Sustainability of biodiesel production in Malaysia by production of bio-oil from crude glycerol using microwave pyrolysis: a review

Biodiesel being one of the most promising renewable biofuels has seen rapid increase in production capacity due to high demand for diesel replacement; along with oversupply of its by-product, crude glycerol. Developing new industrial usage for glycerol is essential to defray the cost and sustainability of biodiesel industry and to promote the biodiesel industrialization. One of the approaches is by the transformation of glycerol into a liquid, referred as bio-oil through pyrolysis technology. Bio-oils produced by pyrolysis processes can be upgraded to produce transportation fuels or for power generation. However, current state of pyrolysis technologies are still major hurdles their development with respect to its commercial applications. Recently, microwave technology has attracted considerable attention as effective method for significantly reducing reaction time, improving the yields and selectivity of target products. Hence, this review strives extensively towards addressing the application of microwave-assisted technology applied to the pyrolysis process as a way of cost-effective and operationally feasible processes to directly utilize crude glycerol. The present review will focus on the pyrolyzed liquid product (bio-oil) derived by employing the microwave-assisted pyrolysis method. This review concludes that microwave-assisted glycerol conversion technology is a promising option as an alternative method to conventional glycerol conversion technology.     

固体酸催化剂SO2-4/SiO2-TiO2的制备及其催化酯化性能

 分别以机械混合法和浸渍法制备了SO2-4/SiO2-TiO2固体酸催化剂,以乙醇和乙酸的酯化反应为模型反应考察了不同SiO2含量及不同温度焙烧的催化剂的活性. 结果表明,机械混合法制备的400 ℃焙烧的SO2-4/40%SiO2-TiO2催化剂活性最高,部分回流时,乙酸几乎全部转化,全回流反应100 min时,其乙酸转化率达到84%. X射线衍射分析表明, SiO2抑制了硫酸氧钛的形成; 催化剂的活性组分包括一定量的四方晶锐钛矿型TiO2、 正交晶硫酸氧钛、少量立方晶金属钛和高比表面积的SiO2. 红外光谱分析表明,添加SiO2后催化剂形成 Ti-O-Si 键,进而使SO2-4与样品表面产生强相互作用; 结合的SO2-4主要以无机螯合状双配位和有机硫酸酯两种结构形式存在. 热重-示差扫描量热分析表明, SiO2的添加使SO2-4不易脱除,同时使锐钛矿TiO2向金红石相的转变温度降低.     

Thermochemical Liquefaction as a Cleaner and Efficient Route for Valuing Pinewood Residues from Forest Fires

Biomass thermochemical liquefaction is a chemical process with multifunctional bio-oil as its main product. Under this process, the complex structure of lignocellulosic components can be hydrolysed into smaller molecules at atmospheric pressure. This work demonstrates that the liquefaction of burned pinewood from forest fires delivers similar conversion rates into bio-oil as non-burned wood does. The bio-oils from four burned biomass fractions (heartwood, sapwood, branches, and bark) showed lower moisture content and higher HHV (ranging between 32.96 and 35.85 MJ/kg) than the initial biomasses. The increased HHV resulted from the loss of oxygen, whereas the carbon and hydrogen mass fractions increased. The highest conversion of bark and heartwood was achieved after 60 min of liquefaction. Sapwood, pinewood, and branches reached a slightly higher conversion, with yields about 8% greater, but with longer liquefaction time resulting in higher energy consumption. Additionally, the van Krevelen diagram indicated that the produced bio-oils were closer and chemically more compatible (in terms of hydrogen and oxygen content) to the hydrocarbon fuels than the initial biomass counterparts. In addition, bio-oil from burned pinewood was shown to be a viable alternative biofuel for heavy industrial applications. Overall, biomass from forest fires can be used for the liquefaction process without compromising its efficiency and performance. By doing so, it recovers part of the lost value caused by wildfires, mitigating their negative effects.     

生物质快速热裂解制取生物油试验研究

本文在快速热解试验装置中对片状的白松样品进行制取生物油的试验研究.考察了运行参数对热解产物分布的影响,重点研究了各个参数对热解气体和生物油组分的影响规律.结果表明,气体产物中主要以CO、CO2、H2和CH4为主,CO、H2和CH4的浓度随着温度升高而上升.生物油主要含有有机酸类、苯酚类和糖类等化合物.在同一载气流量下,随着辐射源温度的增加,大分子产物的产量逐渐减少,小分子产物的产量有所增加.在同一辐射源温度下,随着载气流量的减小,小分子产物的产量呈增加趋势.     

