural, while lignin gave the highest solid residue and produced the lowest yield of bio-oil that was rich in phenolic compounds. After catalytic pyrolysis, xylan gave the highest yield of monocyclic aromatic hydrocarbons, 76.40%, and showed selectivity for benzene and toluene. Cellulose showed higher selectivity for xylene and naphthalene; however, lignin showed enhanced for selectivity of C10 + polycyclic aromatic hydrocarbons. Thus, catalytic pyrolysis method can effectively improve the properties of bio-oil and bio-char.     

CaO伴随纤维素快速热裂解的落体试验研究

采用自由落体-辐射加热的试验方法,对CaO伴随生物质快速热裂解制油的脱氧效果进行了研究.利用气相色谱/质谱联用仪(GC-MS)对油样进行分析,结果表明:纤维素一次裂解的主要产物是左旋葡聚糖(LG);纯纤维素以及33%和56%CaO伴随纤维素裂解油中LG的质量百分含量分别为59.1%、35.8%和25.1%;LG作为热解油中含氧量最高的成分,其质量百分含量随CaO的加入急剧下降,说明CaO的加入可降低热解油的含氧量.计算结果表明:33%和56%CaO伴随纤维素热裂解时,可分别降低油品含氧量约10%和12.5%,说明CaO可直接固定纤维素热裂解平行反应中CO2或类似中间基团,形成有利于葡萄糖单体分裂、重整路线进行的"化学汇"结果.     

Microwave assisted catalytic pyrolysis of bagasse to produce hydrogen

Using Ni/SiC as a catalyst, bagasse was microwave-assisted pyrolysis in a homemade quartz reactor. The results showed that with the continuous increase of Ni content, the experimental catalytic pyrolysis effect on bio-oil became more and more obvious, and the hydrogen yield gradually increased. When Ni content exceeded 8%, the hydrogen yield and bio-oil catalytic pyrolysis efficiency decreased, and the lowest bio-oil yield was 9.55% when Ni content was 15%, With the increase of power, the catalytic cracking efficiency and hydrogen yield of bio-oil increased, With the increase of catalyst dosage, the catalytic efficiency and the hydrogen yield increase gradually. When the catalyst quality exceeds 1/4 of the material, the growth rate of catalytic efficiency decreases, after alkali treatment, the variation law of hydrogen yield and bio-oil is consistent with that without alkali treatment. In contrast, more hydrogen can be produced after alkali treatment. Under the optimum conditions, the hydrogen yield was 35.85 g/kg biomass.     

Kinetic modeling and optimization of biomass pyrolysis for bio-oil production

Thermo-kinetic models for biomass pyrolysis were simulated under both isothermal and non-isothermal conditions to predict the optimum parameters for bio-oil production. A comparative study for wood, sewage sludge, and newspaper print pyrolysis was conducted. The models were numerically solved by using the fourth order Runge–Kutta method in Matlab-7. It was also observed that newspaper print acquired least pyrolysis time to attain optimum bio-oil yield followed by wood and sewage sludge under the identical conditions of temperature and heating rate. Thus, at 10 K/min, the optimum pyrolysis time was 21.0, 23.8, and 42.6 min for newspaper print, wood, and sewage sludge, respectively, whereas the maximum bio-oil yield predicted was 68, 52, and 36%, respectively.     

The effect of oyster shell powder and rice husk ash on the pyrolysis of rice husk for bio-oil

The aim of this study was to investigate the effect of oyster shell powder (OSP) and rice husk ash (RHA) on the pyrolysis of rice husk (RH) for bio-oil. The present study focuses on the effect of catalysts on pyrolysis of RH for bio-oil and the quantity of bio-oil produced. The results showed that both OSP and RHA could improve the yield and quality of bio-oil, and the catalytic effect of OSP was better than that of RHA. With the content of the two catalysts increased, the net increase range of bio-oil yield decreased gradually. With 3 wt.% of OSP or 2 wt.% of RHA, the yield of bio-oil achieved to 57.06% and 56.07% respectively, which increased by 6.03% and 4.20% compared to that of single pyrolysis of rice husk. Both OSP and RHA can increase the bio-oil heating value and decrease the acid value. With the presence of 1–5 wt.% of OSP or RHA in the RH pyrolysis process, the heating value of the bio-oil can be increased by 5.04–10.25% and 4.32–5.78%, the acid value of the bio-oil can be decreased by 5.30–13.54% and 9.81–33.01%, respectively. OSP was better than RHA on the heating value improvement, while RHA was superior to OSP in decreasing the acid value. The gas chromatography/mass spectrometry (GC-MS) analysis of bio-oil composition indicated that the formation of phenols, acids and ketones compounds were inhibited and alcohols and furan compounds were promoted with the addition of OSP and RHA catalysts. The study made the catalytic pyrolysis process more favorable for the production of high heating value fuel.     

