聚丙烯和毛竹共热解的研究

在自制固定床反应器中,对聚丙烯和毛竹共热解进行研究,得到了反应气氛、热解温度、反应物配比、反应时间对共热解的影响规律。实验结果表明,由于毛竹与聚丙烯在热解过程中的相互影响,两者共热解时的液体收率和产物分布均与两者单独热解时不同,油相液体产物的辛烷值随毛竹加入量的增加而增大,在聚丙烯和毛竹的最佳配比下,两者共热解的协同作用最明显,不仅原料的转化率最大,而且所得液体产物的收率最高,H2气氛较之N2气氛更有利于油相产物的生成和毛竹中木质素成分的热解。本文条件下,获得最佳油相液体收率的条件为,聚丙烯/毛竹配比8∶2,热解温度520℃,反应时间4h,H2气氛,油相液体收率达53.9wt.%,辛烷值为77.3。     

高密度聚乙烯与两种典型生物质在Y型分子筛上的催化共热解研究

采用固定床反应器,在氢气气氛下研究了高密度聚乙烯(HDPE)与两种典型生物质(杉木、毛竹)(8:2wt%)的共热解及在Y型分子筛上的催化共热解。结果表明,与HDPE单独热解相比,共热解生成的油相液体的碳数分布变窄,使C5-C11汽油馏分的含量显著增加,而C12-C20以及C20 组分相应降低。共热解最高的总液体收率出现在NaY催化剂上,毛竹与HDPE共热解中达到58·9%。在Y型分子筛加入后,共热解水相产物中乙酸含量明显增加,苯酚类产物含量则显著下降。乙酸生成量最多的是USY催化剂,其次是HY、NaY。在USY催化剂作用下,毛竹与HDPE共热解水相液体所含有机物中,乙酸含量达到38·3%。     

Pd/Al2O3催化剂催化毛竹与聚乙烯共裂解反应研究

我们采用等体积浸渍法制备了Al2O3负载贵金属Pd系列催化剂,分别在N2和H2气氛下,研究了不同Pd负载量的催化剂对毛竹和低密度聚乙烯(LDPE)混合物的催化裂解性能.实验结果表明:Pd的负载量为1.0%时,Pd/Al2O3催化剂在两种气氛下活性均较好,在H2气氛下所得到的油品中烯烃含量较低,异链烷烃和环烷烃含量较高,油品的收率和质量均明显优于在N2气氛下所得到的油品.XRD表征发现,Pd负载量为1.0%的催化剂上,Pd在Al2O3载体上生成了晶形,表明金属钯有利于毛竹和LDPE共裂解生成液体产物.     

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.     

基于裂解气质联用分析的生物质逐级热解研究

为探究生物质快速热解反应历程,利用裂解气质联用仪对生物质进行逐级热解实验,考察在不同温度区间热解液体产物组分的分布规律。实验结果表明,生物质的化学组成和热解温度区间对热解液体产物都有重要影响。桉木在25℃~400℃热解液体产物较少,主要是吡喃和芳香类化合物,其中5,6-二氢-4-羟基-吡喃-2-酮相对峰面积随温度升高而降低;在450℃~500℃热解液体产物种类和产量均较多,主要以酮类和芳香类化合物为主。玉米芯热解规律和桉木的相似,但在25℃~350℃主要以呋喃类化合物为主,主要热解液体产物是2,3-二氢-苯并呋喃和2-甲氧基-4-乙烯基苯酚,在400℃~450℃热解液体产物以酮类化合物为主。生物质主要化学组分在不同温度区间热解得到不同液体产物,对其进行选择性热解,能够有效实现生物质资源的综合利用。     

烟煤与生物质快速共热解产物特性分析

研究了烟煤(YL)分别与富含半纤维素的玉米芯(CB)和富含木质素的松木屑(SD)快速共热解产物产率和气体组成的变化规律。结果表明,烟煤与生物质共热解组分互相作用,造成共热解气、液、固相产率和气体组成的明显变化,且与生物质种类有关。相对于独立热解过程,玉米芯丰富的半纤维素造成热解水蒸气和CO₂浓度较高,且玉米芯中富含的K元素挥发迁移至煤焦表面,对热解半焦与水蒸气、CO₂的气化反应起到催化作用,反应生成的H₂和富氢组分易与热解生成的自由基结合,抑制自由基之间的缩聚反应,使得共热解气体和液体产率增加,而半焦产率减小。烟煤/松木屑共热解过程中,松木屑中富含的Ca元素在煤焦表面迁移,促进了松木屑热解液体在半焦表面裂解反应,生成CO₂、CO和富氢自由基等轻质组分,造成共热解半焦和液体产率降低而气体产率增加。热解产物半焦、焦油、水蒸气、CO₂之间的气化和裂解反应均产生富氢的次生组分,从而提高了共热解气体中CO和烃类气体产率,降低了H₂产率。     

