生物油TG-FTIR分析与热解气化特性研究

以稻壳快速热解产物生物油为对象,在对其进行热重红外检测的基础上,结合生物油及其轻质、重质组分的热解气化实验,研究了生物油热解气化过程及气体产出特性。结果表明,生物油的热解气化分为两个阶段,一是轻质组分的快速挥发热解;二是重质组分的裂解气化与缩合缩聚,活化能分别为35~38 kJ/mol和15~22 kJ/mol。温度升高,热解气化效率增加,以H₂和CO为主的合成气产量增多,但气体产物热值降低。气体中H₂主要来自轻质组分的热解气化,而重质组分则裂解产生较多的CO、CH₄等物质。     

活性炭纤维吸附脱除NO过程中NO氧化路径分析

在小型固定床吸附实验台上开展了黏胶基活性炭纤维吸附脱除NO的实验研究。采用H₂O₂溶液浸渍以及热处理方法对活性炭纤维表面进行修饰,以获得表面孔隙结构接近而含氧官能团含量不同的样品;考察样品在惰性氮气气氛、含氧气氛下吸附脱除NO的效果,以及表面含氧含氮官能团的变化规律。探讨了含氧官能团在NO催化氧化过程中的作用及含氧气氛下O₂对于NO转化为NO₂的影响,分析了活性炭纤维表面吸附的NO向NO₂的主要转化途径。结果表明,在氮气气氛下活性炭纤维表面C-O官能团对吸附态的NO起到氧化作用,吸附态NO被C-O官能团氧化生成-NO₂官能团;在含氧气氛下活性炭纤维吸附NO后表面出现-NO₂、-NO₃官能团,通过长时间实验测定三种样品在含氧气氛下对NO吸附的效果,发现三种样品稳定时催化氧化效果一致,表明含氧官能团对初始NO的物理吸附影响较大,而对整个吸附过程影响较小。吸附在活性炭纤维表面上的NO与环境气氛中的游离态O₂发生氧化反应是NO转变为NO₂的主要途径。     

固相吸附GC-MS分析新装居室室内气体中的有机污染物

采用活性炭对放置一段时间的新装居室内气体和新购书橱内气体进行吸附,吸附气体后的活性炭经乙醚洗脱,洗脱液经氮气浓缩,进行GC—MS分析。分析出室内空气污染物包括烷烃、烯烃、醇、酮、醛、酯以及苯系物等25种有机物,书橱内污染气体共鉴定出24种有机物,其中苯系物量最高,烷烃和烯烃量最低。     

橄榄石基固体热载体影响褐煤热解产物分布的分析

为了提高固体热载体煤热解工艺中焦油的品质,降低焦油中沸点大于360 ℃的重质组分含量,本实验采用固定床反应器,在450~600 ℃下进行褐煤固体热载体快速热解反应.分析对比了橄榄石基和石英砂固体热载体对褐煤热解产物收率、焦油馏分、气体组成的影响.结果发现,Co能改变煤内部挥发分氢元素的分布,橄榄石负载Co热载体能将焦油中重质组分转化为轻质焦油和热解气.热解温度为550 ℃时,与橄榄石相比,负载Co的橄榄石固体热载体使焦油收率提高了19.2%.与石英砂相比,负载Co的橄榄石固体热载体使焦油中重质组分含量降低了17.0%,轻质组分收率达5.1%,其中,轻油、酚油和萘油分别提高了19.6%、17%和15.2%,气体产物中H₂、CH₄含量下降.     

电厂废气中饱和水蒸气对活性炭变压吸附捕集CO2的影响

由于热电厂废气中含有高湿饱和水蒸气,选用疏水材料活性炭为吸附剂,利用真空变压吸附技术研究了活性炭分离电厂废气中水蒸气和二氧化碳的可行性和优越性,研究了水对CO₂捕集的影响。实验分析表明,水在活性炭上的“S”型等温吸附曲线有利于真空条件下被解吸。同时,圆锥模型描述了水蒸气在吸附床内的浓度分布。结果表明,即使水蒸气可以被活性炭吸附,但它的存在不影响CO₂的捕集。每个循环操作可在相对较短的解吸时间和较高的解吸压力下完成。实验中单床三步变压吸附工艺可以使CO₂回收率高达80%,CO₂纯度达43%。     