In-situ catalytic upgrading of biomass-derived vapors using HZSM-5 and MCM-41: Effects of mixing ratios on bio-oil preparation

In this paper, two molecular sieves with different pore sizes, namely HZSM-5 and MCM-41, were mixed using different ratios and used in the in-situ catalytic pyrolysis of rape straw. The effects of different HZSM -5 and MCM -41 mixing ratios on the quality of the bio-oil were studied by physicochemical properties, product yields and compositions. Moreover, Brunauer-Emmett-Teller (BET) catalyst analysis was performed. The results showed that the liquid yield and organic phase decreased first and then increased, whereas the gas yield showed an opposite trend. The density, O/C and kinematic viscosity of the bio-oil organic phase decreased first then increased, whereas the H/C, pH values and higher heating values initially increased, then declined. The oxygen content, H/C, O/C, kinematic viscosity, density, higher heating value and pH value of the bio-oil organic phase obtained at 1:1 mixed ratio were 12.81%, 1.701, 0.126, 5.06 mm²/s, 0.94 g/cm³, 34.31 MJ/kg and 5.41, respectively. The organic phase included numerous organic compounds, such as carboxylic acids, aldehydes, ketones, hydrocarbons, alcohols, ethers and esters. The hydrocarbon content in the bio-oil organic phase gradually increased and the carbonyl groups content gradually decreased as the MCM-41 content increased from 0 to 50%. In contrast, the hydrocarbon content gradually decreased and the carbonyl groups content gradually increased as the MCM-41 content increased from 50% to 100%. The hydrocarbon and carbonyl groups contents were 53.83% and 6.35%, respectively, at the MCM-41 content of 50%. The mixed catalyst activity increased with the increase in MCM-41 content (up to 50%), and tended to be stable once the MCM-41 contents surpassed 50%.     

Oxidative pyrolysis of kraft lignin in a bubbling fluidized bed reactor with air

Fast pyrolysis of kraft lignin with partial (air) oxidation was studied in a bubbling fluidized bed reactor at reaction temperatures of 773 and 823 K. The bio-oil vapors were fractionated using a series of three condensers maintained at desired temperatures, providing a dry bio-oil with less than 1% water and over 96% of the total bio-oil energy.Oxygen feed was varied to study its effect on yield, composition, and energy recovery in the gas, char and oil products. The addition of oxygen to the pyrolysis process increased the production of gases such as CO and CO₂. It also changed the dry bio-oil properties, reducing its heating value, increasing its oxygen content, reducing its average molecular weight and tar concentration, while increasing its phenolics concentration. The lower reaction temperature of 773 K was preferred for both dry bio-oil yield and quality.Autothermal operation of the pyrolysis process was achieved with an oxygen feed of 72 or 54 g per kg of biomass at the reaction temperatures of 773 and 823 K, respectively. Autothermal operation reduced both yield and total energy content of the dry bio-oil, with relative reductions of 24 and 20% for the yield, 28 and 23% for the energy content, at 773 and 823 K.     

半纤维素模化物热裂解动力学研究

在热重红外联用系统中对生物质的主要组分半纤维素的模化物进行了热裂解动力学研究．在用红外压片微观结构分析方法验证木聚糖典型结构模型的基础上,得到不同升温速率下的热重曲线表明,随着升温速率的增加,各个阶段的起始和终止温度向高温侧轻微移动,主反应区间加宽以及炭产量逐渐增加;计算得到的木聚糖两阶段活化能分别为118．59 kJ／mol和66．69 kJ／mol．与纤维素热解气的联机红外分析谱图相比可知,木聚糖热解析出气体过程复杂,其中CO在全过程都有析出,而CH4主要来源于一次挥发分的二次分解．