催化热解废轮胎制衍生油

催化热解废轮胎对于资源利用及环境保护具有重要意义,近年来引起人们关注.在废轮胎胶粉热解反应中加入催化剂,不仅会加速胶粉裂解速率,缩短反应时间,而且可以通过催化剂择形催化改变产物分布,从而提高目的产物衍生油的收率和性能.国内外对废轮胎催化热解已做了大量研究,以期提高衍生油中高附加值单环芳烃的含量,同时降低S, N和Cl含量,虽然已取得较大进展,但衍生油收率较低,大大降低了该技术的可行性.
　　本文采用带搅拌器的1000 mL不锈钢反应器,在常压条件下研究了反应温度和催化剂类型对废轮胎胶粉热解反应及产物衍生油性能的影响,通过元素分析、馏程模拟和色谱-质谱等表征手段检测了衍生油的理化性能.结果表明,在废轮胎胶粉热解反应过程中,随反应温度上升,出油速率先增加后降低.至500 oC时,热解衍生油收率最高达55.65 wt%,所得衍生油呈黑棕色,具有轻质油含量低、S和N含量高、粘度低和流动性好的特点,其轻质芳烃含量低,却含有大量可以转变为芳烃的脂肪烃类.因此,为了提高衍生油中轻质油和轻质芳烃收率,降低S和N含量,尽量维持较高的衍生油收率,在热解反应过程中引入少量ZSM-5, USY,β, SAPO-11和ZSM-22等常见催化剂,利用催化剂独特的孔道结构和酸分布,达到定向催化和转化的目的,提高轻质芳烃含量.同时,为了克服催化剂与胶粉难以接触进行反应的问题,在反应温度升至200 oC时,维持一定时间保证胶粉发生溶胀和液化反应形成液体烃类,使得催化剂不仅能够均匀分散于液体烃中与其接触进行反应,而且有效提高了反应物料与催化剂之间传质传热效率,使得裂解反应在均相中进行,降低因传热不均匀而造成的结焦和过度裂化反应.在催化热解过程中,1.0 wt%催化剂的加入可明显缩短反应时间,在保证衍生油收率基本不变的情况下,获得的衍生油呈黄棕色,轻质油收率较高为70–75 wt%, S和N含量分别降至0.3–0.58wt%和0.78–1.0 wt%.以具有较高酸性和孔径分布的ZSM-5, USY,β和SAPO-11为催化剂时,衍生油中总芳烃含量可达到50 wt%,其中单环芳烃含量高达45 wt%.     

废轮胎回转窑中试热解炭表面组分XPS分析

以X射线光电子能谱（XPS）对废轮胎回转窑中试热解炭表面组分进行实验分析,研究热解炭本体与表面的异同,热解温度、热解炭粒径的影响。与商用炭黒比较,废轮胎热解炭本体中含有更多的Zn、Si、S、Mg等杂质元素,各组分与热解温度没有大的相关性;热解炭表面在热解过程中形成了一吸附沉积层,表面层中杂元素的质量分数极低;低于500℃时,热解不完全,吸附沉积物较少。热解炭按粒径存在一定分布,粒度<0.074 mm的粉末状热解炭来自表面磨损脱落的粉末,各种杂元素的质量分数很低;Zn元素的相对质量分数随热解炭粒径的减小而减少。对热解炭进行深度剖析发现,吸附层是极薄的,表面层对本体的影响是极小的;定量分析结果表明,以C质量分数为100,则O为4～6,S、N约为1,Zn小于0.6,而商用炭黑中S约为0.3,不含N、Zn。     

射频等离子体热解废轮胎的研究

Disposal of the huge piles of used tires is increasingly becoming a problem all over the world. Incineration may utilize the energy content of waste tires, but it is associated with the generation of SO2, NOx and other hazardous emissions. Pyrolysis is an alternative disposal method with the possibility for recovery of valuable products from used tires. Recently, waste processing technology based on plasma processes has received much attention due to a number of advantages such as high treatment rate, small space volume, etc. In this paper, the pyrolysis of waste tire using a capacitively coupled radio-frequency （RF） plasma reactor was investigated. The lab-scale RF plasma reactor was operated with RF powers between 1 600 W and 2 000 W, pressures between 3 000 Pa and 8 000 Pa （ absolute pressure） and temperatures between 1 200 K and 1 800 K. In the tire powder pyrolysis experiments, two product streams are obtained： combustible gas and char. The physical properties （surface area, porosity, particle morphology） as well as chemical properties （elemental composition, heating value and surface functional groups） of char were examined to exploit the potential applications of the char. The results indicate that the RF plasma pyrolysis would be a useful technology for waste disposal.     