吸汞载银活性炭纤维和吸汞活性炭纤维的热脱附特性研究

70℃下分别对载银活性炭纤维(载银量14.07%)和活性炭纤维的片状吸附体进行气态汞吸附实验,测定出载银活性炭纤维汞饱和吸附量为192.3 mg/g,活性炭纤维汞饱和吸附量为29.4 mg/g,分别为普通活性炭的48倍～192倍和7倍～29倍.采用热重分析法(TGA)研究了两种吸附剂汞饱和后的热脱附再生特性.结果表明,汞饱和载银活性炭纤维的汞脱附发生在100℃～650℃,在70 min内从50℃升温至650℃,才乏脱附率为94.73%;汞饱和活性炭纤维的汞脱附发生在100℃～230℃,在40 min内从50℃升温至350℃ ,汞脱附率为69.93%.扫描电镜分析发现,载银活性炭纤维因吸附汞而富集的银,经热脱附后变成均匀弥散于纤维表面的亚微米级和纳米级球状银颗粒;吸汞活性炭纤维经热脱附后物理吸附汞基本消失,而氧化汞颗粒反而变多,说明物理吸附的汞易于脱附,氧化汞难以脱附,同时在热脱附过程中存在金属汞向氧化汞的转化.     

煤炭解耦燃烧过程N迁移与转化Ⅱ:单组分气相化学反应实验

在理想平推流反应器中进行了模拟热解气对模拟烟气中NO、N₂O的还原实验研究,考察了反应温度、过剩空气系数λ、热解气中CH₄、CO、H₂、NH₃浓度、烟气中NO、N₂O浓度变化对NO、N₂O出口浓度的影响。实验结果表明,当模拟热解气仅含其中一种气体时,在反应温度973~1 223 K时热解气中CH₄、CO、H₂基本不与NO发生反应,当λ小于或等于1.0时可降低N₂O浓度0%~30%;热解气中NH₃可降低NO 10%~60%,但NH₃不与N₂O发生反应。     

TiO2/ACF的制备及光催化降解四氯乙烯性能

以钛酸四丁酯为前驱物,活性炭纤维(ACF)为载体,蔗糖为胶粘剂,采用真空吸附水解的方法制得了TiO₂/ACF催化剂.采用BET、XRD、SEM等手段对其物理化学特性进行表征,以四氯乙烯光降解反应为探针反应,考察了TiO₂/ACF催化剂的光催化降解性能.实验结果表明,采用真空吸附水解法可以将TiO₂很好地负载到活性炭纤维表面上.通过优化条件制备的TiO₂/ACF催化剂在光照2h条件下,可以将水中溶解量的四氯乙烯降解90%以上.催化剂可以多次循环使用,光催化反应活性不变.     

棕榈纤维制备活性炭纤维及其对水中三氯生的吸附研究

以棕榈纤维为原材料、磷酸为活化剂制备活性炭纤维,通过单因素实验和正交实验深入探讨反应条件对活性炭纤维吸附性能的影响,并确定最佳制备条件。系统研究三氯生在活性炭纤维上的吸附热力学、动力学以及溶液p H值对吸附的影响,并研究比较乙醇洗脱与加热煅烧法对吸附饱和后的活性炭纤维的再生效果。结果表明,磷酸溶液质量分数和碳化温度对活性炭纤维吸附性能影响较大,活化剂浸渍时间对其影响较小,活性炭纤维的最佳制备条件为:磷酸溶液浓度25%,碳化温度400℃,活化时间36h。所制备的活性炭纤维的BET比表面积为1358.478m~2/g、微孔面积为1240.131m~2/g、平均孔径为1.886nm。活性炭纤维对三氯生的吸附等温线符合Langumuir方程,吸附是放热反应。动力学研究表明,吸附反应符合准二级动力学方程,且在5h后基本达到平衡。随着p H值的升高,材料对三氯生的吸附量略有下降。乙醇洗脱和加热煅烧均可有效再生吸附饱和后的活性炭纤维。     

蒲县藻煤藻类体热解产物单组分生成动力学

用快速热解气相色谱法以及热解气相色谱－质谱联用技术，鉴定了山西蒲县藻煤藻类体的热解产物组成。利用等温一级反应动力学模型，计算了蒲县藻煤藻类体热解产物中正构烷烃、正构烯烃、苯（Ｂ）、甲苯（Ｔ）、萘以及热解总产物（Ａｒ）等组分生成动力学参数，探讨了这些动力学参数与和生烃的关系。     

