以纸浆黑液为催化剂高变质无烟煤热天平水蒸气催化气化动力学

以纸浆黑液为催化剂，用等温热重法研究4种高变质无烟煤常压纯水蒸气催化气化反应动力学．采用催化剂有效因子修正缩芯模型，测定温度为750～950℃反应控制时无烟煤碳转化率与时间的关系，并用修正缩芯模型和修正体积模型进行较好拟合，得出这4种无烟煤水蒸气催化气化的反应速率常数、活化能和指前因子，活化能范围为112．838～204．566kJ／mol．除灰含量最高的永安加筛煤以外，其他3种煤的反应速率常数都比加碳酸钠的高．     

有机钠催化剂对无烟煤的催化气化动力学

以十二烷基苯磺酸钠和柠檬酸三钠为催化剂,利用常压热分析仪对福建省创宏无烟煤进行了水蒸气气化动力学实验.在850～950,℃下测定了催化剂加载量为0～15%时,转化率随气化时间的变化;并采用缩核模型对实验数据进行拟合,给出相应的动力学参数.结果表明,十二烷基苯磺酸钠和柠檬酸三钠均能明显提高反应的气化速率,降低气化反应活化能;表面活性剂十二烷基苯磺酸钠的催化效果优于络合剂柠檬酸三钠,且与碳酸钠催化效果相当,是一种良好的煤催化气化催化剂.     

高变质无烟煤催化气化动力学及补偿效应

以碳酸钠为催化剂,利用热天平研究了福建建欣高变质无烟煤常压下水蒸气气化反应动力学,在800～950℃测定了碳酸钠加载量从0～18%时该无烟煤气化反应特性,确定了实验条件下碳酸钠催化剂加载饱和浓度,结果表明,加载催化剂后建欣无烟煤气化反应活化能大幅降低.得到了建欣无烟煤与水蒸气气化反应动力学缩芯模型,并给出相应的动力学参数.分析表明,该催化气化反应体系活化能E与频率因子A0之间存在动力学补偿效应,得出其补偿效应方程为ln,A0=8.66×10-5E-0.2827,等动力学温度为1 389 K.     

CaO和MgO复合催化神木煤焦-CO_2气化的特性研究

利用常压等温CO_2气化的方法,研究了单组分CaO、MgO及CaO/MgO不同复合配比对神木煤焦催化气化的反应特性影响。结果表明:分别添加单组分催化剂CaO和MgO后,煤焦的气化反应活性得到了明显增强,并且CaO的催化作用要强于MgO;2种单组分催化剂添加量存在一个最优值,且均为15%,此时催化强度分别是原煤焦的5.67和2.37倍,当催化剂添加量超过这个最优值后,催化剂对气化的催化作用开始减弱;添加10%的不同CaO/MgO配比的复合催化剂,其催化效果明显强于相同含量的2种单组分,且900℃时存在一个最佳配比比例4:1,最佳配比下,催化强度是原煤焦的5.32倍,是添加10%CaO的1.69倍,是添加10%MgO的2.83倍。Takarada法计算了复合催化剂各工况下的反应性指数R,更直接地反映出了不同配比的复合催化剂对煤焦气化的影响。用未反应核收缩模型能够很好地描述煤焦-CO_2的气化反应过程;添加单组分催化剂煤焦的活化能相比原煤焦变化不大,而添加复合催化剂煤焦的活化能有一定程度的升高。     

生物质催化热解气化热重分析研究

采用热重分析与气相色谱分析(TG-GC)相结合的方法,开展了以麦秸为主要研究对象的生物质催化热解气化实验研究,探讨了以NiO和CaO为催化剂,水蒸气气氛下的麦秸挥发分析出特性、半焦的气化特性、气化反应动力学特性以及催化剂对麦秸气化产物的影响.实验结果表明麦秸水蒸气气氛下的反应活性明显提高,气化反应过程中热解阶段视为一级反应,半焦气化视为缩核反应.非催化条件下麦秸的半焦气化在800℃以上才进行,添加NiO与CaO均促进了麦秸与水蒸气的气化反应,提高了气化过程的碳转化率和反应速率,但二者对半焦气化的促进机理以及气体产物的催化选择性有明显差异.添加NiO时H2产率最大,达到34mol/kg麦秸,且使气化反应温度明显降低.添加CaO不仅促进了H2和CO的生成,而且CH4产率也明显提高,表明CaO更有利于大分子碳氢化合物的裂解.     

