城市生活垃圾低温慢速热解实验研究

通过城市生活垃圾在固定床反应器中的低温热解实验,分析了最终热解温度对产物质量分布和热解气成分的影响。实验条件为:最终热解温度300～550℃,升温速度为10℃/min,物料粒径1 cm,氮气流量为1 L/min,固相停留时间为30 min。研究发现,随着最终热解温度的升高,热解半焦质量分数从57.55%迅速降低到31.45%,热解气质量分数从11.66%增加到24.15%,热解油质量分数先增加后减少,500℃时达到最大值36.67%。当最终热解温度从300℃增加到550℃时,CO的体积分数从45.62%逐渐降低到24.84%;CO_2的体积分数先增加后减少,350℃时达到最高值57.25%;H_2,CH_4,C_2H_6,C_2H_4和C_2H_2的体积分数逐渐增大,当最终热解温度为550℃达到最大值,分别为4.47%,12.91%,9.59%,7.49%和2.76%。     

废印制线路板真空热解产物分析

在自行设计的间歇式固定床真空热解装置中热解废印制线路板(PCB),对热解产物进行了分析.在热解温度为550 ℃、热解压力为20 kPa、恒温时间为60 min的条件下,得到的热解产物质量分数为:热解渣70%;热解油3%～4%;不可冷凝热解气26%～27%.经气相色谱-质谱联用(GC-MS)分析,热解油经常压蒸馏后得到的低沸点液态油中含有29种化合物,主要有苯酚、对异丙基酚、3-乙基酚、4-甲酚及2-溴苯酚,还含有少量含溴化合物和含氯化合物.热解油经简单的蒸馏就可达到回收酚类化合物的目的.热解渣经风选可实现铜与黏附有碳黑的玻璃纤维的分离,其中铜质量分数约30%,黏附有碳黑的玻璃纤维质量分数约70%.     

废聚苯乙烯泡沫塑料的催化裂解

为了对废聚苯乙烯泡沫塑料（WPS）资源化利用,通过对WPS进行催化裂解的方法,研究了催化剂种类和裂解温度对裂解时间、裂解油产率、苯乙烯回收率以及裂解油纯度的影响。研究结果表明,催化剂种类和裂解温度对裂解反应有着重要影响。裂解温度升高,裂解油产率提高,裂解时间缩短,但苯乙烯选择性下降;低于380 ℃时,氧化钙的裂解油产率和裂解时间优于氧化铝和氯化铝,但苯乙烯的选择性劣于氧化铝和氯化铝;高于400 ℃时,氯化铝、氧化铝和氧化钙的催化活性接近。在实验条件下,WPS催化裂解的最佳催化剂为氯化铝,380 ℃下的裂解时间为25 min,裂解油产率为85.48%,裂解油中苯乙烯含量为80.66%（w）,且副产物较少。     

淬火油泥的热解动力学分析及协同作用研究

采用热重差热分析法和傅里叶变换红外光谱分析联用的方法（TG-FTIR）研究淬火油泥（QOS）的热解过程,解析了热解过程的动力学特性,分析了其中的矿物油（MO）和残渣（SR）在QOS热解过程中的相互作用。实验结果表明：QOS热解过程包含油分热解阶段和矿物质分解阶段;低温段热解温度为150~520 ℃,高温段热解温度为800~980 ℃;SR的热解过程分为油分热解反应和残渣中Fe₂O₃的还原反应;MO的热解过程只有轻质油分的挥发和重质油分的热解。FTIR表征结果显示：QOS热解过程析出的气体主要为CO₂、CO和有机化合物;SR热解过程中CO₂的特征峰强度高于其他气体的特征峰强度;MO热解过程中烷烃的特征峰强度高于其他气体的特征峰强度,且MO主要以轻质油分为主。在QOS的热解过程中,初温~480 ℃时,SR所含的Fe₂O₃对MO的热解起促进作用,300 ℃左右时促进效果最明显。     

废轮胎与煤共热解失重特性研究

采用热解重量分析法研究了废轮胎粉、炼焦煤粉(简称煤粉)及混合样的热解特性。实验结果表明,废轮胎粉的热解出现三个显著的失重峰,煤粉热解仅出现一个显著失重峰。与煤粉热解相比,废轮胎粉热解开始失重温度和失重基本结束的温度相对较低,失重速率较大,且失重量较大。煤粉与废轮胎粉的显著失重存在重叠的温度区间(360～450℃),说明废轮胎粉与煤粉可以进行共热解。随废轮胎粉质量分数增加,共热解物料总失重率增加。废轮胎粉与煤粉共热解存在协同效应,在280～540℃时协同效应抑制共热解挥发分的逸出,导致失重量降低,最大失重速率峰温升高;高于540℃后,协同效应促进共热解反应,使共热解总失重率增大。     

