木屑炭水蒸气催化气化制取合成气研究

以木屑炭为原料,K2CO3作为催化剂,以固定床气化炉为实验设备,进行水蒸气催化气化木屑炭的探究。考察木屑炭水蒸气气化的炭转化率、产氢率、气体组成体积分数和H2/CO比值随K2CO3催化剂质量分数(0~8%)、水蒸气流量(0.15~0.35 g/(min·g))、气化温度(800~950℃)变化的规律。实验结果表明:K2CO3催化剂可显著提升碳转化率及产氢率,K2CO3质量分数为8%时,碳转化率和产氢率分别达到86.3%和125.6 g/kg,同时合成气中CO体积分数显著增加,H2/CO比值降至2.43。增加水蒸气流量,合成气中H2含量显著增大,H2/CO比值随之增大。温度可有效促进炭气化过程,950℃时碳转化率和产氢率分别达到84.3%和127.1 g/kg,但合成气中CO体积分数增大,H2/CO比值降至2.48。实验得到H2/CO比值在2.43~5.16范围的合成气。气化反应温度在900℃、水蒸气0.2 g/(min·g)、K2CO3质量分数3%时,碳转化率可达80.4%,产氢率109.6 g/kg,合成气中(H2+CO)体积分数82.4%,同时H2/CO比值高达3.05。     

木屑水蒸气气化热重分析及合成气释放特性

试验研究了木屑在水蒸气气氛下的热失重行为及气化过程中合成气释放特性。首先采用TG-DTA对木屑样品进行了水蒸气气氛下的热重行为分析,结果表明,木屑气化过程可以分为挥发分释放和半焦气化两个阶段,分别可由二级反应动力学和三维扩散Ginstling-Broushtein方程描述,对应的表观活化能分别为87.014kJ/mol和103.35 kJ/mol。此外,在自制的固定床气化反应装置上,研究了生物质气化过程中挥发分释放和半焦气化阶段合成气释放特性。另外,半焦水蒸气气化阶段对气体中合成气含量和H2/CO起到决定性作用,通过合理调控半焦气化阶段反应条件,可以得到合适化学当量比的生物质合成气。     

松木屑水蒸气催化气化制氢及其大物料量气化动力学研究

利用松木屑在自制固定床气化系统上进行水蒸气催化气化实验研究.考察反应温度、水蒸气/生物质比(S/B)以及催化剂加入量对气体成分、产氢率和潜在产氢率的影响.结果表明:反应温度为850℃、S/B为3.27、催化剂量,木屑进料量比为2%时合成气品质较优,氢气浓度可达40.13%,产气率为0.718m3·kg-1.该文也进行大物料量松木屑催化气化等温热重实验研究,加入催化剂使木屑气化反应活化能降低,加快了反应进程.     

林产废弃物高温水蒸气气化制取清洁燃气

基于下吸式固定床气化炉,自建了生物质蒸汽气化实验平台,使用松木屑预处理后的成型颗粒进行富氢气化实验,研究分析了不同温度下的燃气组分、产氢率、燃气产率、燃气热值和冷煤气效率等指标.结果表明:高温水蒸气能有效促进水蒸气重整反应正向进行;随着温度的升高(700℃升高至900℃),H_2体积分数增大了50%,产氢率升高了2.5倍,燃气产率升高了近70%,冷煤气效率提高了37%;参与气化反应的高温水蒸气拥有较高的比焓,能够有效促进水蒸气重整反应向生成H_2的方向进行;气化温度的升高可以促进反应向正向进行,提高气体产物产量;以松木屑为例的林产废弃物高温水蒸气气化产气优良,在实验过程中稳定燃烧,理论上可应用于工业生产.     

CaO对松木锯末水蒸气气化过程的影响

采用CaO在生物质气化过程中通过吸收CO2促进产氢的方法,对生物质松木锯末进行水蒸气气化实验研究。分析了CaO、水蒸气、温度和停留时间对产气组分的影响。实验结果表明:添加CaO能显著提高产氢量。当Ca/B0.5时,产氢量随着Ca/B的增加而显著增加,当Ca/B0.5后,产氢量略微下降。添加CaO后促进了水煤气反应的进行。当温度高于800℃时,添加CaO后,生物质气化挥发分释放阶段与半焦气化阶段出现了重叠,半焦气化反应提前发生。随着温度和停留时间的延长,H2浓度逐渐升高,且在较长时间内维持在较高的浓度。     

