Two-step steam pyrolysis of biomass for hydrogen production

In this study, different char based catalysts were evaluated in order to increase hydrogen production from the steam pyrolysis of olive pomace in two stage fixed bed reactor system. Biomass char, nickel loaded biomass char, coal char and nickel or iron loaded coal chars were used as catalyst. Acid washed biomass char was also tested to investigate the effect of inorganics in char on catalytic activity for hydrogen production. Catalysts were characterized by using Brunauer–Emmet–Teller (BET) method, X-ray diffraction (XRD) analyzer, X-ray fluorescence (XRF) and thermogravimetric analyzer (TGA). The results showed that the steam in absence of catalyst had no influence on hydrogen production. Increase in catalytic bed temperature (from 500 °C to 700 °C) enhanced hydrogen production in presence of Ni-impregnated and non-impregnated biomass char. Inherent inorganic content of char had great effect on hydrogen production. Ni based biomass char exhibited the highest catalytic activity in terms of hydrogen production. Besides, Ni and Fe based coal char had catalytic activity on H₂ production. On the other hand, the results showed that biomass char was not thermally stable under steam pyrolysis conditions. Weight loss of catalyst during steam pyrolysis could be attributed to steam gasification of biomass char itself. In contrast, properties of coal char based catalysts after steam pyrolysis process remained nearly unchanged, leading to better thermal stability than biomass char.     

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.     

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.     

Distribution of Nitrogen Species During Vitrinite Pyrolysis and Gasification

The formation of HCN and NH₃ during pyrolysis in Ar and gasification in CO₂ and steam/Ar was investigated. Vitrinites were separated and purified from different rank coal from lignite to anthracite. Pyrolysis and gasification were carried out in the drop-tube/fixed-bed reactor at temperatures of 600–900°C. Results showed that with increase of reaction temperature the yield of HCN increased significantly during pyrolysis and gasification. Decrease of coal rank also increased the yield of HCN. Vitrinite from lower rank of coal with high volatile content released more HCN. The yield of NH₃ was the highest at 800°C during pyrolysis and gasification. And the yield of NH₃ from gasification in steam/Ar was far higher than that from gasification in CO₂, where the hydrogen radicals play a key role. Nitrogen retained in char was also investigated. The yield of char-N decreased with an increase of pyrolysis temperature. Vitrinite from lower rank coal had lower yield of char-N than that from the high rank coal.     

Exergy analysis of biomass staged-gasification for hydrogen-rich syngas

Using Aspen Plus simulations, exergy analyses of hydrogen-rich syngas production via biomass staged-gasification are carried out for three configurations, namely, staged-gasification with pyrolysis gas combustion and char gasification (C-1), staged-gasification with pyrolysis gas reforming and char gasification (C-2), and staged-gasification with pyrolysis gas reforming and char combustion (C-3). The results show that, for the gasification and reforming processes, the exergy loss of pyrolysis gas with tar reforming is less than that of char gasification. As for the system, it is conducive to generating hydrogen by making full use of the hydrogen element (H) in biomass instead of the H in water. The benefits of C-1 are that it removes tar and produces higher yield and concentration of hydrogen. However, C-2 is capable of obtaining higher exergy efficiency and lower exergy loss per mole of H₂ production. C-3 theoretically has greater process performances, but it has disadvantages in tar conversion in practical applications. The appropriate gasification temperature (T_G) are in the range of 700–750 °C and the appropriate mass ratio of steam to biomass (S/B) are in the range of 0.6–0.8 for C-1 and C-3; the corresponding parameters for C-2 are in the ranges of 650–700 °C and 0.7–0.8, respectively.     

Kinetic characteristics of in-situ char-steam gasification following pyrolysis of a demineralized coal

This study aims to examine the char-steam reactions in-situ, following the pyrolysis process of a demineralized coal in a micro fluidized bed reactor, with particular focuses on gas release and its kinetics characteristics. The main experimental variables were temperatures (925 °C?1075 °C) and steam concentrations (15%–35% H₂O), and the combination of pyrolysis and subsequent gasification in one experiment was achieved switching the atmosphere from pure argon to steam and argon mixture. The results indicate that when temperature was higher than 975 °C, the absolute carbon conversion rate during the char gasification could easily reach 100%. When temperature was 1025 °C and 1075 °C, the carbon conversion rate changed little with steam concentration increasing from 25% to 35%. The activation energy calculated from shrinking core model and random pore model was all between 186 and 194 kJ/mol, and the fitting accuracy of shrinking core model was higher than that of the random pore model in this study. The char reactivity from demineralized coal pyrolysis gradually worsened with decreasing temperature and steam partial pressure. The range of reaction order of steam gasification was 0.49–0.61. Compared to raw coal, the progress of water gas shift reaction (CO + H₂O ? CO₂ + H₂) was hindered during the steam gasification of char obtained from the demineralized coal pyrolysis. Meanwhile, the gas content from the char gasification after the demineralized coal pyrolysis showed a low sensitivity to the change in temperature.     

