生物油重质组分模型物热解行为及其动力学研究

采用TG-FT-IR在非等温条件下对生物油重质组分酚、醛和糖类模型代表物(丁香酚、香草醛、左旋葡聚糖)进行热解特性及其热解动力学分析。TG-DTG曲线和FT-IR测试数据显示,重质组分模型物热解的先后次序是酚类、醛类、糖类物质。香草醛、丁香酚均为一个主热解阶段,主要产物为水、烷烯烃、CO₂、CO和小分子酚、芳香醛。左旋葡聚糖热解分两阶段进行,热解发生在较高温区(180~370℃),主要热解产物有CO₂、烷烯烃、醛、酮和环醚,少量的CO和水。混合物热解分为三个阶段,产物与单一模型物热解产物相似,但有少量缩醛低聚物。对比单一组分,混合物中羰基和羟基组分在较高温区(≥300℃)存在相互作用,生成难分解的缩聚物。其中,糖类是影响重质组分热解速率的主要物质。根据热重数据对热解各阶段进行动力学拟合,确定了模型物热解反应动力学三因素。平均表观活化能和反应级数分别为:E_{左旋葡聚糖}第一、第二阶段分别为115.80 kJ/mol(0.5级)、141.19 kJ/mol(2/3级); E_混合物第一阶段为54.46 kJ/mol(1级)、第二阶段为50.67 kJ/mol(2/5级); E_丁香酚为42.29 kJ/mol(0.7级); E_香草醛为36.53 kJ/mol(0.95级)。     

不同蒸馏压力下的生物油分子蒸馏分离特性研究

采用分子蒸馏分离技术对热敏性生物油在不同蒸馏压力下的分离特性进行了研究。经过分子蒸馏分离后,生物油被分离为蒸出馏分油与残留馏分油,蒸出馏分油的得率随着压力的下降而显著增大,在700 Pa时达到了56.50%(质量分数)。在馏分油的物理性质方面,蒸出馏分油富集了生物油内的大部分水分,残留馏分油内水分得到了较好的脱除,其中,700 Pa下残留馏分油的水分含量降至4.20%(质量分数)。结合生物油及馏分油的GC-MS分析结果,对乙酸、苯酚、糠醛以及左旋葡聚糖等生物油内典型化合物在不同蒸馏压力下的分布特性进行了研究,获得了相应化合物在分子蒸馏过程中的富集规律。结合分离因子评估模型对生物油内14种代表化合物的富集特性进行了量化评价。     

富钙生物油煅烧过程中孔结构变化特性的研究

在热重分析仪上进行富钙生物油煅烧实验。结果表明,富钙生物油的煅烧过程分为三个阶段,分别是生物油部分组分的脱CO₂和H₂O阶段、有机酸钙盐分解阶段、碳酸钙分解阶段。其中,有机酸钙盐分解对煅烧产物的孔结构有重要影响。在450℃~600℃,气体析出的气蚀作用与生物油中高分子化合物的碳化沉积现象同时存在,两者共同作用,但后者占主导,高分子化合物的碳化沉积主要发生在500℃~600℃。600℃以后,碳酸钙开始分解,释放出CO₂,气蚀作用使煅烧产物内部形成新的微孔,产物具有发达的孔结构。相同煅烧温度下,富钙生物油煅烧产物的孔隙特性明显优于CaCO₃。     

生物油制氢中催化剂与吸收剂研究

本文利用固定床反应器考察了自制催化剂在生物油水溶性组分重整制氢反应中的表现以及耦合水蒸气预处理的CO2吸收剂对反应的影响。通过比较自制催化剂与商业催化剂Z417在重整反应中的催化性能,以及预处理吸收剂对重整反应的改进作用,结果表明：在反应温度为800℃,水油比为4．9的条件下,自制催化剂Ni／CeO2-ZrO2的氢产率...     

玉米秸秆生物油-柴油乳化油的燃烧特性

试验用生物油是玉米秸秆快速热解液化的产物,主要成分为含氧有机混合物和水,不宜直接作为燃料使用,但与柴油乳化后可实现其在发动机中应用.在一台未作改动的直喷式柴油机上研究了玉米秸秆生物油质量分数分别为10%(B10)和20%(B20)的生物油-柴油乳化油的燃烧特性.结果表明:与0号柴油相比,乳化油的滞燃期延长,预混燃烧放热...     