污泥热解残渣水蒸气气化制取富氢燃气

采用固定床反应器,进行了污泥热解残渣水蒸气气化制取富氢燃气的研究。考察了反应温度、固相停留时间、水蒸气流量及催化剂对气化效果及气体产物组成的影响。结果表明:随着反应温度的升高,气体产率由0.096 7 m3/kg逐渐增加到0.460 0 m3/kg,燃气中H2含量由17.87%逐渐增加到52.44%;在最佳固相停留时间为15min时,气体产率达到0.540 m3/kg;最佳水蒸气流量为1.19 g/min,此时产气量达到最大值0.61 m3/kg,H2含量为64.7%;添加催化剂有利于气体中H2含量的提高。     

中药渣水蒸气气化制备合成气研究

以中药渣为原料进行水蒸气气化实验,研究气化温度、水蒸气与生物质质量之比(S/B)对产气流量、气体产率、产气组分、碳转化率、燃气热值以及气化效率的影响。研究结果表明:气化温度的升高能够促进气化反应的进行,提高产气品质和气化效率;一定量的气化剂水蒸气可提高气化效率,但是过量的水蒸气会影响气化效果;气化温度为800℃,S/B为1.0时,气化效果最佳,气化效率高达72.91%;中药渣具备良好的水蒸气气化特性。研究结果可为中药渣资源利用提供理论参考。     

造纸废渣水蒸气气化制取富氢燃气实验研究

目前造纸废渣的主要处理方式为焚烧,虽然该工艺简单有效,但会产生二噁英等有害物质,因此部分地区环保部门开始限制新建焚烧项目。针对造纸废渣处理难的问题,结合废物特性,探索使用气化工艺对其进行处理。在700～900℃利用水蒸气与造纸废渣共同反应制取富氢燃气,并进一步研究了CaO、MgO作为催化剂对气化反应的影响。结果显示：气化温度为900℃,产气中H₂的比例超过50%;两种催化剂均可催化大分子有机物分解为气体小分子,导致燃气热值及气化效率提高。     

生物质水蒸气气化制氢模拟研究

利用ASPEN PLUS软件建立了生物质水蒸气气化制氢模型,对各种影响因素进行了深入分析。结果表明:随着碳转化率的增加,H2浓度略有降低,H2产量大幅增加,在碳转化率为1时达到最大值142.54 g/kg;随着水蒸气/生物质质量比的增加,H2浓度和产量大幅增加,而后趋于稳定,水蒸气/生物质质量比取2比较适宜。适当的升温和低压对制备H2有利,在加压条件下,H2浓度与产量达到最大值的温度升高。     

木屑高温空气气化实验研究

提出了一种生物质高温气化的新方法。选取木屑为气化物料，在700℃、800℃和1000℃分别进行高温气化实验。实验表明：高温气化有利于提高合成燃气热值，强化气化反应；合成燃气中CO2和CxHy的含量度热值随温度的变化规律与理论结果基本吻合，热值达到6．19MJ／m^3。证实了生物质高温气化技术的可行性。     

煤焦水蒸气催化气化动力学分析

利用固定床反应器研究了K、Ca、Ni和Fe金属对600～900℃内煤焦水蒸气气化的催化效果,分析了适用于原煤焦、脱灰煤焦和添加K、Ca、Ni和Fe金属后的煤焦水蒸气气化动力学模型。     

Kinetics of woodchips char gasification with steam and carbon dioxide

Kinetics of woodchips char gasification has been examined. Steam and CO₂ were used as the gasifying agents. Differences and similarities between kinetics of steam gasification and CO₂ gasification have been discussed. Comparison was conducted in terms of gasification duration, evolution of reaction rate with time and/or conversion, and effect of partial pressure on reaction rate. Reactor temperature was maintained at 900 °C. Partial pressure of gasifying agents varied from 1.5 bars to 0.6 bars in intervals of 0.3 bars. Steam and CO₂ flow rates were chosen so that both gasifying agents had equal amount of oxygen content. CO₂ gasification lasted for about 60 min while steam gasification lasted for about 22 min. The average reaction rate for steam gasification was almost twice that of CO₂. Both reaction rate curves showed a peak value at certain degree of conversion. For steam gasification, the reaction rate peak was found to be at a degree of conversion of about 0.3. However, for CO₂ gasification the reaction rate peak was found to be at a conversion degree of about 0.1. Reaction rates have been fitted using the random pore model (RPM). Average structural parameter, ψ for steam gasification and CO₂ gasification was determined to be 9 and 2.1, respectively. Average rate constant at 900 °C was 0.065 min⁻¹ for steam gasification and 0.031 min⁻¹ for CO₂ gasification. Change in partial pressure of gasifying agents did not affect the reaction rate for both steam and CO₂ gasification.     