Gasification reactivity and synergistic effect of conventional and microwave pyrolysis derived algae chars in CO2 atmosphere

This research focuses on the isothermal and non-isothermal CO₂ gasification of an algal (Chlorella) char prepared via two different thermal processing systems, i.e. conventional and microwave-assisted pyrolysis. It was found that chars prepared via microwave irradiation showed higher CO₂ gasification reactivity than that of chars prepared via the conventional method. Meanwhile, the activation energy of microwave char was found to be 127.89 kJ/mol, which was 46.3 kJ/mol lower than that of conventional char, indicating improved reactivity of microwave char. The systematic characterisation of both conventional and microwave chars shows that the higher reactivity of microwave char could be attributed to its large BET surface area, low crystalline index and high active sites. In addition, it was found that microwave heating contributed to high reactivity of chars through generating large amount of primary char, the formation of hot spot and high specific surface area and pore volume. Results of co-gasification under isothermal conditions revealed the existence of greater synergistic effects between coal char and microwave algae char than those of coal char and conventional algae char. Furthermore, based on the relative Rs (average gasification rate), a novel index proposed to quantify the interactions in co-gasification process, Australian coal char/microwave assisted char blend experienced 10% higher interactions compared to Australian coal char/conventional assisted char blend.     

Rapid pyrolysis and CO2 gasification of anthracite at high temperature

Anthracite could be burnt efficiently at high temperature utilizing oxy-coal technology. To clarify the effects of temperature and atmosphere on char porosity characteristics, char morphology, fuel-N conversion, and reducing products release, rapid pyrolysis and CO₂ gasification of anthracite was carried out in a high temperature entrained-flow reactor to simulate the condition in a pulverized coal furnace. Developed pore structure was formed in the gasification chars, which could be contributed to charCO₂ reaction at high temperatures. More mesopores were formed in internal carbon skeleton and retained against collapse and coalescent for gasification chars than pyrolysis chars. Compared with pyrolysis char, smoother and denser surface was observed in gasification char with the irregular bulges disappeared due to the destruction of external carbon skeleton. Char-N could be oxidized to NO in CO₂ atmosphere and then reduced to N₂ by (CN) on the char surface. Char-N release was greatly promoted due to gasification reaction along with poly-condensation at high temperature; and the preact release of char-N would result in a larger portion of NO_x reduction in the following reduction zone with the oxygen-staging combustion technology compared with that in air-staging combustion. Complementally, homogeneous reduction in NO_x emission would play a minor effect for anthracite in oxy-coal combustion because of the deficiency of CH₄ and HCN, especially at high temperature.     

High-temperature pyrolysis behavior of two different rank coals in fixed-bed and drop tube furnace reactors

In order to explore the high-temperature pyrolysis behavior and mechanism, two different rank coals (Shenhua bituminous coal and Baiyinhua lignite coal) were pyrolyzed in fixed-bed and drop tube furnace (DTF) reactors. Pyrolysis gas production was online quantified by a drainage method while the gas composition was detected by the gas chromatography. The physical and chemical characteristics of pyrolysis char were observed by N₂ absorption and FTIR. Results show that pyrolysis gas release rate and total production increase with the higher temperature. The gas production of SH coal (618–749 ml/g) is always higher than that of BYH coal (418–510 ml/g) due to its higher volatile content. The main high-temperature pyrolysis gas products are H₂ (∼50% vol), CO, CH₄ and CO₂. Carbon-reduction reaction at high temperatures can further form H₂ and CO while the rupture of aromatic heterocyclic ring can generate CH₄. High-temperature pyrolysis can greatly remove the coal moisture, develop their pore structures, crack the chemical functional groups (O–H, –CH₃, CO, C–O, etc.) and upgrade the coal rank. Different coal structures and pyrolysis heating rates result in various gas evolution and char formation behaviors. Higher heating rate can help to quickly generate large amounts of free radicals and change the pyrolysis behaviors.     

