CO2 gasification of wood charcoals derived from vacuum and atmospheric pyrolysis

The gasification of biomass derived char obtained via vacuum and atmospheric pyrolysis of Populus tremuloides has been studied in the ranges of 725–960°C and 0.1 to 6 MPa. CO₂ was used as the oxidizing gas. The results show that char reactivity is influenced by the preheating rates and that pressure effects are significant between 850°C and 950°C. A correlation based on the expression: df/dt = k₀{exp(-E/RT)}(1 - f)^af^βP^yCO₂ was used to fit the experimental data. In general, vacuum pyrolysis derived char showed a higher reactivity than atmospheric pyrolysis chars. An explanation based on a higher oxygen content of the vacuum pyrolysis char is suggested.     

高碱低阶煤热解及热解半焦研究进展

我国碱金属、碱土金属(AAEM)含量高的低阶煤储量丰富。高碱含量造成锅炉受热面结渣沾污及气化炉结块腐蚀等难题,低阶煤内水高、氧含量高、挥发分高、发热量低以及易氧化自燃等特性为其储、运、用带来极大的难题。热解可生产优质燃料和高附加值化工原料,也是燃烧、气化、直接液化等过程的起始阶段和/或伴随反应,煤在热解阶段发生的反应、经历的变化,对煤转化利用的效率和清洁程度起重要、甚至决定性作用。笔者对煤热解与热解半焦研究及进展进行综述性评价,着重探讨煤中AAEM对热解过程及半焦的影响。结果表明,热解研究装置模拟的工况与现代煤化工过程中煤热解所处环境相差甚远,半焦样的代表性不强使热解研究成果的指导意义不大;对煤中不同赋存形态AAEM的分离方法有待完善,还需筛选、尝试新的萃取试剂;基本掌握了煤热解过程中AAEM的变迁行为,但尚缺乏控制煤中AAEM危害的有效方法。高碱低阶煤的安全高效洁净转化利用技术仍待突破。     

A model for the evaporation of biomass pyrolysis oil droplets

This paper presents a numerical model for the evaporation and pyrolysis of a single droplet of pyrolysis oil derived from biomass. Continuous thermodynamics theory for multi-component droplet evaporation is used, with the fuel being represented by four fractions: organic acids, aldehydes/ketones, water, and pyrolytic lignin, each of which is described by a separate distribution function. Pyrolysis of the lignin fraction is included, and detailed properties for all fractions are presented. The model is compared with the results of suspended droplet experiments, and is shown to give good predictions of the times of the major events in the lifetime of a droplet.     

干馏温度对高炉喷吹用半焦可磨性能的影响研究

为了研究干馏温度对高炉喷吹用低温干馏半焦可磨性能的影响,采用哈氏可磨性指数测定仪研究了3种原煤在不同干馏温度下制得半焦的可磨性,并采用激光粒度分析仪考查了半焦的破碎特征。研究表明,半焦的可磨性指数随着干馏温度的提高,呈现先升高后降低的趋势,低温干馏半焦的最大可磨性指数对应的最佳干馏温度为540℃;煤的可磨性预测方程不能预测半焦的可磨性;半焦的破碎过程以体积破碎为主,也进行表面破碎,干馏温度对半焦的破碎特征影响较大,半焦破碎后的粒度大小与可磨性存在对应关系。在煤低温干馏的规模化生产过程中,可以通过适当降低现有干馏操作条件优化半焦的可磨性能,以利于低温干馏半焦在高炉喷吹中的应用。     

Effect of lignite pyrolysis conditions on calcium oxide dispersion and subsequent char reactivity

A demineralized North Dakota lignite was loaded with 2.9 wt% Ca by ion exchange. Chars were prepared by pyrolysis in N₂ at 1275 K and residence times between 0.3 s and 1 h. Major differences were observed in their subsequent reactivities in 0.1 MPa air. X-ray diffraction analysis was carried out to obtain information on the state and dispersion of the Ca species on the various chars. The results clearly indicate that CaO is the predominant species responsible for catalysis of lignite char gasification. It is concluded that pyrolysis residence time also has a profound effect on CaO dispersion. Thus, a correlation was established between a fundamental physical property (catalyst dispersion) and the observed gasification behaviour of lignite chars prepared under different pyrolysis conditions.     