废旧硅橡胶酸性热解残渣热解馏出物组分分析

在不同温度下对废旧硅橡胶酸性热解残渣进行热解,通过气相色谱-质谱联用技术对馏出油的组分进行分离与鉴定.实验结果表明:当热解温度为180℃时,馏出油组分相对较单一,主要是低沸点硅油类物质,可再次回收利用,实现清洁生产;当热解温度为340℃时,馏出油组分多且复杂,主要为高沸点硅油类物质,还有硅油类物质氧化和高温热解后的产物...     

生物质热解半焦水蒸气气化制取富氢燃气实验研究

实验以CaO作为CO_2的吸附剂,在固定床反应器中完成了蓝藻热解半焦水蒸气气化实验。研究水蒸气气化过程中CaO的存在和原料粒径的不同对实验产生的影响。实验结果表明,蓝藻热解半焦水蒸气气化过程中,CaO的存在能显著增加氢气的产率,原料粒径的不同对气体产率和成分的影响几乎可以忽略,粒径为0.3～0.45 mm时,获得最大气体产率和氢气体积占比分别为2.05 Nm~3/kg和63.74%。     

稀土改性NaY型分子筛催化热解废轮胎

采用稀土氧化物改性NaY型分子筛（Ⅰ型催化剂）,100 gⅠ型催化剂中添加0.5 g CeO₂得到Ⅱ型催化剂,100 gⅠ型催化剂中添加0.5 g La₂O₃和0.5 g CeO₂得到Ⅲ型催化剂。分别采用Ⅰ型、Ⅱ型和Ⅲ型催化剂催化热解废轮胎（粒径0.2 mm）,Ⅱ型和Ⅲ型催化剂的产油起始温度和终止温度均低于Ⅰ型催化剂。在催化剂加入量为2.5 g、废轮胎加入量为100 g 的条件下,Ⅲ型催化剂催化热解反应的产油率和油气总产率均高于Ⅰ型和Ⅱ型催化剂。Ⅱ型和Ⅲ型催化剂催化热解主要产生轻组分气体,Ⅱ型催化剂C₄选择性最高,Ⅲ型催化剂C₃选择性最高。     

废植物热解制气制油制炭的研究

主要考察了不同废植物的热解产气产油（液）产炭效果及不同过程条件的热解产气产油产炭效果。可用作热解制气制油制炭的废植物包括一切草木本植物,含有大量的木质素和纤维素,属于可再生能源。废植物热解制气制油制炭,可以使大量的被遗弃废植物得到充分利用,变废为宝,同时,可以帮助解决未来可能出现的能源危机,为废弃物的资源化、为未来的能源发展提供了新的方向。另外,由于废植物的广泛可取,废植物热解制气特别适用于在中小城市和农村推广应用,改善人们的生活条件和居住环境,进一步缩小城乡差距,为国家的经济发展做出贡献。     

含油污泥热解过程模拟和质能平衡分析

钢铁行业对钢材冷却时会产生大量含油污泥,对环境造成了严重污染。对含油污泥的热解过程进行了实验和仿真模拟研究,并对实验中分离出的热解油进行组分分析。轻质油中脂肪族化合物、杂环化合物和芳香族化合物分别占97.8%、1.85%和0.35%。重质油中脂肪族化合物和杂环化合物分别占93.27%和6.73%。另外通过Aspen Plus建立模型,并根据模型数据对热解过程的收支平衡进行分析。研究表明热解产物携带能量从大到小依次为热解油、残渣、热解气和水。含油污泥产出的挥发分质量占比为69.4%,能够有效利用的化学能较多。     

The important role of microwave receptors in bio-fuel production by microwave-induced pyrolysis of sewage sludge