Detailed kinetic analysis and modelling of the dry gasification reaction of olive kernel and lignite coal chars

The dry gasification process of solid fuels is a promising pathway to mitigate and utilize captured CO₂ emissions toward syngas generation with tailored composition for several downstream energy conversion and chemical production processes. In the present work, comprehensive kinetic analysis and reaction modelling studies were carried out for olive kernel and lignite coal chars gasification reaction using pure CO₂ as gasifying agent. Chars reactivity and kinetics of the gasification reactions were thoroughly examined by thermogravimetric analysis at three different heating rates and correlated with their physicochemical properties. The reactivity of olive kernel char, as determined by the mean gasification reactivity and the comprehensive gasification characteristic index, S, was almost three times higher compared to that of the lignite coal char. It was disclosed that the fixed carbon content and alkali index (AI) have a major impact on the reactivity of chars. The activation energy, E_a, estimated by three different model-free kinetic methods was ranged between 140 and 170 kJ/mol and 250–350 kJ/mol for the olive kernel and lignite coal chars, respectively. The activation energy values for the lignite coal char significantly varied with carbon conversion degree, whereas this was not the case for olive kernel char, where the activation energy remained essentially unmodified throughout the whole carbon conversion range. Finally, the combined Malek and Coats-Rendfrem method was applied to unravel the mechanism of chars-CO₂ gasification reaction. It was found that the olive kernel char-CO₂ gasification can be described with a 2D-diffusion mechanism function (D2) whereas the lignite coal char-CO₂ gasification follows a second order chemical reaction mechanism function (F2).     

Hydrogen production in underground coal gasification (UCG)

In this article, the rationales of the hydrogen production in underground coal gasification are explained. The experimental conditions and process of the underground gasification in the Liuzhuang Mine, Tangshan, Hebei Province are introduced, and the experimental results are analyzed. By adopting the new method of two-stage underground coal gasification with long channels and big sections, the daily water gas production reaches about 22,950 m³, with the maximum output of 53,550 m³, in which H₂ content is between 41 and 74%, with both CO and CH₄ contents over 7%. The daily average output of H₂ is 13,192 m³. Experimental results show that the two-stage underground gasification with multi-point air (steam) feed cannot only improve the average temperature of the gasifier effectively, but also shorten the cyclical time for the two stages by a wide margin, which makes the time longer by 0.96–1.18 times and 1.27–1.91 times, respectively, when water gas with a high content of H₂ is produced, as opposed to that of a traditional mode of pumping air (seam) with fixed points for field and model tests.     

Evolution of pore structure and fractal characteristics of coal char during coal gasification

This study classifies the evolutionary properties of coal char pore structure which occur during coal gasification. CO₂ gasification of various coal samples was carried out in a fixed bed reactor. The resulting chars were analysed using N₂ isothermal adsorption/desorption and scanning electron microscopy (SEM), coupled with fractal theory. Analytical results indicate that the pore structure of coal char underwent micropore evolving, enlarging and overlapping, while more mesopores and macropores developed with continued gasification. The surface area of coal char increased to its maximum value when carbon conversion reached approximately 50%. Fractal calculation results showed that two types of fractal structures associated with the coal char surface and pore structure underwent stereome development and elapsing. However, the evolutionary properties were unique for different coal samples. High rank coal had a complex spatial structure with more micro-pores, whereas lower rank coal had a much flatter spatial structure.     

Laboratory studies on cavity growth and product gas composition in the context of underground coal gasification

Systematic laboratory scale experiments on coal blocks can provide significant insight into the underground coal gasification (UCG) process. Our earlier work has demonstrated the various features of the early UCG cavity shape and rate of growth through lab-scale experiments on coal combustion, wherein the feed gas is oxygen. In this paper, we study the feasibility of in situ gasification of coal in a similar laboratory scale reactor set-up, under conditions relevant for field practice of UCG, using an oxygen-steam mixture as the feed gas. By performing the gasification reaction in a cyclic manner, we have been able to obtain a product gas with hydrogen concentrations as high as 39% and a calorific value of 178 kJ/mol. The effect of various operating parameters such as feed temperature, feed steam to oxygen ratio, initial combustion time and so on, on the product gas composition is studied and the optimum operating conditions in order to achieve desired conversion to syngas, are determined. We also study the effect of various design and operating parameters on the evolution of the gasification cavity. Empirical correlations are proposed for the change in cavity volume and its dimensions in various directions. The results of the previous study on the combustion cavity evolution are compared with this gasification study.     