Inhibition of steam gasification of biomass char by hydrogen and tar

The influence of hydrogen and tar on the reaction rate of woody biomass char in steam gasification was investigated by varying the concentrations in a rapid-heating thermobalance reactor. It was observed that the steam gasification of biomass char can be separated into two periods. Compared with the first period, in the second period (in which the relative mass of remaining char is smaller than 0.4) the gasification rate is increased. These effects are probably due to inherent potassium catalyst. Higher hydrogen partial pressure greatly inhibits the gasification of biomass char in the first and second periods. By calculating the first-order rate constants of char gasification in the first and second periods, we found that the hydrogen inhibition on biomass char gasification is caused by the reverse oxygen exchange reaction in the first period. In the second period, dissociative hydrogen adsorption on the char is the major inhibition reaction. The influence of levoglucosan, a major tar component derived from cellulose, was also examined. We found that not only hydrogen but also vapor-phase levoglucosan and its pyrolysates inhibited the steam gasification of woody biomass char. By mixing levoglucosan with woody biomass sample, the pyrolysis of char proceeds slightly more rapidly than with woody biomass alone, and gas evolution rates of H₂ and CO₂ are larger in steam gasification.     

High temperature steam gasification of wastewater sludge

High temperature steam gasification is one of the most promising, viable, effective and efficient technology for clean conversion of wastes to energy with minimal or negligible environmental impact. Gasification can add value by transforming the waste to low or medium heating value fuel which can be used as a source of clean energy or co-fired with other fuels in current power systems. Wastewater sludge is a good source of sustainable fuel after fuel reforming with steam gasification. The use of steam is shown to provide value added characteristics to the sewage sludge with increased hydrogen content as well total energy. Results obtained on the syngas properties from sewage sludge are presented here at various steam to carbon ratios at a reactor temperature of 1173 K. Effect of steam to carbon ratio on syngas properties are evaluated with specific focus on the amounts of syngas yield, syngas composition, hydrogen yield, energy yield, and apparent thermal efficiency. The apparent thermal efficiency is similar to cold gas efficiency used in industry and was determined from the ratio of energy in syngas to energy in the solid sewage sludge feedstock. A laboratory scale semi-batch type gasifier was used to determine the evolutionary behavior of the syngas properties using calibrated experiments and diagnostic facilities. Results showed an optimum steam to carbon ratio of 5.62 for the range of conditions examined here for syngas yield, hydrogen yield, energy yield and energy ratio of syngas to sewage sludge fuel. The results show that steam gasification provided 25% increase in energy yield as compared to pyrolysis at the same temperature.     

Modelling and experimental investigations on gasification of coarse sized coal char particle with steam

The steam gasification characteristics of coal char produced two sub-bituminous coals of different origin have been investigated through modelling and experiments. The gasification experiments are carried out in an Isothermal mass loss apparatus over the temperature range of 800–900 °C using a gas mixture of 65% steam and 35% N₂. A fully transient single particle gasification model, based on the random pore model, is developed incorporating reaction kinetics, heat and mass transport inside the porous char particle and the gas film. Stefan-Maxwell equation and Knudson diffusion are incorporated in the multi-component diffusion of species and pore diffusion. The model is validated with the experimental data of the present authors as well as that reported in the literature. The particle centre temperature is found to increase, then decrease and increase again to reach the reactor temperature finally, and the trend is more prominent for the larger particles. The pore opening phenomenon is more evident in SBC2 char, leading to a final char porosity of 0.65 vis-à-vis 0.52 in SBC1 and making it more reactive. Temporal evolution of contours of carbon conversion and concentration of other gaseous species like steam, H₂O, H₂, CO and CO₂ in the particle are computed to investigate the gasification process. A higher temperature is found to favour both the rate peak and the total production of H₂ for both the chars. The total H₂ production from SBC2 char is found to be 0.0189 mol and 0.0236 mol at 800 and 850 °C, while the same for SBC1 char is0.0232 mol and 0.0290 mol respectively. The reaction follows the shrinking core model at the outset, shifting to the shrinking reactive core model subsequently.     