Microwave receptor plays an important role in the microwave pyrolysis of sewage sludge in view of its significant influence on the yield and property of bio-fuel products. The yield and the chemical compositions of bio-fuels (gases and oils) obtained from sewage sludge mixed with different receptors (graphite, residue char, active carbon or silicon carbide) were investigated in this study by Gas Chromatography (GC), Gas Chromatography-Mass Spectrometry (GC-MS), and Fourier Transform Infrared Spectroscopy (FTIR). The results showed that the use of silicon carbide gave rise to the highest final temperature of 1130 °C, resulting in the highest yield of gas fraction (up to 63.2 wt.%). The low heating rate (200 °C/min) which was attributed to the addition of residue char promoted condensation reactions and resulted in an increase in solid yield. The existence of active carbon could prolong the resistance time of volatiles in the hot zone owing to its porous structure, generating the maximum concentration of H₂ + CO (60%) in the pyrolysis gas. When graphite was used, the final low temperature favoured the cyclization of the alkenes, giving rise to a higher concentration of mononuclear aromatics in the pyrolysis oils. The model established in this study revealed that the quantity and quality of the products obtained from the microwave pyrolysis highly depended on the process conditions, which were influenced by the receptor significantly.     

Vacuum pyrolysis of waste tires with basic additives

Granules of waste tires were pyrolyzed under vacuum (3.5-10kPa) conditions, and the effects of temperature and basic additives (Na(2)CO(3), NaOH) on the properties of pyrolysis were thoroughly investigated. It was obvious that with or without basic additives, pyrolysis oil yield increased gradually to a maximum and subsequently decreased with a temperature increase from 450 degrees C to 600 degrees C, irrespective of the addition of basic additives to the reactor. The addition of NaOH facilitated pyrolysis dramatically, as a maximal pyrolysis oil yield of about 48wt% was achieved at 550 degrees C without the addition of basic additives, while a maximal pyrolysis oil yield of about 50wt% was achieved at 480 degrees C by adding 3wt% (w/w, powder/waste tire granules) of NaOH powder. The composition analysis of pyrolytic naphtha (i.b.p. (initial boiling point) approximately 205 degrees C) distilled from pyrolysis oil showed that more dl-limonene was obtained with basic additives and the maximal content of dl-limonene in pyrolysis oil was 12.39wt%, which is a valuable and widely-used fine chemical. However, no improvement in pyrolysis was observed with Na(2)CO(3) addition. Pyrolysis gas was mainly composed of H(2), CO, CH(4), CO(2), C(2)H(4) and C(2)H(6). Pyrolytic char had a surface area comparable to commercial carbon black, but its proportion of ash (above 11.5wt%) was much higher.     

Quality improvement of pyrolysis oil from waste rubber by adding sawdust

This work was aimed at improving the pyrolysis oil quality of waste rubber by adding larch sawdust. Using a 1 kg/h stainless pyrolysis reactor, the contents of sawdust in rubber were gradually increased from 0%, 50%, 100% and 200% (wt%) during the pyrolysis process. Using a thermo-gravimetric (TG) analyzer coupled with Fourier transform infrared (FTIR) analysis of evolving products (TG–FTIR), the weight loss characteristics of the heat under different mixtures of sawdust/rubber were observed. Using the pyrolysis–gas chromatography (GC)–mass spectrometry (Py–GC/MS), the vapors from the pyrolysis processes were collected and the compositions of the vapors were examined. During the pyrolysis process, the recovery of the pyrolysis gas and its composition were measured in-situ at a reaction temperature of 450 °C and a retaining time of 1.2 s. The results indicated that the efficiency of pyrolysis was increased and the residual carbon was reduced as the percentage of sawdust increased. The adding of sawdust significantly improved the pyrolysis oil quality by reducing the polycyclic aromatic hydrocarbons (PAHs) and nitrogen and sulfur compounds contents, resulting in an improvement in the combustion efficiency of the pyrolysis oil.     

Conventional and fast pyrolysis of automobile shredder residues (ASR)

This work aims at comparing performance and product yields in conventional pyrolysis and fast pyrolysis of automotive shredded residues. In both processes, carbon conversion to gaseous and liquid products was more than 80%. Gas production was maximised in conventional pyrolysis (about 35% by weight of the initial ASR weight), while fast pyrolysis led to an oil yield higher than 55%. Higher heating values (HHV) of both conventional pyrolysis gas and fast pyrolysis oil increased from 8.8 to 25.07 MJ/Nm3 and from 28.8 and 36.27 MJ/kg with increasing pyrolysis temperature.     