基于分子蒸馏的模拟生物油温和加氢研究

在固定床反应器上开展模拟生物油温和加氢实验,确定300℃/4 MPa为最佳工况,此条件下反应物除苯酚和愈创木酚外完全转化,液体产物选择性为85.0%,有效氢碳比从1.266提高到1.554,液体产物组成优化,酚类和酸类含量明显下降,反应活性明显改善,有利于后续催化裂化反应。     

Zn-P复合改性HZSM-5在线催化热解获取生物油的研究

为进一步提高精制生物油的制取效率和燃料品质,采用Zn和P对HZSM-5分子筛进行复合改性,使用XRD、SEM EDS、ICP-AES、BET等方法表征改性HZSM-5分子筛,考察了Zn、P改性对精制生物油理化特性和液相产物的化学组成以及对HZSM-5抗结焦性能的影响。结果表明,Zn、P在HZSM-5表面负载均匀,Zn、P改性未影响HZSM-5的晶体骨架结构,改性HZSM-5的比表面积随着Zn负载量的上升而减少;Zn负载量为3%时,催化热解得到的精制生物油含氧量为10.67%,热值为36.76 MJ/kg,pH值为5.85,精制生物油品质得到显著提升;液相产物中酸类、醛类和酮类等不期望物质相对含量显著下降,芳香族化合物相对含量显著增加,芳香族化合物相对含量为91.93%,其中,芳香烃为74.63%;HZSM-5因负载P使得其相对结焦量明显降低,显著增强了HZSM-5的稳定性;Zn改性促进了氢原子转移和碳正离子的形成,有利于提高HZSM-5分子筛的芳构化性能。     

From lignin-derived bio-oil to lignin-g-polyacrylonitrile nanofiber: High lignin substitution ratio and maintaining good nanofiber morphology

In this work, lignin-based nanofibers were produced from corn stalk lignin (CSL)/lignin-derived bio-oil (LBO) and polyacrylonitrile (PAN) co-polymers via electrospinning. During depolymerization, the addition of phosphotungstic acid (PTA) promoted the CSL catalytic conversion to some extent, the decrease of β-O-4 aryl ether bond, molecular weight (Mw) and polydispersity (PDI) was obvious. Compared with CSL, LBO can promotes the formation of uniform and smooth lignin-based nanofibers under high replacement rates condition and maintaining good morphology. Subsequent reactions between LBO and PAN fragments formed a better-integrated co-polymers structure containing linear PAN backbone. The Td of LBO-g-PAN was improved to 153 °C and the Tg was decreased to 96.5 °C. Rheological conclusions displayed that the viscosity of PAN/LBO/DMF was 0.082 Pa s, illustrating the polymer substance could be continuously spun into filament without causing degradation of the polymer substance. LBO-g-PAN also had high thermal stability, yielding of residual mass was 56.32 wt% at 700 °C.     

污泥的热解提油-半焦燃烧工艺的实验研究

本文提出了双流化床中污泥的热解提油-半焦燃烧工艺,组织实验论证并进行了探索研究。结果表明,双流化床中可以实现污泥热解提油工艺和半焦燃烧工艺的耦合,即获得了污泥热解产生的油和气,又实现了污泥的焚烧无害化处理。污泥在双流化床中发生热解反应时,干燥无灰基污泥的油产率为24.1%,是煤的2.4倍,干燥无灰基污泥的轻油产率为8.44%,是煤的9倍。该工艺中,污泥中热量的43.1%转化为油,10.4%转化为热值10.54MJ/m~3的气体燃料,46.5%的热量残留在污泥半焦中,在燃烧炉内燃烧放热。     

生物油部分氧化气化制备合成气研究

以生物油为原料,在常压和空气氛围下进行非催化部分氧化气化实验制备合成气,考察了气化温度、氧油比对合成气形成特性及合成气品质的影响,并对生物油非催化部分氧化气化制备合成气的主要反应过程进行了讨论。结果表明,升高温度可以促进生物油经非催化部分氧化气化制合成气过程中相关转化反应的进行,合适的氧油比有利于合成气的增加。当温度为1 050℃,空气量为0.2 L/min,进料量为72 g/h时,生物油经部分氧化产生的气体中H₂含量最高,CH₄、CO和CO₂很少;H₂/CO和H₂/(CO+CO₂)均达到最大值,分别为4.3和3.2。