生物柴油-生物油乳化油的燃烧排放特性

在一台未作改动的直喷式柴油机上研究了生物油质量分数分别为10%和20%的生物柴油生物油乳化油的燃烧与排放特性。结果表明:与生物柴油相比,燃用乳化油时燃烧始点推迟,预混燃烧放热峰值升高,扩散燃烧放热峰值、最高燃烧压力和燃烧温度降低,燃烧持续期缩短,且随着生物油含量增加以上趋势更明显。燃用含10%生物油的乳化油时燃油经济性较生物柴油略低,与0号柴油相当,而燃用含20%生物油的乳化油时燃油经济性则低于生物柴油和0号柴油。乳化油的NO_x排放明显低于生物柴油,而碳烟排放高于生物柴油,但低于0号柴油。     

粗生物油催化裂解制取低碳轻烯烃

利用La/HZSM-5催化剂,研究了催化裂解粗生物油及其模型化合物(包括甲醇、乙醇、乙酸、丙酮和苯酚)制取轻烯烃的过程. 获得的最大轻烯烃产率为0.19 kg/kg粗生物油. 研究表明,温度、重时空速和镧对HZSM-5分子筛的改性等因素可用来调制烯烃产率和选择性. 分子筛中添加镧,可适当的调节催化剂酸度和强弱酸位比例,从而提高烯烃选择性、产率和催化剂稳定性. 生物油制备轻烯烃的效率与原料的化学成分和氢碳有效比(H/Ce? )密切相关. 此外,比较了粗生物油催化裂解和热裂解过程,同时利用模型化合物研究了生物油转化为轻烯烃的相关反应历程和机理.     

Lignin bio-oil-based electrospun nanofibers with high substitution ratio property for potential carbon nanofibers applications

We reported a new approach for development of lignin bio-oil-based electrospun nanofibers (LENFs) that had high substitution ratio (up to 80 wt%) and good morphology. This approach was particularly unique and translatable as it used small molecule lignin bio-oil with high reactivity and low heterogeneity obtained via lignin depolymerization reaction to produce well-oriented LENFs. Firstly, effects of various blends solutions ratios and electrospinning parameters on the characteristics of the obtained LENFs were analyzed. The results showed that the optimal parameters that resulted in the best electrospun nanofibers were as follows: blend solution ratio, the 20 wt% blend solution containing 80 wt% straw lignin bio-oil (SLB) and 20 wt% polyacrylonitrile (PAN), flow rate, 1 mL/h, voltage, 20 kV, rotational speed, 500 r/min and the distance between needle and collection screen, 20 cm. Secondly, used the best LENFs, we also applied to prepare lignin bio-oil-based carbon nanofibers (LCNFs) and estimated its properties by scanning electron microscope (SEM), X-ray diffraction (XRD) patterns, Raman spectroscopy and tension testing. Our results demonstrated that compared with pure PAN carbon nanofibers (PCNFs), the as-prepared LCNFs had similar smooth surfaces, similar crystallinity and similar mechanical properties. This work can promote the utilization of lignin depolymerization main-products to produce lignin-based materials, while also help to reduce use of high-cost PAN.     

Preparation and application of an environmentally friendly compound lubricant based biological oil for drilling fluids

As the basic raw material of bio-oil based eco-friendly lubricant, a special selected by-product vegetable acidified oil (AO) was modified by vulcanization, esterification, or vulcanization followed by esterification. The optimized vulcanization process conditions are 1% sulfur powder catalyzed, temperature 130 ℃, reaction time 2 h, while the optimized esterification process requires 20% glycerol and 1% H₂SO₄ catalysis, reaction temperature 220 ℃, reaction time 3 h. We compounded modified AO, diluent, pour point depressant and emulsifier into an advanced drilling lubricant F-1. F-1 has excellent performances in bentonite drilling fluids, the extreme pressure lubrication coefficient reduction rate (Δf) in fresh water mud is 86.84%, and 85.76% in 4% NaCl salt water mud. After aging at 150 ℃ for 16 h, its Δf is improved compared with room temperature. Adding F-1 to the basic bentonite mud system, the filtration loss of drilling fluids decreased from 10 mL to 6.5 mL, the apparent viscosity and plastic viscosity experienced little change before and after aging. The new bio-oil compound lubricant has an excellent temperature resistance, a high salt contamination resistance and cost-effective. Vulcanization and esterification processes help to improve the lubricity and reduce foaming rates.     

FLASH PYROLYSIS OF BIOMASS PARTICLES IN FLUIDIZED BED FOR BIO-OIL PRODUCTION

Biomass utilization could relieve the pressure caused by conventional energy shortage and environmental pollution. Advantage should be taken of the abundant biomass in China as clean energy source to substitute for traditional fossil fuels. At present, flash pyrolysis appears to be an efficient method to produce high yields of liquids that could either be directly used as fuel or converted to other valuable chemicals. Experiments were carried out of pyrolyzing biomass particles in a hot dense fluidized bed of sand to obtain high-quality bio-oil. Among four kinds of biomass species adopted in our experiment, Padauk Wood had the best characteristics in producing bio-oil. GC-MS analysis showed bio-oil to be a complex mixture consisting of many compounds. Furthermore, an integrated model was proposed to reveal how temperature influences biomass pyrolysis. Computation indicated that biomass particles underwent rapid heating before pyrolysis.