煤气化过程的神经网络直接辨识

煤在水蒸汽环境中气化时,煤的热解和焦的气化同时发生,两个过程有一些相同的产物,因此无法通过测量确定两个过程各自的进行情况。如果用煤的热解模型和焦的气化模型共同描述煤在水蒸汽中的气化过程,由于缺乏必要的数据,难以保证模型参数的合理性。要直接描述煤热解和焦气化形成的综合过程,传统的数学回归方法又难以胜任。本文用神经网络方法对煤在水蒸汽中气化的综合过程进行了直接辨识,取得了较好的模拟效果,并对煤在水蒸汽中的气化过程有了更深入的了解,为煤气化过程的“活性焦比”模型提供了支持。     

Coal conversion submodels for design applications at elevated pressures. Part II. Char gasification

This paper surveys the database on char gasification at elevated pressures, first, to identify the tendencies that are essential to rational design of coal utilization technology, and second, to validate a gasification mechanism for quantitative design calculations. Four hundred and fifty-three independent tests with 28 different coals characterized pressures from 0.02 to 3.0 MPa, CO₂ and steam mole percentages from 0 to 100%, CO and H₂ levels to 50%, gas temperatures from 800 to 1500 °C, and most of coal rank spectrum. Only a handful of cases characterized inhibition by CO and H₂, and only a single dataset represented the complex mixtures of H₂O, CO₂, CO, and H₂ that arise in practical applications. With uniform gas composition, gasification rates increase for progressively higher pressures, especially at lower pressures. Whereas the pressure effect saturates at the higher pressures with bituminous chars, no saturation is evident with low-rank chars. With fixed partial pressures of the gasification agents, the pressure effect is much weaker. Gasification rates increase for progressively higher gas temperatures. In general, gasification rates diminish for coals of progressively higher rank, but the data exhibit this tendency only for ranks of hv bituminous and higher.

These tendencies are interpreted with CBK/G, a comprehensive gasification mechanism based on the Carbon Burnout Kinetics Model. CBK/G incorporates three surface reactions for char oxidation plus four reactions for gasification by CO₂, H₂O, CO and H₂. Based on a one-point calibration of rate parameters for each coal in the database, CBK/G predicted extents of char conversion within ±11.4 daf wt% and gasification rates within ±22.7%. The predicted pressure, temperature, and concentration dependencies and the predicted inhibiting effects of CO and H₂ were generally confirmed in the data evaluations. The combination of the annealing mechanism and the random pore model imparts the correct form to the predicted rate reductions with conversion. CBK/G in conjunction with equilibrated gas compositions accurately described the lone dataset on complex mixtures with all the most important gasification agents, but many more such datasets are needed for stringent model evaluations.

Practical implications are illustrated with single-particle simulations of various coals, and a 1D gasifier simulation for realistic O₂ and steam stoichiometries. The rank dependence of gasification rates is the determining factor for predicted extents of char conversion at the gasifier outlet. But soot gasification kinetics will determine the unburned carbon emissions for all but the highest rank fuels. Only gasification kinetics for gas mixtures with widely variable levels of H₂O, H₂, and CO are directly relevant to gasifier performance evaluations.     

Experimental investigation on the influence of the pyrolysis operating parameters upon the char reaction activity in supercritical water gasification

Supercritical water gasification of coal is a clean and efficient method for coal utilization which can convert coal into H₂ and CO₂. In order to further reduce costs, a novel two-step cascade utilization method was proposed in this study: conducting traditional pyrolysis first and then gasifying the pyrolysis char in supercritical water. The influences of different pyrolysis operating parameters on gaseous products and char gasification in supercritical water were investigated. Quartz tube reactors were used to ensure the complete collection of gaseous products in pyrolysis process. The experimental results showed that both carbon and hydrogen conversion efficiency increased with temperature, and the increasing trend became not obvious after reaction for 5 min. The thermo-gravimetric curves showed that volatilization removal process was completed at the pyrolysis time of 5 min and higher pyrolysis temperatures were beneficial to the subsequent gasification process. The result also showed that residual weight was 15%–20% of the initial weight. Hydroxyl radicals kept stable during pyrolysis process with the absorption peak intensity increasing first and then decreasing, and mineral substance disintegrated gradually as time increased. As pyrolysis temperature increased, the peak of CC double bonds decreased, turning into stable functional groups and carbonyl group increased. Dispersive pores occurred at the surface of coal as residence time increased with particle size decreasing, specific surface area and reactivity increasing. The results might be used for the design of a cascade utilization system based on coal gasification in supercritical water.     