CaO和Fe（N03）3复合催化锦界煤焦-C02气化的实验研究

在搭建的固定床实验台上对CaO和Fe（NO3）3复合催化锦界煤焦-CO2常压等温气化的反应特性进行了研究．结果表明：复合催化剂最佳质量添加比例为1％Ca、29／6Fe,且在最佳添加量下气化时间比原煤焦和单组分催化剂下的气化时间分别缩短了103rain和18rain,催化强度系数分别是原煤焦、单组分催化剂CaO和Fe（N03）3的5．71倍、1．65倍和2．04倍,气化温度降低了100K,气化温度降低程度介于单组分催化剂CaO和Fe（NO3）3之间;复合催化过程生成的部分Ca（NO3）2与CaO的活性不同,即Ca的催化强度与其前驱物的形式有一定关系;添加单组分催化剂的煤焦活化能与原煤焦的活化能基本相同,不同添加比例的复合催化剂的煤焦活化能增加的程度不同,且在最佳添加比例下增加程度最小,其值为15．4％．     

纤维素废弃物稀酸水解残渣制氢研究

对纤维素废弃物水解残渣催化气化制氢进行了研究,考察了气化温度、催化温度、催化剂颗粒粒径和S/B (单位时间内进入气化器中水蒸汽质量与生物质质量之比)4个主要参数对气体组成和氢气产率的影响并和以木屑为原料催化气化制氢进行了比较。在试验范围内提高气化温度、催化温度和S/B的值以及减小催化剂颗粒粒径对提高氢产率有利,其中气化温度和S/B对提高氢产率影响较大。气化温度在800～850℃内较为理想,催化剂颗粒的适宜粒径为2～3mm,S/B取1.5～2.0较佳;和木屑制氢相比,使用水解残渣制取的气体中CO和CO_2的体积百分比小,H_2/CO的值大,氢气含量高,有利于后续处理,且氢产率大,对制氢有利。     

钠离子及灰分对煤焦CO_2气化反应性的影响

文章通过热重分析仪对原煤1、原煤2、原煤2脱灰、原煤2+Na Cl、原煤2+Na OH进行了热重试验,并计算了碳转化率和气化比速率。分析了煤中的钠离子和灰分对煤焦CO2气化反应活性的影响。结果表明:煤焦中的碳逐渐与气化剂反应时,煤中的钠熔融,富集在碳颗粒表面上,阻碍气化剂与煤焦内表面接触,使气化反应性降低。脱灰后外加碱金属煤的气化反应性大于脱灰煤,体现了碱金属钠对于煤焦CO2气化反应性的催化作用。当气化温度逐渐上升时,Na Cl、Na OH的催化效果越来越明显;在1 100℃在前,Na Cl的催化效果略高于Na OH,在1100℃之后,Na OH的催化效果高于Na Cl;因为气化温度过高时,以Na Cl形式存在的Na从煤焦中逸出,减弱了碱金属催化剂的催化效果。     

黑液热转化技术及其热动力学模型

黑液中含有大量的有机物和无机物,随意排放会污染环境。传统的资源化处理方法多种多样,目前备受关注的黑液处理法为热转化法。黑液的热转化技术主要分为热裂解、气化技术、水热转化技术。通过3种热分析的动力学模型,从多个角度了解黑液的整个热力学反应过程。综述了近年来国内外关于黑液热转化技术及其动力学的研究成果,为黑液的热处理提供借鉴依据。     

基于生物质稻秸气化的催化剂研究

利用浸渍法和沉淀法分别制备了Ni/Al₂O₃（NiAlI）和Ni/白云石（NiDoP）两类生物质气化催化剂,采用氢气还原热重实验和固定床气化实验对两类催化剂进行性能验证,分析了催化剂制备方法、活性组分、还原温度、负载量、还原度、比表面积等因素对气化效果的影响。结果显示沉淀法制备的NiDoP中Ni以Mg_0.4Ni_0.6O固溶体形式存在,其适宜的还原温度范围为400～600℃,浸渍法制备的NiAlI中Ni以NiAl₂O₄形式存在,其适宜的还原温度范围为800～900℃。500℃还原后的20NiDoP较20NiAlI具有更好的催化性能,900℃时20NiDoPA催化下的氢产率达34mol/（kg daf）,碳转化率达96%。添加5%K₂CO₃改性后的20NiDoP催化剂中,K₂O在气化过程中起了显著的催化作用。此外,在生物质气化催化剂制备过程中需综合考虑比表面积和负载量的相互关系。     

炭化气氛对黑液煤浆及不同煤种气化反应特性的影响

煤气化前阶段的炭化气氛(温度、时间)影响到煤焦的气化反应特性.采用不同的炭化温度和炭化时间制备了黑液水煤浆、普通水煤浆以及其他5种煤的焦样,得到了各种煤焦气化反应的碳转化率;同时,通过扫描电子显微镜分析手段鉴别焦炭表面孔隙分布情况.试验结果表明,相同炭化气氛下得到的7种不同煤焦中,黄陵煤焦的气化活性最高,说明煤化程度越高反应性越低;由于黑液中有机物和无机物钠盐的影响,黑液水煤浆焦的气化特性高于普通水煤浆焦和新汶煤焦.煤焦的气化反应性,不仅与煤阶有关,还和煤焦中含氧官能团和无机化合物的含量有关,同时煤浆中外在添加的无机物组分也影响到煤焦的气化活性.     