熔融盐对印刷线路板热解影响实验研究

在固定床反应器中进行热解实验，考察不同热解终温、不同熔融盐添加量下印刷线路板热解过程中碳的气相转化率，并对热解液体和固体产物进行特性分析。结果表明,熔融盐的存在可以明显提高热解过程碳的气相转化率，减少液体产物产率。在未添加熔融盐的条件下，热解终温900℃时，碳的气相转化率为35.94%，液体产物产率为28.29%。添加 (71%Na2CO3-29%K2CO3) 熔融盐后，热解终温700℃时，碳的气相转化率为40.76%,液体产物产率为22.34%。添加 (8.3%Na2CO3-91.7%NaOH) 熔融盐后，碳的气相转化率达到59.36%，液体产物产率减少为6.88%。元素分析结果表明，熔融盐的存在可以减少固体残渣中的含碳量，而液体产物的H/C原子比为1.12～1.20。     

生物质热解过程中NO、NH3和HCN的释放特性

在氩气气氛下,利用固定床反应器对稻草（DC）、麦杆（MG）和锯末（JM）三种生物质进行热解实验,采用傅里叶变换红外光谱仪（FT-IR）在线检测热解气体产物中的含氮组分,分析各种气相含氮组分的释放规律。实验结果表明,由于锯末中木质素含量较高,锯末热解开始快速释放NO、NH₃和HCN的温度明显高于稻草和麦杆。稻草热解过程中生成的NH₃、HCN和NO量最大。低温下NH₃的生成至少部分与生物质中氨基结构的分解有关,HCN的生成温度较高。不同生物质热解过程中NO、NH₃和HCN释放特性的差异,是由生物质大分子结构不同、灰分含量及成分不同、N含量不同等决定的,以及氮在生物焦、焦油和气相间的分配差异造成的。     

高硫强粘结性煤与生物质共热解的研究

用 5种高硫强粘结性煤与 2种生物质在 1kg h回转炉内共热解 ,对产品产率、煤与生物质中硫和氮的热解脱除、焦炭的光学组织进行了研究。结果表明 ,初次焦油的生成率和二次裂解率随热解温度的变化可分别用正态分布函数和韦布尔分布函数模拟 ;生物质可阻止强粘结性煤热解过程中颗粒之间的粘结 ,得到粒状焦炭 ;生物质热解生成较多的H2 ,有利于煤中硫和氮的脱除 ;随着温度的升高、煤粒度的减小和煤变质程度的降低 ,热解脱硫和脱氮率增大 ;煤热解产生的中间相与生物质之间的物理化学作用阻碍光学各向异性组织的形成和发展。     

生物质气化燃气中固体颗粒物的恒温临氧热解机理研究

在固定床反应器中考察了不同气氛下PBG恒温热解特性的差异,结合XPS与~(13)C NM R等技术手段分析了400℃恒温热解条件下PBG固相产物的化学结构变化。结果表明,PBG在400℃恒温热解时,生物质气化燃气(BAG)与N_2气氛下更易生成焦油,其析出量分别为50.71与37.45 mg/g,而临氧燃气气氛(BAG+2%O_2)下焦油析出量仅为11.96 mg/g,说明适量O_2的存在可有效抑制焦油的生成。进一步进行化学结构分析表明,在燃气(BAG)恒温热解条件下,PBG主要发生以脱氢脱氧为主的芳香化缩聚反应,易形成焦油类的大分子多环芳烃;而在临氧燃气(BAG+2%O_2)恒温热解条件下,PBG表面的有机基团易与O_2发生表面氧化反应,生成表面含氧官能团,在一定程度上抑制了芳香环缩聚反应,进而有利于降低焦油类物质的产率。因此,在生物质气化燃气实际高温过滤过程中适当添加氧(如:2%O_2),可有效降低PBG焦油收率,且不会形成大分子多环芳烃,有助于解决粗燃气过滤的过滤介质堵塞问题。     