Catalysis of lignite char gasification by exchangeable calcium and magnesium

A Montana lignite was pretreated in either HCI—HF or ammonium acetate. The former treatment replaced cations associated with carboxyl groups by hydrogen, as well as removing essentially all mineral matter. The latter treatment replaced cations by ammonium ions but left the mineral matter intact. The pretreated lignites were then loaded with varying amounts of Ca and Mg, separately or jointly, by ion exchange. Reactivities of chars produced from these exchanged lignites, as well as the raw and pretreated lignites, were determined in air, CO₂ and steam. Gasification of exchanged lignites was strongly catalysed by Ca; its activity was not affected by the presence of Mg on the char. At a comparable Ca loading, gasification rates of the 1273 K raw lignite char in the various atmospheres was higher than that of the acid treated 1273 K char but lower than that of the ammonium acetate treated 1273 K char. The former finding is attributed to chlorine retention in the lignite and char; the latter, to enhanced sulphur release during lignite pyrolysis.     

油品蒸发损耗及油气回收技术

石油及其产品在加工和储运过程中产生的蒸发损耗是困扰石油加工储运和环保行业的重要课题,推广和采用油气回收技术十分迫切和重要。本文介绍了常见的4种油气回收技术吸附法、吸收法、冷凝法和薄膜选择渗透法,分析了各种油气回收方法的发展方向,特别介绍了活性碳纤维作为新型油气回收吸附材料的应用前景。     

Fe2O3对高变质程度脱灰煤热解反应性与半焦结构的影响

利用热天平研究了共混合法负载Fe₂O₃高变质程度脱灰煤的热解反应性,结果表明煤粉负载Fe₂O₃后热解反应性高于无负载的热解反应性。负载Fe₂O₃煤样在程序升温加热的马弗炉中制备出半焦,利用FTIR、XRD和RAMAN 等分析了半焦结构。由TG和FTIR可知,负载Fe₂O₃煤样热解时,热解转化率增加,热解后自由基增加。由XRD可知,Fe₂O₃没有使得煤样半焦的002峰衍射角发生明显变化,但使L_a和L_c参数明显降低,说明半焦的微晶结构石墨化程度降低。另外,在XRD分析谱图中发现部分Fe₂O₃被还原成FeO。由RAMAN可知,Fe₂O₃使半焦的G峰峰面积降低,D峰峰面积增加,说明半焦的有机结构有序化程度降低。     

Gasification of wood char and effects of intraparticle transport

Kinetic parameters for gasification of hybrid poplar spp. char have been measured. A differential reactor was used to obtain rate data for catalytic and non-catalytic reactions of small wood char particles (1–2 mm in size) at 100 kPa for temperatures in the range 400–700 °C, steam partial pressures between 45–100 kPa, and space velocities in the range 2.0–7.3 s^?1 During pyrolysis of wood without the addition of either K₂CO₃ or Na₂CO₃, the cellular structure of the wood was preserved. Additionally, this cellular structure remained intact during most of the gasification process. Addition of K₂CO₃ and Na₂CO₃ before pyrolysis caused a degradation of the regular cellular structure and an increase in the rate of gasification of the resulting char. Effectiveness factor calculations were made for particles of various sizes and results indicate that diffusion control of the gasification reaction becomes important for particles larger than 0.5 CM.     