废轮胎回转窑中试热解炭的重金属离子吸附特性

对废轮胎回转窑中试热解炭的重金属离子Pb2＋、Cr3＋和Cr6＋吸附特性进行了研究,分析了溶液pH值、接触时间、吸附剂用量以及溶液初始浓度对重金属去除率的影响。结果表明,溶液pH值对热解炭的重金属去除率有显著影响,阳离子Pb2＋、Cr3＋的去除率随pH的增加而增大,在弱酸和中性环境中去除率接近100％;Cr6＋在强酸性溶液中被还原成为Cr3＋,经二次吸附,总Cr去除率可达99％以上;Pb2＋和Cr3＋的去除率随热解炭用量和吸附时间的增大而增加,热解炭用量和吸附时间有一个最佳值。Pb2＋和Cr3＋的吸附为单分子层吸附,可用Langnuir和两段Freundlich等温吸附式描述,Freundlich拟合指数表明,热解炭具有较好的吸附性能。经酸洗后的热解炭对Pb2＋的去除率变低。     

Effect of particle size on pyrolysis characteristics of Elbistan lignite

In this study, the relationship between particle size and pyrolysis characteristics of Elbistan lignite was examined by using the thermogravimetric (TG/DTG) and differential thermal analysis (DTA) techniques. Lignite samples were separated into different size fractions. Experiments were conducted at non-isothermal conditions with a heating rate of 10°C min⁻¹ under nitrogen atmosphere up to 900°C. Pyrolysis regions, maximum pyrolysis rates and characteristic peak temperatures were determined from TG/DTG curves. Thermogravimetric data were analyzed by a reaction rate model assuming first-order kinetics. Apparent activation energy (E) and Arrhenius constant (A _r) of pyrolysis reaction of each particle size fraction were evaluated by applying Arrhenius kinetic model. The apparent activation energies in the essential pyrolysis region were calculated as 27.36 and 28.81 kJ mol⁻¹ for the largest (−2360+2000 μm) and finest (−38 μm) particle sizes, respectively.     

氯化钙催化纤维素热裂解动力学研究

用差示热重分析仪对氯化钙纤维素热裂解动力学催化影响进行了研究。结果表明，氯化钙对焦炭的形成具有强烈的促进效果，使热裂解最终残留物产率从5％提升到10％以上，氯化钙的存在影响到热失重初始阶段活性纤维素的生成，使热重曲线向低温侧移动，并在低温段产生了小的失重速率峰。通过热重分析发现，氯化钙催化条件下纤维素热裂解动力学参数被分为了三段，分别对应于活性纤维素的生成、炭化和活性纤维素转化为挥发分产物三个区间，并依次成为整体失重过程的控制步骤。结合Broido-Shafizadeh机理分析以及与纯纤维素热裂解动力学参数的对比，氯化钙对这三个主要反应步骤都产生了促进效果，其中以催化焦炭的生成最为明显，在促进焦炭化的过程中，降低了气体产物的生成比率。     

芦苇浆黑液在流化床上的热解实验研究

为了掌握芦苇浆黑液的热解行为,利用流化床在530、580、630、680、730和780 ℃ 六个床温下对芦苇浆黑液在氮气氛围下的热解过程进行了实验研究,分析了床温对气相产物、碳的转化率、NO_x和SO₂的排放浓度、焦油成分和热解焦微观形貌的影响。结果表明,热解气中的主要成分为CO、CH₄、CO₂和H₂,床温的升高有利于H₂和CO的生成,而不利于CH₄和CO₂的生成;可燃气体积分数随着床温的升高而升高,其值从59.2%(530 ℃)升高到66.1%(780 ℃);床温较高时,热解产生的焦油量较少,其中,多环芳烃化合物的相对含量较多,该值在780 ℃时最高为46.88%。     