压力对塔里木原油四组分热解性能的影响

压力对深层油藏原油热化学过程的影响尚存在较大争议,为研究其在油藏原油热解成气过程中的作用机理,我们在450℃、5~40 MPa压力下对塔里木原油四组分(饱和分、芳香分、胶质和沥青质)进行了封闭体系的热解实验,通过气相色谱(GC)和气相色谱/质谱(GC/MS)分别对原油四组分热解反应的气体产物及饱和分热解过程的液态产物进行了分析。结果表明,在450℃、24 h及不同压力下,沥青质热解产气率高于胶质、芳香分和饱和分;四组分的气相热解产物中,C1的产率明显高于C2~C5组分。增大压力抑制沥青质、胶质及芳香分的热解产气过程而促进饱和分的热解产气过程。随压力的增大,饱和分热解的液态产物的主峰组分碳数先减小,再增大。压力低于20 MPa时,饱和分热解过程中以裂解反应为主;高于30 MPa时,增大压力有利于缩合反应。研究结果可为认识深层油藏原油的稳定程度及天然气的成因提供一定的理论参考。     

油气吸附分离过程的研究

本文以油气回收的吸附剂筛选为出发点。研究了93号汽油在不同系列吸附剂上的吸附、脱附性能,以及活性炭微孔结构对吸附性能的影响,并与美国类似吸附剂作了比较。结果表明：所用吸附剂的吸附容量自欺欺人优于一般市售活性炭,可望应用于国内炼油厂,加油站和油田的油气吸附回收利用。     

Valorization of two waste streams into activated carbon and studying its adsorption kinetics,equilibrium isotherms and thermodynamics for methylene blue removal

Wastes must be managed properly to avoid negative impacts that may result. Open burning of waste causes air pollution which is particularly hazardous. Flies, mosquitoes and rats are major problems in poorly managed surroundings. Uncollected wastes often cause unsanitary conditions and hinder the efforts to keep streets and open spaces in a clean and attractive condition. During final disposal methane is generated, it is much more effective than carbon dioxide as a greenhouse gas, leading to climate change. Therefore, this study describes the possible valorization of two waste streams into activated carbon (AC) with added value due to copyrolysis. High efficiency activated carbon was prepared by the copyrolysis of palm stem waste and lubricating oil waste. The effects of the lubricating oil waste to palm stem ratio and the carbonization temperature on the yield and adsorption capacity of the activated carbon were investigated. The results indicated that the carbon yield depended strongly on both the carbonization temperature and the lubricating oil to palm stem ratio. The efficiency of the adsorption of methylene blue (MB) onto the prepared carbons increased when the lubricating oil to palm stem ratio increased due to synergistic effect. The effects of pH, contact time, and the initial adsorbate concentration on the adsorption of methylene blue were investigated. The maximum adsorption capacity (128.89 mg/g) of MB occurred at pH 8.0. The MB adsorption kinetics were analyzed using pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models. The results indicated that the adsorption of MB onto activated carbon is best described using a second order kinetic model. Adsorption data are well fitted with Langmuir and Freundlich isotherms. The thermodynamic parameters; ΔG°, ΔH° and ΔS° indicate that the adsorption is spontaneous and endothermic.     

焦炭与重质油共气化联产烯烃技术研究

针对中国乙烯、丙烯等低碳烯烃生产原料供需日益尖锐的矛盾和重质油利用技术的不足,提出焦炭与重质油共气化联产烯烃技术。阐述了焦炭与重质油共气化联产烯烃的技术原理及过程设计,并以固定床为反应器,焦炭和常压渣油为原料进行实验模拟。结果表明,当裂解温度为750℃~800℃,停留时间τ＜0.5s时,渣油在焦炭介质中裂解,其低碳烯烃含量最高;渣油在模拟气化裂解区、750℃下裂解时,得到出口气体中低碳烯烃（C2H4＋C3H6）、烷烃（CH4＋C2H6）及合成气（H2＋CO）的体积分数分别为20%、28%及46%。应用扫描电镜观察了焦炭介质表面上结焦生成物的形貌,发现通氧气后结焦生成物残留量较少。实验模拟结果证明,焦炭与重质油共气化技术可以制备低碳烯烃并联产合成气,且能有效地解决重质油裂解造成的结焦问题。     

Production of fungicidal oil and activated carbon from pistachio shell

The main objective of this study was to evaluate the feasibility of pistachio shell as a biomass feedstock for the production of fungicidal oil and a precursor for the production of activated carbon by physical activation. For this purpose, pistachio shell was pyrolyzed in a fixed bed reactor at the different temperatures (300-600 °C). The pyrolysis products were identified as gas, bio-oil, aqueous solution and char. The product distribution from pyrolysis process did not significantly change when the pyrolysis temperature was above 300 °C. The pyrolysis gas product had low calorific value since it contained the high proportion of carbon oxides. Because of their high oxygen content, the bio-oils were found not to be used as a fuel. Thus, the bio-oil was tested again four different types of fungi (pathogenetic, wood decaying and saprophyting). It was shown fungicidal activity again all tested fungi at the concentration of 10-50 mg ml⁻¹. The pyrolysis char was evaluated as a precursor for the production of activated carbon. The surface area and micropore volume of the activated carbon produced from the char by CO₂ activation at 900 °C were found to be 708 m² g⁻¹ and 0.280 cm³ g⁻¹, respectively.     