Reaction kinetics of gasification of black liquor char

CO₂ gasification of black liquor char, prepared from kraft spent pulping liquor is studied thermogravimetrically up to 775°C. The gasification rate is described by Langmuir-Hinshelwood type kinetics and activation energy is similar to that found for alkali metal impregnated porous carbons. However the rate is about 20 times larger than that of coal char mixed with 10-20% Na₂ CO₃. CO inhibition is relatively small and the rate is first order in carbon up to 80% conversion. The behavior is explained by a fine and three-dimensional dispersion of sodium salts in the char. The rate is insensitive to pulping conditions over the range of industrial practice.     

Rapid pyrolysis of brown coal and oil shale

A brown coal, peat and oil shale were subjected to a rapid pyrolysis process and medium-heat-value gases together with tar were collected. The char residue was of high activity and suitable for gasification to create a two-stage gasification system. The coal-tar is used for manufacturing liquid fuels and chemicals.     

甘肃油页岩红外光谱分析及热解特性

基于热重分析仪（TG）、傅里叶变换红外光谱分析仪（FTIR）和质谱分析仪（MS）三机联用对甘肃油页岩进行光谱和热解实验。通过分析光谱谱图,得到了样品中的化学成分和化学结构的相关信息。结果表明,其化学结构的特征在于相对较高量的脂肪族基团。在TG/FTIR/MS三联机上研究了甘肃油页岩的热解特性,实验结果表明：整个热解过程主要有两个阶段,即低温段和高温段。大部分的热解行为发生在低温段（400～600℃）,此阶段里油页岩的失重量占总失重量的70%,可挥发物质迅速热解,热解产生的气体有H2、H2O、CO2、CH4、CO、轻质烃等。而在高温段（600～850℃）的热解气体产率很小,失重量只占总重量的2.167%。这个阶段主要是含碳酸盐的矿物质分解而产生一定量的气体。本文主要研究两个热解阶段产生的气体。对产生气体的种类、时间和产生机理进行了研究,并得出热解的化学反应动力学参数。     

Fe2O3对高变质程度脱灰煤热解反应性与半焦结构的影响

利用热天平研究了共混合法负载Fe₂O₃高变质程度脱灰煤的热解反应性,结果表明煤粉负载Fe₂O₃后热解反应性高于无负载的热解反应性。负载Fe₂O₃煤样在程序升温加热的马弗炉中制备出半焦,利用FTIR、XRD和RAMAN 等分析了半焦结构。由TG和FTIR可知,负载Fe₂O₃煤样热解时,热解转化率增加,热解后自由基增加。由XRD可知,Fe₂O₃没有使得煤样半焦的002峰衍射角发生明显变化,但使L_a和L_c参数明显降低,说明半焦的微晶结构石墨化程度降低。另外,在XRD分析谱图中发现部分Fe₂O₃被还原成FeO。由RAMAN可知,Fe₂O₃使半焦的G峰峰面积降低,D峰峰面积增加,说明半焦的有机结构有序化程度降低。     

沥青矿石转化轻质燃料油及活性炭

利用沥青矿石与液体催化剂在高温常压条件下判断反应进程。研究反应温度、反应物配比的影响。研究表明,少量液体催化剂的加入,极大程度地提高沥青矿石的轻质量燃料油收率,又能使剩下的残渣转化成活性炭。     

Rate retardation phenomenon during gasification of Wandoan coal char

During the course of coal gasification, the rate per unit weight of remaining char often decreases as the coal conversion increases. The present study has tried to elucidate the reason why this rate retardation occurs. Possible reasons can be roughly divided into two categories; one due to the change of the mineral matter in char, and one related to the variation of carbon structure. Char samples at different conversion levels were prepared from raw and demineralized Wandoan coal. Their reactivities and other properties were examined, and their relationship was considered. The principal reason for the rate retardation in the present case was attributed to the loss of catalytic activity of mineral matter as the conversion increases.     