Production of liquid fuels and chemicals from pyrolysis of Bangladeshi bicycle/rickshaw tire wastes

Tire wastes in the form of used bicycle/rickshaw tires available in Bangladesh were pyrolyzed in a fixed-bed fire-tube heating reactor under different pyrolysis conditions to determine the role of final temperature, sweeping gas flow rate and feed size on the product yields and liquid product composition. Final temperature range studied was between 375 and 575 °C and the highest liquid product yield was obtained at 475 °C. Liquid products obtained under the most suitable conditions were characterized by elemental analyses, FT-IR, ¹H NMR and GC–MS techniques. The results show that it is possible to obtain liquid products that are comparable to petroleum fuels and valuable chemical feedstock from bicycle/rickshaw tire wastes if the pyrolysis conditions are chosen accordingly.     

煤在合成气、氢气和氮气气氛下的热解研究

采用固定床反应器，在合成气气氛下对中国寻甸褐煤、蒙古Shiveeovoo褐煤和Khoot油页岩进行了热解研究。升温速率10 ℃/min，褐煤热解温度400 ℃～800 ℃，油页岩热解温度300 ℃~600 ℃，研究结果与氢气和氮气气氛下的热解进行了比较。结果表明,与加压热解不同，褐煤在不同气氛下常压热解半焦和焦油收率差别不大，但对油页岩，合成气和氢气气氛下热解焦油收率高于氮气，气体收率低于氮气。黄铁矿硫在不同气氛下热解均极易脱除，并部分转化为有机硫。油页岩的总硫脱除率远低于褐煤，与油页岩的高灰分含量有关。与氮气甚至氢气相比，合成气下寻甸褐煤的高总硫脱除率和低有机硫含量与合成气中的CO有关。但CO在油页岩热解脱硫中不起作用，也与油页岩高灰分含量有关。研究结果也表明合成气可代替氢气进行加氢热解。     

Thermal self-sustainability of biochar production by pyrolysis

The pyrolysis of several agricultural and biofuel production residues (grape residues, sugarcane residues, dried distiller's grain, palm oil residues, apple pomace and forestry residue) has been carried out in a pilot bubbling fluidized bed pyrolyzer operating under a range of temperature from 300 to 600 °C and two vapor residence times (2 and 5 s), with the aim of determining their pyrolysis behavior including products yields and heat balance. The composition of the product gases was determined, from which their heating value was calculated. The liquid bio-oil was recovered with cyclonic condensers. The thermal sustainability of the pyrolysis process was estimated by considering the energy contribution of the product gases and of the liquid bio-oil in relation to the pyrolysis heat requirements. The most promising biomass feedstocks for the sustainable production of biochar were indentified. Furthermore, this study presented the char yield in relation to the excess heat that could be obtained by combusting the gas and bio-oil coproducts of biochar production, as functions of pyrolysis temperature and vapor residence time.     

Online upgrading of organic vapors from the fast pyrolysis of biomass

The online upgrading process that combined the fast pyrolysis of biomass and catalytic cracking of bio-oil was developed to produce a high quality liquid product from the biomass. The installation consisted of a fluidized bed reactor for pyrolysis and a packed bed reactor for upgrading. The proper pyrolysis processing conditions with a temperature of 500℃ and a flow rate of 4m3·h-1 were determined in advance. Under such conditions, the effects of temperature and weight hourly space velocity (WHSV) on both the liquid yields and the oil qualities of the online catalytic cracking process were investigated. The results showed that such a combined process had the superiority of increasing the liquid yield and improving the product quality over the separate processes. Furthermore, when the temperature was 500℃, with a WHSV of 3h-1, the liquid yield reached the maximum and the oxygenic compounds also decreased obviously.     

Thermal degradation of polymers: Part XXVIII — Vacuum pyrolysis of poly(m-acetamidostyrene): Products volatile at ambient temperature

The products obtained on degradation of poly(m-acetamidostyrene) (Pm-AAS) in vacuo are described. The effects of molecular weight and pyrolysis temperature are discussed and compared with those observed for polystyrene (PS) under identical conditions.The liquid products of pyrolysis were separated and identified by gas-liquid chromatography and mass spectrometry. Monomer was not present in the liquid fraction from Pm-AAS and product analysis revealed significant differences in the degradation behaviour relative to PS. This behaviour was ascribed to differences in volatility of the parent monomers, their relative susceptibility to thermal polymerisation and the ability of the side grouping to undergo cleavage in the substituted polymer. Mechanisms involving side group cleavage are proposed and discussed to account for the products obtained. Quantitative studies are also described and compared with results from PS.     