甲烷在石墨化热解碳黑和活性炭上的吸附

为研究影响碳基吸附剂吸附超临界温度气体的主要因素,选择石墨化热解碳黑BP280和Ajax活性炭,分析超临界温度高压甲烷在其上的吸附平衡。应用容积法,在压力0~20.5 MPa、温度253 K~313 K测定甲烷的吸附平衡数据,并由等量吸附线标绘和亨利定律常数确定等量吸附热。引入通用吸附等温方程,再由方程的Langmuir标绘确定最大吸附容量,进而通过方程的线性化计算吸附平衡态中甲烷分子的作用能。结果表明,甲烷在两种吸附剂上的最大吸附容量均随温度而变化,并都小于液态甲烷的密度;甲烷在碳黑和活性炭上的等量吸附热分别为11.9 kJ/mol~12.5 kJ/mol和17.5 kJ/mol~22.5 kJ/mol,体现了两种吸附剂不同的表面能量分布;甲烷分子间作用能随吸附量的变化特点反映了超临界温度甲烷以类似于压缩气体状态聚集的特点和吸附剂结构上的差异。碳基吸附剂的比表面积和微孔容积是影响其储存甲烷容量的重要因素。     

Fe/炭黑、Ni/炭黑催化剂对渣油加氢反应的影响

使用模型化合物在微型反应釜中研究了载体炭黑对渣油内部氢转移反应的影响。结果表明,炭黑可以明显地促进四氢萘到蒽的氢转移反应。使用等体积浸渍法制备了Fe/炭黑、Ni/炭黑催化剂并对Fe/炭黑催化剂进行了XRD、SEM表征,结果表明,金属硫化物附着在炭黑颗粒的表面,直径为1μm左右。在高压反应釜中研究了载体炭黑和以炭黑为载体的催化剂对克拉玛依常压渣油430℃加氢反应的影响,并于传统的水溶性分散型催化剂的抑焦性能进行了对比。 结果表明,Fe/炭黑、Ni/炭黑催化剂可以明显地抑制渣油加氢反应的生焦,水洗后的催化剂效果比未经水洗的催化剂抑制生焦的效果好;Ni/炭黑催化剂抑焦效果比Fe/炭黑催化剂好;Fe/炭黑催化剂比同等浓度的水溶性Fe催化剂抑焦效果好。对反应产物馏分的分析表明,Fe/炭黑催化剂可以有效地抑制渣油缩合生焦,同时在一定程度上抑制裂化反应。     

Influence of conditions for preparation of fullerene-containing carbon black on its microwave properties and yield of fullerenes

Conditions for preparation of the fullerene-containing carbon black with the maximum yield of fullerenes were determined. A correlation between the dielectric constant of the carbon black in the microwave range and the yield of fullerenes was found. The relation of the fullerene-containing carbon black structure to the conditions of its preparation and dielectric constant are discussed.     

Kinetics of carbon deposition from ethylene on Pt(110) surface

The formation of carbonaceous deposits on Pt(110) surface due to ethylene decomposition in the temperature range of 770–970 K has been studied. Both kinetic and XPS data show that chemisorbed carbon (with no C−C bonds, but only C−Pt bonds) forms at T=770–870 K, the saturation coverage θ_s being about 1 ML. At higher temperatures, θ_s increases by a factor of 1.5, indicating the formation of more densely packed carbon species (DPC) due to C−C bonding. A kinetic model has been proposed to describe the process of carbon conversion.     