Catalytic pyrolysis of car tire waste using expanded perlite

In this study, the non-catalytic and catalytic pyrolysis experiments were conducted on the sample of tire waste using expanded perlite as an additive material to determine especially the effect of temperature and catalyst-to-tire ratio on the products yields and the compositions and qualities of pyrolytic oils (NCPO and CPO). Non-catalytic studies, which were carried out under the certain conditions (a nitrogen flow of 100 mL/min and a heating rate of 10 °C/min), showed that the highest yield of pyrolytic oil (NCPO) was 60.02 wt.% at 425 °C. Then, the catalytic pyrolysis studies were carried out at catalyst-to-tire ratio range of 0.05-0.25 and the highest catalytic pyrolytic oil (CPO) yield was 65.11 wt.% at the ratio of 0.10 with the yield increase of 8.48 wt.% compared with the non-catalytic pyrolysis. Lastly, the pyrolytic oils were characterized with applying a various techniques such as elemental analyses and various chromatographic and spectroscopic techniques (GC-MS, ¹H NMR, FT-IR, etc.). The characterization results revealed that the pyrolytic oils which were complex mixtures of C₅-C₁₅ organic compounds (predominantly aromatic compounds) and also the CPO compared to the NCPO was more similar to conventional fuels in view of the certain fuel properties.     

Hydrogen-rich fuel gas production from refuse plastic fuel pyrolysis and steam gasification

In this study, experimental conditions were optimized to maximize the production of hydrogen gas from refuse plastic fuel (RPF) by pyrolysis and steam gasification processes conducted in a laboratory-scale reactor. We carried out gasification using 10-g RPF samples at different temperatures (700°-1000°C) with and without steam. The effect of the amount of steam (0–0.25 g/min) for RPF steam gasification was also studied. The effect of K₂CO₃ as a catalyst on these processes was also investigated. Experimental results showed that the hydrogen gas yield increased with temperature; with respect to the gas composition, the hydrogen content increased mainly at the expense of other gaseous compounds, which highlights the major extension of secondary cracking reactions in the gaseous fraction at higher temperatures.     

Characterization of products obtained from pyrolysis and steam gasification of wood waste,RDF, and RPF

Pyrolysis and steam gasification of woody biomass chip (WBC) obtained from construction and demolition wastes, refuse-derived fuel (RDF), and refuse paper and plastic fuel (RPF) were performed at various temperatures using a lab-scale instrument. The gas, liquid, and solid products were examined to determine their generation amounts, properties, and the carbon balance between raw material and products.The amount of product gas and its hydrogen concentration showed a considerable difference depending on pyrolysis and steam gasification at higher temperature. The reaction of steam and solid product, char, contributed to an increase in gas amount and hydrogen concentration. The amount of liquid products generated greatly depended on temperature rather than pyrolysis or steam gasification. The compositions of liquid product varied relying on raw materials used at 500 °C but the polycyclic aromatic hydrocarbons became the major compounds at 900 °C irrespective of the raw materials used. Almost fixed carbon (FC) of raw materials remained as solid products under pyrolysis condition whereas FC started to decompose at 700 °C under steam gasification condition.For WBC, both char utilization by pyrolysis at low temperature (500 °C) and syngas recovery by steam gasification at higher temperature (900 °C) might be practical options. From the results of carbon balance of RDF and RPF, it was confirmed that the carbon conversion to liquid products conspicuously increased as the amount of plastic increased in the raw material. To recover feedstock from RPF, pyrolysis for oil recovery at low temperature (500 °C) might be one of viable options. Steam gasification at 900 °C could be an option but the method of tar reforming (e.g. catalyst utilization) should be considered.     

Characteristics of products and PCDD/DF emissions from a pyrolysis process of urethane/styrofoam waste from electrical home appliances

A plastic fraction consisting mainly of polyurethane/styrofoam waste is generated after separating valuable spare parts and metals from used electrical home appliances. In Korea, such waste is currently incinerated in cement kilns or is landfilled. However, owing to its high volatile matter content, conversion into gaseous or liquid pyrolysis products is a preferable alternative. A pyrolysis process of polyurethane and styrofoam waste from electrical home appliances was evaluated by characterizing the products generated at 500°–800°C. The para meters determined were the yields of gas, oil, and char; the characteristics of the remaining char; and the con centration of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzo-furans in the product gas. As expected, the char yield decreased at higher temperatures, whereas gas and oil yields showed increasing tendency. The oil products could be used as storable fuels with a calorific value of 6000–8000 kcal/kg. Fine pores were observed in the char. The adsorption and decolorizing ability of the char were almost the same as those of activated carbon, so that pyrolysis char has potential for use as a sorbent. Further feasibility studies will be needed before utilizing pyrolysis technology to recover either fuels or usable products from polyurethane/styrofoam waste.