Effect of temperature on Lu’an bituminous char structure evolution in pyrolysis and combustion

In the process of pyrolysis and combustion of coal particles, coal structure evolution will be affected by the ash behavior, which will further affect the char reactivity, especially in the ash melting temperature zone. Lu’an bituminous char and ash samples were prepared at the N₂ and air atmospheres respectively across ash melting temperature. A scanning electron microscope (SEM) was used to observe the morphology of char and ash. The specific surface area (SSA) analyzer and thermogravimetric analyzer were respectively adopted to obtain the pore structure characteristics of the coal chars and combustion parameters. Besides, an X-ray diffractometer (XRD) was applied to investigate the graphitization degree of coal chars prepared at different pyrolysis temperatures. The SEM results indicated that the number density and physical dimension of ash spheres exuded from the char particles both gradually increased with the increasing temperature, thus the coalescence of ash spheres could be observed obviously above 1100°C. Some flocculent materials appeared on the surface of the char particles at 1300°C, and it could be speculated that β-Si₃N₄ was generated in the pyrolysis process under N₂. The SSA of the chars decreased with the increasing pyrolysis temperature. Inside the char particles, the micropore area and its proportion in the SSA also declined as the pyrolysis temperature increased. Furthermore, the constantly increasing pyrolysis temperature also caused the reactivity of char decrease, which is consistent with the results obtained by XRD. The higher combustion temperature resulted in the lower porosity and more fragments of the ash.     

浑源煤焦CO_2气化反应的影响因素及动力学特性分析

研究了热解温度、热解时间以及气化温度对浑源煤焦CO2气化反应的影响,并获得了气化反应的动力学模型.结果表明：浑源煤焦的气化活性随热解温度的提高而降低;每个热解温度都对应着一个最佳热解时间,且存在最佳热解时间随温度升高而缩短的趋势;提高气化温度能够显著提高煤焦的气化反应性能,气化温度对气化反应的影响大于热解温度的影响;低温度煤焦的气化活性随气化温度的提高而增加更为剧烈;900℃及以上的高温使活性点数增加,从而使煤焦间的活性差距分布均匀;浑源煤焦的气化反应适宜用体积模型来描述,所求取的动力学参数之间存在补偿效应,其等动力学温度约为1 199.6℃.     

Calcium species evolution mechanism during coal pyrolysis and char gasification in H2O/CO2

The release mechanism of Ca during coal pyrolysis and char gasification in H₂O, CO₂ and their mixtures was studied. Sequential chemical extraction was used to determine the modes of occurrence of Ca in coal and char. The released Ca from coal pyrolysis and char gasification were captured and analyzed by activated carbon adsorption and X-ray photoelectron spectroscopy (XPS). Model compounds CaS and CaSO₄ were adopted to further reveal the released form of Ca under different atmospheres. The results indicate that Ca in coal is mainly released as CaCl₂ during the pyrolysis process, and the possible migration mechanism of Ca during pyrolysis was proposed. Ca in coal is mainly released in the form of CaCl₂, CaCO₃, and CaSO₄ during the gasification, and Ca is released as CaCl₂ under all conditions. In addition, Ca will be released as CaCO₃ under CO₂ atmosphere, as CaSO₄ under H₂O and H₂O/CO₂ atmospheres at 800 °C and 900 °C, released as CaSO₄ under all conditions at 1000 °C. This is closely related to the formation of CaO₂ intermediates during the gasification process.     

Underground in situ coal thermal treatment for synthetic fuels production

Underground coal thermal treatment (UCTT) is a promising concept that was recently proposed for extracting high-value hydrocarbon fuels from deep coal seams, which are economically unattractive for mining. UCTT is essentially an in situ pyrolysis process that converts underground coals into synthetic liquid and gaseous fuels, while leaving most of the carbon underground as a char matrix. The produced synthetic fuels have higher H/C ratios than coals. The remaining char matrix is an ideal reservoir for CO₂ sequestration because pyrolysis significantly increases the surface area of the char. The UCTT concept is relatively new, and there is little research in this area. However, underground oil shale retorting, which is also an in-situ hydrocarbon fuels conversion process, shares key features with UCTT and has gained momentum in demonstration and commercial development. As such, there is a large body of literature available in this area. A review of the studies on underground oil shale retorting that are closely related to UCTT will shed light on the UCTT process. This paper presents a review of the recent literature on underground oil shale retorting that are most relevant to UCTT process. The review provides a background to the reader by comparing the properties of coal with oil shale, with an emphasis on the feasibility of applying oil shale retorting techniques to UCTT process. The review further discusses the coal and oil shale conversion issues and uses the knowledge of the latter as guidance for the development of UCTT. Published data on pyrolysis of large coal blocks at conditions relevant to UCTT process is scarce. Therefore, literature on conventional coal pyrolysis is reviewed for optimization of the UCTT process. Despite the abundant studies on pulverized coal pyrolysis, there are still many open questions on whether they can be directly applied to UCTT. A comparison of the unique environment of UCTT with conditions of conventional pulverized coal pyrolysis clearly shows there are knowledge gaps. Future research needs are then proposed to close these gaps.