Effect of CO2 and steam gasification reactions on the oxy-combustion of pulverized coal char

For oxy-combustion with flue gas recirculation, elevated levels of CO₂ and steam affect the heat capacity of the gas, radiant transport, and other gas transport properties. A topic of widespread speculation has concerned the effect of gasification reactions of coal char on the char burning rate. To asses the impact of these reactions on the oxy-fuel combustion of pulverized coal char, we computed the char consumption characteristics for a range of CO₂ and H₂O reaction rate coefficients for a 100 μm coal char particle reacting in environments of varying O₂, H₂O, and CO₂ concentrations using the kinetics code SKIPPY (Surface Kinetics in Porous Particles). Results indicate that gasification reactions reduce the char particle temperature significantly (because of the reaction endothermicity) and thereby reduce the rate of char oxidation and the radiant emission from burning char particles. However, the overall effect of the combined steam and CO₂ gasification reactions is to increase the carbon consumption rate by approximately 10% in typical oxy-fuel combustion environments. The gasification reactions have a greater influence on char combustion in oxygen-enriched environments, due to the higher char combustion temperature under these conditions. In addition, the gasification reactions have increasing influence as the gas temperature increases (for a given O₂ concentration) and as the particle size increases. Gasification reactions account for roughly 20% of the carbon consumption in low oxygen conditions, and for about 30% under oxygen-enriched conditions. An increase in the carbon consumption rate and a decrease in particle temperature are also evident under conventional air-blown combustion conditions when the gasification reactions are included in the model.     

Reaction characteristics through catalytic steam gasification with ultra clean coal char and coal

The direct production of methane through steam–coal gasification processing using a catalyst is one of the most attractive routes for the effective utilization of coal. In this study, a thermobalance was used to verify basic characteristics of carbon and steam reactivity using the ultra clean coal (UCC) char of Roto South with potassium carbonate at different conditions. The reactivity between carbon and steam was the highest at 800 °C, with catalyst (K₂CO₃) addition, 10 wt%, and the steam flow rate of 500 ml/min. At the optimized condition of thermobalance, syngas components of Roto South coal, which were produced in fixed-bed reactor, were observed through a Non-dispersive infrared sensor (NDIR) for 60 min. Methane concentration among the produced gases highly accounted for 36 vol% at 6 min. The volatile matter (VM) of coal was related to high methane production. From the X-ray diffraction (XRD) results, the crystallinity structure of K₂CO₃ was detected, as other potassium salts form, after 20 min.     

Catalytic effect of sodium components on the microstructure and steam gasification of demineralized Shengli lignite char

The catalytic effect of sodium on the demineralized Shengli (SL⁺) lignite char microstructure and the performance of steam gasification were studied. Various sodium compounds including NaNO₃, CH₃COONa, Na₂CO₃ and NaOH were loaded on the demineralized coal samples, respectively, and the steam gasification was tested on the fix-bed reactor. The char samples were characterized by X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS) and FT-IR spectroscopy. Experimental results showed that sodium hydroxide loaded samples exhibited the highest gasification reactivity among the coal samples prepared. With the increase of the alkalinity of sodium compounds, the carbon crystallite structure tended to be disordered. In the process of pyrolysis, the introduction of sodium species promoted the ring-opening and polycondensation process of the chemicals in the coal samples. The possible reaction mechanism might be inferred that the sodium ions may replace the hydrogen ions in the oxygen-containing functional groups to form sodium phenolate intermediate, which may be critical for the catalytic effect of sodium species during gasification. It was speculated that the ring-opening of the condensation aromatic nucleus was the rate-limiting step in the whole process of gasification.     

Hydrogen-rich gas from catalytic steam gasification of eucalyptus using nickel-loaded Thai brown coal char catalyst

Hydrogen gas production from eucalyptus by catalytic steam gasification was carried out in an atmospheric pressure of two-stage fixed bed. The gasifier was operated with the temperature range of 500–650 °C and steam partial pressure of 16, 30 and 45 kPa; nickel-loaded Thai brown coal char was used as a catalyst. The yields and compositions of the gasification products depend on the operating conditions, especially, the reaction temperature and the steam. The yield of H₂ increased at elevated temperatures, from 26.94 to 46.68%, while that of CO dramatically decreased, from 70.21 to 37.71 mol%. The highest H₂ yield, 46.68%, was obtained at the final gasifying temperature of 650 °C. Eucalyptus catalytic steam gasification indicated that the maximum H₂/CO ratio reached 1.24 at the gasification temperature of 650 °C and the steam partial pressure of 30 kPa. It can be concluded that eucalyptus is appropriate for synthesis gas production from eucalyptus volatiles by catalytic steam gasification while using nickel-loaded brown coal char as a catalyst.     

Hydrogen-rich gas from catalytic steam gasification of biomass in a fixed bed reactor: Influence of temperature and steam on gasification performance

The catalytic steam gasification of biomass was carried out in a lab-scale fixed bed reactor in order to evaluate the effects of temperatures and the ratio of steam to biomass (S/B) on the gasification performance. The bed temperature was varied from 600 to 900 and the S/B from 0 to 2.80. The results show that higher temperature contributes to more hydrogen production.