ATRP of butyl acrylates from functionalized carbon black surfaces

The functionalization of carbon black surface with atom transfer radical polymerization (ATRP) initiating sites and subsequent ATRP of n‐butyl acrylate (n‐BA) and t‐butyl acrylate (t‐BA) from the surface of carbon black is reported. The polymerizations were carried out using CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as the primary catalytic system in anisole at 70 °C. The initiator density on carbon black surface was tuned and the effect of initiator density on the polymers grafted on the surface was illustrated. Polymerizations were also performed in the presence of a sacrificial initiator to indirectly monitor the molecular weight evolution of polymers formed in the system. Block copolymerization of t‐BA initiated from poly(n‐BA) grafted carbon black was conducted to achieve water‐dispersible carbon black composites after cleavage of the t‐butyl groups. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4695–4709, 2005     

塔克拉玛干沙漠黑碳气溶胶的特性及来源

长期监测并采集塔克拉玛干沙漠腹地的大气颗粒物及黑碳气溶胶样品.在塔克拉玛干沙漠腹地,沙尘气溶胶中的黑碳在PM10中的年平均含量高达1.14%,这说明在人迹罕至的塔克拉玛干沙漠地区,其上空的沙尘气溶胶也已经受到人为活动的影响.黑碳气溶胶具有明显的季节变化和日变化,冬季最高,平均达2261.7ngm-3,依次为冬季春季秋季夏季.黑碳气溶胶日变化特征与城市地区恰好相反,夜间高于白天,午夜0:00～2:00出现峰值,而在上午8:00～11:00出现低值.非沙尘暴期间黑碳对PM10的贡献是沙尘暴时期的11倍.塔里木盆地周边绿洲带人为活动,尤其是新疆南北部地区跨越春秋冬三季的居民采暖所产生的黑碳经由局地、区域或长途传输是塔克拉玛干沙漠腹地黑碳气溶胶的主要来源,也是沙漠黑碳气溶胶具有明显的季节特征和日变化的主要原因.随着沙尘气溶胶的长途传输,沙漠每年大约输出6.3×104吨黑碳气溶胶,这势必会对全球的气候与环境变化产生一定影响.     

Complementary effects of multiwalled carbon nanotubes and conductive carbon black on polyamide 6

This article introduces a newly innovative idea for preparation of superconductive ternary polymeric composites of polyamide 6 (PA6), conductive carbon black (CCB), and multiwalled carbon nanotubes (MWCNTs) with different weight ratios by a melt‐mixing technique. The complementary effects of CCB and MWCNTs at different compositions on rheological, physical, morphological, thermal, and dynamic mechanical and electrical properties of the ternary composites have been examined systematically. We have used a novel formulation to produce high‐weight fraction ternary polymer composites that show extremely higher conductivity when compared with their corresponding binary polymer composites at the same carbon loading. For example, with an addition of 10 wt % MWCNTs into the CCB/PA6 composite preloaded with 10 wt % CCB, the electrical conductivity of these ternary composites was about 5 S/m, which was 10 times that of the CCB/PA6 binary composite (0.5 S/m) and 125 times that of the MWCNT/PA6 binary composite (0.04 S/m) at 20 wt % carbon loading. The incorporation of the MWCNTs effectively enhanced the thermal stability and crystallization of the PA6 matrix in the CCB/PA6 composites through heterogeneous nucleation. The MWCNTs appeared to significantly affect the mechanical and rheological properties of the PA6 in the CCB/PA6 composites, a way notably dependent on the MWCNT contents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1203–1212, 2010     

Study of viscoelastic properties of white carbon black reinforced synthetic polyisoprene

The viscoelastic properties of synthetic polyisoprenes(PI) reinforced by white carbon black(WCB) have been investigated and compared with WCB reinforced natural rubber(NR), including cure characteristics, physio-mechanical and dynamic mechanical properties. Compared with NR, PI loaded with the same amount of WCB(PI/WCB) exhibited shorter scorch time and optimal cure time, indicating that WCB fillers are comparatively easier to conjugate with PI. The tensile strength and elongation at break decreased with WCB filling in both PI and NR vulcanizates. The hardness of the rubber vulcanizates increased with the WCB filling in the rubber matrix. PI/WCB blends exhibited smaller hardness data, lower tensile strength, as well as lower elongation at break and tensile stress. Increasing the amount of WCB in rubber matrix induced the Payne effect. However, the Payne effect is much more obvious for the PI/WCB system, and PI/WCB also displayed higher storage modulus whereas lower loss modulus and loss tangent than NR/WCB, which could all be attributed to the poor dispersibilities of WCB in the PI matrix.     