钨过氧酸盐离子液体催化过氧化氢氧化苯甲醇制苯甲酸

用甲基三辛基氯化铵和钨酸钠一步法合成甲基三辛基季铵钨酸盐离子液体[(CH3)N(n-C8H17)3]2W2O11,以该离子液体为催化剂,在无反应溶剂条件下催化过氧化氢氧化苯甲醇生成苯甲酸。 考察了反应温度、催化剂用量以及氧化剂过氧化氢用量对苯甲酸产率的影响。 确定优化条件：反应温度70 ℃,苯甲醇用量5 mmol,催化剂用量是底物的0.4%(摩尔分数),30%过氧化氢用量2 mL,苯甲醇的转化率可达99%,苯甲酸选择性为98%。 该方法具有反应条件温和、产率高和选择性好的优点。     

吴家坪煤在流化床热解过程中含硫气体产物的分析

在氧气体积分数分别为3.0%、5.6%、 8.7%的O2 N2混合气，热解温度500℃～800℃, 停留时间30min下，对吴家坪煤在流化床反应器热解过程中的含硫气体进行了分析。热解过程中主要的含硫气体是H2S、COS和SO2, 且它们的逸出规律一致：随着温度和氧气体积分数的增高, 逸出速率加快。 氧气体积分数对煤中的H2S、COS的影响是相似的, 随着氧气体积分数增加, 相对于3.0% O2 N2 气氛, H2S和COS的逸出量占气相中总硫的比例在5.6% O2 N2 气氛下降, 在8.7% O2 N2 气氛下又有所上升; 而氧气体积分数对SO2的影响与之相反, 在5.6% O2 N2 气氛下, 气相中93%以上是以SO2形式逸出的, 在8.7% O2 N2 气氛下, SO2的比例又下降很多。这是由于8.7% O2 N2 气氛下, 更多的氧气参与了C—C键断裂的反应, 使脱去的硫转化到焦油中，从而也生成了大量的CO，使得在8.7% O2 N2气氛下CO/SO2比明显大于5.6% O2 N2气氛下的。     

纤维素热裂解过程中活性纤维素的生成和演变机理

在辐射加热闪速热裂解实验台上获取了一种可溶性的黄色固体中间产物, 在两个不同辐射热流下其产量随着反应的进行均呈现升高-稳定-再升高的变化趋势. 高效液相色谱分析发现, 其主要成分包括低聚糖、葡萄糖、左旋葡聚糖、丙酮醛等. 将其中的纤维二糖、纤维三糖等低聚糖, 以及葡萄糖等单糖的混合物归为活性纤维素. 在高热流下, 活性纤维素的相对产量呈现先升后降的趋势, 在可溶性产物中的含量可高达68%(w, 质量分数), 且聚合度较高的低聚糖占主导地位. 在低热流下活性纤维素产量相对较低, 最高达到约57%(w), 更多地由聚合度较低的糖类组成. 在高温下活性纤维素极不稳定, 易降解生成聚合度更低的糖类, 甚至焦炭、挥发份和气体产物. 最后提出了一个改进的机理模型, 描述了活性纤维素的生成和演变的反应路径.     

Fast pyrolysis of rice straw,sugarcane bagasse and coconut shell in an induction-heating reactor

With the application of induction heating, a fast pyrolysis was used for producing valuable products from rice straw, sugarcane bagasse and coconut shell in an externally heated fixed-bed reactor. The effect of process parameters such as pyrolysis temperature, heating rate and holding time on the yields of pyrolysis products and their chemical compositions were investigated. The maximum yield of ca. 50% on the pyrolysis liquid product could be obtained at the proper process conditions. The chemical characterization by elemental (CHNO), calorific, Fourier transform infrared (FT-IR) spectroscopy and gas chromatography/mass spectrometry (GC–MS) showed that the pyrolysis liquid products contain large amounts of water (>65 wt.%), and fewer contents of oxygenated hydrocarbons composing of carbonyl groups, resulting in low pH and low heating values. The results were very similar to bio-oils obtained from other biomass materials. The residual solid (char or charcoal) was also characterized in the present study.