Catalytic effect of black liquor on the gasification reactivity of petroleum coke

CO₂ gasification of petroleum coke using black liquor as a catalyst was performed in a thermogravimetric analyzer (TGA) under temperatures 1223–1673 K at ambient pressure to evaluate the effect of black liquor loading on petroleum coke gasification. It was found that the gasification reactivity of petroleum coke was improved greatly by black liquor. The gasification reactivity was affected by different loading methods in the order: wet grinding > dry grinding > physical impregnation > dry mix. The catalytic activity of black liquor was higher than that of pure alkali metal. The effect of temperature on the gasification reactivity of petroleum coke was changed by black liquor. The reactivity reaches its maximum at 1573 K. The reactivity of petroleum coke was found higher than that of Shenfu coal when black liquor loading is 5 wt.% (of petroleum coke), clearly demonstrating that black liquor could be an effective catalyst for petroleum coke gasification.     

Gasification of diosgenin solid waste for hydrogen production in supercritical water

The potential of diosgenin solid waste (DSW) to be a proper feedstock for hydrogen production from supercritical water gasification was assessed through thermodynamic analysis and experimental study. The thermodynamic analysis of DSW gasification in SCW was performed by Aspen Plus software based on the principle of minimum Gibbs free energy. The effects of temperature (500–650 °C), flow ratio of feedstock slurry to preheated water on the gasification were studied. K₂CO₃ and black liquor were used to catalyze the gasification of DSW. The morphological structures of DSW and residue char were characterized by SEM. The results showed that DSW was almost completely gasified at 650 °C without catalyst and the carbon gasification efficiency reached up to 98.55%. K₂CO₃ could significantly promote the gasification reactivity of DSW at a lower temperature. H₂ yield was remarkably improved by adding black liquor. The SEM analysis indicated that parts of the organic matters reacted to form gases and liquid products, and K₂CO₃ was found to migrate into the residue char during the reactions.     

Fuel conversion characteristics of black liquor and pyrolysis oil mixtures: Efficient gasification with inherent catalyst

Alkali metals inherent in black liquor (BL) have strong catalytic activity during gasification. A catalytic co-gasification process based on BL with pyrolysis oil (PO) has the potential to be a part of efficient and fuel-flexible biofuel production systems. The objective of the paper is to investigate how adding PO into BL alters fuel conversion under gasification conditions. First, the conversion times of single fuel droplet were observed in a flat flame burner under different conditions. Fuel conversion times of PO/BL mixtures were significantly lower than PO and comparable to BL. Initial droplet size (300–1500 μm) was the main variable affecting devolatilization, indicating control by external heat transfer. Char oxidation was affected by droplet size and the surrounding gas composition. Then, the intrinsic reactivity of char gasification was measured in an isothermal thermogravimetric analyser at T = 993–1133 K under the flow of CO₂–N₂ mixtures. All the BL-based samples (100% BL, 20% PO/80% BL, and 30% PO/70% BL on mass basis) showed very high char conversion. Conversion rate of char gasification for PO/BL mixtures was comparable to that of pure BL although the fraction of alkali metal in char decreased because of mixing. The reactivities of BL and BL/PO chars were higher than the literature values for solid biomass and coal chars by several orders of magnitude. The combined results suggest that fuel mixtures containing up to 30% of PO on mass basis may be feasible in existing BL gasification technology.     

Waste to energy by industrially integrated supercritical water gasification - Effects of alkali salts in residual by-products from the pulp and paper industry

Supercritical water gasification (SCWG) is a method by which biomass can be converted into a hydrogen-rich gas product. Wet industrial waste streams, which contain both organic and inorganic material, are well suited for treatment by SCWG. In this study, the gasification of two streams of biomass resulting from the pulp and paper industry, black liquor and paper sludge, has been investigated. The purpose is to convert these to useful products, both gaseous and solids, which can be used either in the papermaking process or in external applications. Simple compounds, such as glucose, have been fully gasified in SCWG, but gasification of more complex compounds, such as biomass and waste, have not reached as high conversions. The investigated paper sludge was not easily gasified. Improving gasification results with catalysts is an option and the use of alkali salts for this purpose was studied. The relationship between alkali concentration, temperature, and gasification yields was studied with the addition of KOH, K₂CO₃, NaOH and black liquor to the paper sludge. Addition of black liquor to the paper sludge resulted in similarly enhancing effects as when the alkali salts were added, which made it possible to raise the dry matter content and gasification yield without expensive additives.     