废轮胎热解油品的组成与硫含量研究

本文就废轮胎热解是油品组成进行了分析,结果表明,载气种类对油品的组成及硫含量影响较大,在Ｎ２条件下,油品中含有较多的轻质油品,轻质油中中富含高附加值的化学品萜二烯。Ｈ２及Ｈ２Ｏ气氛下的油品中轻质油品含量远低Ｎ２气氛以质油品含量。载气流速对油品的组成影响不大。硫含量分析表明,在Ｎ２条件下各油品的硫含量均高于Ｈ２及Ｈ２Ｏ气氛下的硫含量;各油品中轻质油品硫含量最低,在Ｈ２及Ｈ２Ｏ气氛可下可小于１００ｐｐｍ,中质油品硫含量次之,重质油硫含量最高。     

Feedstock recycling of synthetic and natural rubber by pyrolysis in a fluidized bed

An indirect heated fluidized bed process has been used for the pyrolysis of synthetic and natural rubber. The throughput capacity for the continuously running plant was 500–3000 g/h. The results are compared to a pilot plant for the pyrolysis of whole tires. Beside the recovery of oil and carbon black it was another goal of the study to investigate how much monomer material such as isoprene and isobutene can be obtained from synthetic and natural rubber. The pyrolysis parameters were optimized such as pyrolysis temperature, kind of fluidizing gas, and residence time of the gas in the pyrolysis reactor. Main products of the pyrolysis of tires are an aromatic-rich oil and carbon black, which can be reused. While it was possible to obtain only 2–4 wt% of isobutene, the isoprene content reached 22 wt% from natural rubber.     

Parametric Study of a Pressure Swing Adsorption Process

The performance of a pressure swing adsorption (PSA) process for production of high purity hydrogen from a binary methane-hydrogen mixture is simulated using a detailed, adiabatic PSA model. An activated carbon is used for selective adsorption of methane over hydrogen. The effects of various independent process variables (feed gas pressure and composition, purge gas pressure and quantity, configuration of process steps) on the key dependent process variables (hydrogen recovery at high purity, hydrogen production capacity) are evaluated. It is demonstrated that many different combinations of PSA process steps, their operating conditions, and the feed gas conditions can be chosen to produce an identical product gas with different hydrogen recovery and productivity.     

Coal pyrolysis in a fluidized bed reactor simulating the process conditions of coal topping in CFB boiler

Simulating the conditions of pyrolytic topping in a fluidized bed reactor integrated into a CFB boiler, the study was devoted to the reaction fundamentals of coal pyrolysis in terms of the production characteristics of pyrolysis oil in fluidized bed reactors, including pyrolysis oil yield, required reaction time and the chemical species presented in the pyrolysis oil. The results demonstrated that the maximal pyrolysis oil yield occurred on conditions of 873 K, with a reaction time of 3 min and in a reaction atmosphere gas simulating the composition of pyrolysis gas. Adding H₂ and CO₂ into the reaction atmosphere decreased the pyrolysis oil yield, while the oil yield increased with increasing the CO and CH₄ contents in the atmosphere. TG-FTIR analysis was conducted to reveal the effects of reaction atmosphere on the chemical species present in the pyrolysis oil. The results clarified that the pyrolysis oil yield reached its maximum when the simulated pyrolysis gas was the reaction atmosphere, but there were slightly fewer volatile matters in the pyrolysis oil than the oil generated in the N₂ atmosphere. All of these results are expected not only to reveal the composition characteristics of the pyrolysis oil from different conditions of the coal topping process but also to optimize the pyrolysis conditions in terms of maximizing the light pyrolysis oil yield and quality.     

分析测试新方法(204~209)裂解气相色谱-质谱法测定氨纶废丝中油剂的含量

氨纶是一种聚氨酯弹性纤维,应用领域广阔. 在对氨纶生产过程中产生的大量废丝进行回收重复利用时,所添加的油剂会对甬道发生堵塞,因此在氨纶废丝回收之前需要对其进行清洗来控制油剂的含量. 运用裂解气相色谱-质谱法(PY-GC/MS)建立了1种测试氨纶废丝中油剂残余含量的方法. 方法简单快捷,无需任何样品前处理,为氨纶废丝的清洗工作,尤其是工业化清洗生产提供了准确可靠的数据.