Mechanical and rheological properties of poly(ethylene-co-ethyl acrylate) as a function of carbon black content

Carbon black (CB) filled poly(ethylene-co-ethyl acrylate) (EEA-CB) is used as conductive phase in conductive polymer composites (CPC). Electrical conductivity of CPC obtained from blends of immiscible polymers results from CB particles localization within the material, which depends on composition and processing conditions. It is particularly important to control viscosity of such systems as this parameter determines both the phase morphology and conductive pathway structure. The small scale, at which CB particle aggregation/dispersion phenomena occur within CPC, makes direct observations difficult. But the effect of carbon black particles/polymers interactions is clearly visible by means of rheological measurements. A strong reinforcing effect of CB on CPC in both solid and liquid states has been noticed. This phenomenon has been analyzed using classical models as a function of temperature and CB content. The results confirm the necessity of CPC rheology control especially during the process to achieve good reproducibility of electrical properties.     

基于TG-FTIR的生物质催化热解试验研究

运用热重－傅里叶红外光谱联用技术(TG-FTIR),以麦秸为研究对象,探讨催化与非催化条件下生物质的热解挥发分析出特性,分析研究热解温度、催化剂种类对生物质热解主要析出产物的影响。通过热重TG和DTG曲线,获得了相关热解特性参数及动力学参数。结果表明,添加NiO和CaO存在两个失重峰,并促进麦秸热解反应进行,降低表观活化能,其中NiO对提高热解析出产率作用更显著。通过红外光谱对热解产物实时测量的分析表明,CO与CO2的析出与失重峰基本一致,而CH4的析出滞后于前两者。添加NiO和CaO有利于减少热解产物中的CO2的浓度,促进挥发分产物CO、CH4的生成。其中CaO更有利于生物质在温度800℃以下的热解性能改善,而NiO在800℃以上具有更好的催化作用。     

Simultaneous growth of spheroidal and tubular carbon structures during the pyrolysis of benzene

Spheroidal carbon structures, formed during the pyrolysis of benzene, are deposited selectively in the more low-temperature zone of the reactor. It is suggested that the spheroidal and tubular carbon structures are formed as a result of condensation of the molecules of benzene and its homologs. The curvature of the obtained structure appears at the moment of interaction between molecules in one of which the atoms are not coplanar as a result of the presence of carbon with sp³ hybridization. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 2, pp. 82–86, March–April, 2006.     

Effect of carbon black content on electrical and microwave absorbing properties of polyaniline/carbon black nanocomposites

Carbon black coated with polyaniline, forming a core-shell structure, was synthesized by in situ polymerization at different carbon black contents (5-30 wt.%) and introduced into epoxy resin to be a microwave absorber. The spectroscopic characterizations of the formation processes of polyaniline/carbon black composites were studied using Fourier transform infrared, ultraviolet-visible spectrophotometer, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and electron spin resonance. Microwave absorbing properties were investigated by measuring reflection loss in the 2-18 and 18-40 GHz microwave frequencies range using the free space method. The results showed that a wider absorption frequency range could be obtained by adding different carbon black contents in polyaniline.     

Kinetics of carbon dioxide mechanosorption by Ca-containing silicates

Kinetics of mechanically induced CO₂ extensive sorption by silicate minerals (labradorite, diopside, okermanite, ghelenite and wollastonite) was considered. Mechanical activation of the silicates was carried out in a planetary mill in CO₂ at atmospheric pressure. Carbon dioxide was consumed by the silicates in the form of carbonate ions and its content in the samples after 30 min of mechanical treatment reached 3–12 mass% CO₂ depending on mineral composition. Equations that reasonably good represent kinetics of CO₂ mechanosorption by silicates were proposed. These equations enable to calculate mechanosorption coefficients that characterize the diffusivity of CO₂ into disordered silicate matrix under intensive mechanical impact. Thermal analysis of the mechanically activated silicates showed that there was positive correlation between temperature of complete carbonate decomposition and mechanosorption coefficient.