Evaluation of effect of evaporation on supercritical water gasification of black liquor by energy and exergy analysis

Supercritical water gasification (SCWG) is a promising innovative black liquor handling method. The low concentration of black liquor is a burden for the system scale and investment cost. In this study, we introduced black liquor evaporator to increase the concentration using self-generated steam and power, and studied its influence on the energy and exergy efficiency. The results showed that increasing black liquor concentration from 10 wt% to 20 wt% reduced the energy efficiency but increased the exergy efficiency of the system without evaporator. With the evaporator, an optimal target concentration existed for the exergy efficiency owing to the influence of the target concentration on the balance between the energy consumption and saving brought by the evaporator. With black liquor condensed from 15 wt% to 21.82 wt%, maximum exergy efficiency of the system (41.95%) was obtained. For lower-concentration black liquor, more water needs to be evaporated to get the optimal concentration and evaporator was more desired because it brought greater improvement on the exergy efficiency. The increasing effect number of multi-effect evaporator shifted the optimal concentration to higher values, which increased from 19.93 wt% to 23.13 wt% when the effect number increased from 4 to 7. The exergy efficiency of the system was also improved, and the improvement was more significant at higher target concentration.     

黑液气化的热力学平衡模型分析

通过黑液气化模型研究气化空气量、气化压力和气化原料湿度对气化平衡温度、气化气热值及产气量的影响.结果显示:对于AssiDom(a)n Kraftliner黑液样品,在压力增大,当量比为0.22～0.25,湿度Z为0.05～0.10的条件下可以获得较好的气化效果.     

Hydrogen production from supercritical water gasification of alkaline wheat straw pulping black liquor in continuous flow system

Supercritical water gasification of alkaline black liquor was investigated in a continuous flow system. The experiments were carried out at 400–600 °C, 25 MPa, with residence times ranging from 4.94 to 13.71 s. The results showed that the increase of temperature and residence time and the decrease of feeding concentration enhanced the gasification. The gaseous product contained high level of hydrogen (40.26–61.02%). Maximum COD removal efficiency (88.69%) was obtained at 600 °C. The alkalis in black liquor were found to be precipitated in the reactor during the gasification, which decreased the pH of the effluent to the neutral region (6.4–8.0). The precipitated alkalis were dissolved in the water when the fluid temperature in the reactor was cooled to about 360 °C which increased the pH of the effluent to 11.0. A simplified kinetic study for COD removal efficiency was done by the pseudo-first order reaction assumption. The apparent activated energy was 74.38 kJ/mol and the apparent pre-exponential factor was 10^4.05 s⁻¹.     

Comparison between isothermal and microwave gasification of lignite char for high syngas production

Using the water of lignite as gasification agent, this paper mainly studies the influence of microwave and isothermal gasification on the syngas production and H₂/CO ratio to obtain the maximum possible amount of high-quality syngas. The results show that microwave heating produced syngas had an immensely superior performance over conventional heating. The total gas yields of 1,000 W microwave gasification is 1.75 times more than that of the 1,000°C isothermal gasification. Moreover, the values of H₂/CO ratio obtained from microwave gasification was higher than 1,000°C isothermal gasification.     

Comparison of pulp-mill-integrated hydrogen production from gasified black liquor with stand-alone production from gasified biomass

When gasified black liquor is used for hydrogen production, significant amounts of biomass must be imported. This paper compares two alternative options for producing hydrogen from biomass: (A) pulp-mill-integrated hydrogen production from gasified back liquor; and (B) stand-alone production of hydrogen from gasified biomass. The comparison assumes that the same amount of biomass that is imported in Alternative A is supplied to a stand-alone hydrogen production plant and that the gasified black liquor in Alternative B is used in a black liquor gasification combined cycle (BLGCC) CHP unit. The comparison is based upon equal amounts of black liquor fed to the gasifier, and identical steam and power requirements for the pulp mill. The two systems are compared on the basis of total CO₂ emission consequences, based upon different assumptions for the reference energy system that reflect different societal CO₂ emissions reduction target levels. Ambitions targets are expected to lead to a more CO₂–lean reference energy system, in which case hydrogen production from gasified black liquor (Alternative A) is best from a CO₂ emissions’ perspective, whereas with high CO₂ emissions associated with electricity production, hydrogen from gasified biomass and electricity from gasified black liquor (Alternative B) is preferable.