焦渣吸附-催化氧化法处理鲁奇炉煤气废水研究

对褐煤焦渣吸附、Fenton试剂氧化联合处理鲁奇炉煤气废水作了研究,分别考察了焦渣、H2O2、Fe2+投加量以及pH值、温度、时间等因素对COD去除率的影响,确定了最佳处理条件。实验结果表明,可使废水的COD值由1 880 mg/L降至90 mg/L,去除率达到95.16%,符合国家一级排放标准。同时,采用吸附-氧化法联合处理,不仅降低了直接使用Fenton试剂氧化的处理成本,而且为焦渣开辟了新的用途。     

含油污泥回转式连续热解--质能平衡及产物分析

含油污泥是石油开采和石油化工行业中最常见的工业固体废物,而热解技术由于具有能量或物质回收效率高,环境污染小的特点,也已成为继焚烧技术之后又一重要的固体废物处理技术.在一台处理量为1～2 kg•h^-1的回转式连续反应器上进行了含油污泥热解的实验研究,以氩气为反应气氛,热解温度为550℃,并对气、液、固三相产物进行了详细的分析.结果表明：实验的质量和能量平衡误差分别在10%和15%以内,有效地回收了含油污泥中的挥发性有机物VOCs和半挥发性有机物SVOCs,气液固产物的质量比分别为10%、20%和70%,其中热解气体(含载气)的热值为11 MJ•m^-3,主要成分为甲烷、二氧化碳、乙烷和氢气等;同时测定了热解油的物化性质、馏分和元素组成,并结合GC-MS分析了主要芳香烃的分布,分析所得热解油以柴油馏分（75%）为主,热值可达43 MJ•kg^-1左右,可直接作燃料油使用,但其杂原子和芳香烃含量较高,油品质量与成品油还有一定差距;此外对热解固体残渣的分析显示,残渣以沙粒为主,含碳量在4%～6%之间,且固定了大多数金属元素(Pb、Cr、Ni除外),可用于铺路或建材.     

Reactive intermediate in the alkali-carbonate-catalysed gasification of coal char

Based on results from a variety of experimental measurements, a detailed mechanism is postulated for the action of the inorganic catalyst in char gasification. In this mechanism, a catalyst such as potassium carbonate in contact with char undergoes a chemical and physical transformation to form a molten potassium oxide film that covers the char surface. This film serves as an oxygen transfer medium between the gaseous reactant (H₂O or CO₂) and the char. At the catalyst/char interface, an oxidation-reduction reaction occurs and the anions in the catalyst react with the oxidized char to form a phenolate-type functional group that subsequently splits out CO. The anions are replenished by reaction between the oxidizing gas (H₂O or CO₂) and the oxide at the gas/catalyst interface. Net transport of oxygen from gas to char occurs by diffusion of the species in the molten catalyst film.     

Diagnostics of structural alterations in coal: Porosity changes with pyrolysis temperature

The results of thermogravimetry, mercury and adsorption methods, together with porosity determination and emanation thermal analysis, are compared for two British bituminous coals: Manvers Wath and Markham Main, to characterize their structural alterations.     

Influence of coal preoxidation and the relation between char structure and gasification potential

A study was carried out to ascertain the effects of coal preoxidation and carbonization conditions on the structure and relative gasification potential of a series of bituminous coal chars. Chars were prepared from two freshly mined bituminous coals and preoxidized samples derived from them. Carbonization conditions included a wide range of heating rate (0.2–10000K s^?1), temperature (1073–1273 K) and time (0.25–3600 s). Char properties were characterized in terms of analysis of char morphology, surface area, elemental composition, and gasification reactivity in air. Over the range of conditions used, preoxidation substantially reduced coal fluid behaviour and influenced macroscopic char properties (char morphology). Following slow heating (0.2 K s^?1), preoxidized coals yielded chars having higher total surface areas and higher reactivities toward gasification in air than did similar chars prepared from fresh coal. Following rapid heating (10000 K s^?1) and short residence times (0.25 s), chars prepared from preoxidized and fresh coals exhibited similar microstructural and chemical properties (surface area, $\text{C}\text{H}$ ratios, gasification rates). Carbonization time and temperature were found to be the critical parameters influencing char structure and gasification potential.