焦炉荒煤气重整提质制氢的热力学分析

为了验证吸附强化焦炉荒煤气重整制氢工艺的可行性,并为相关的实验研究提供理论依据,文章采用HSC Chemistry软件对焦炉荒煤气全组分蒸汽重整反应进行热力学分析,研究反应温度、反应压力、S/C,CaO/C对H_2产率、浓度等的影响。研究结果表明:焦炉荒煤气蒸汽重整反应能够有效地脱除焦油组分,随着S/C的增大,H_2产率会得到明显提升,且最佳H2产率所对应的反应温度会随之降低,当S/C为5∶1,反应温度为700℃时,H_2产率为1.62 mol/mol,但H_2浓度仅为75%左右;CO_2吸附剂的加入会强化蒸汽重整反应,H_2产率、浓度均会显著提升,最佳重整反应区的反应温度会随之降低,当反应温度为500~600℃,S/C为5∶1,CaO/C为3∶1时,H2产率、浓度能够分别达到1.83 mol/mol,98%以上。     

甘油水蒸气重整制氢及其CO_2原位吸附强化的研究

文章采用共沉淀方法合成了不同配比的Ni O/Al2O3催化剂,采用固定床反应器研究了不同配比的催化剂对甘油水蒸气重整制氢的影响。通过气体产品含量、甘油及水蒸气转化率等指标的分析得出:甘油和水蒸气转化率及氢气产率在450~650℃时随温度升高而增加,其中Ni O/Al2O3(Ni O=27.43%,Al2O3=72.57%)催化剂由于Ni含量较高,表现出高制氢催化活性,其氢气产率在650℃时达到最高的12.7%,甘油转化率也达到最高值96.9%。进行CO2原位吸附的甘油重整吸附强化制氢时,得到了更高纯度的氢。进行多次循环再生实验时,随着循环次数的增多,由于吸附剂再生不完全,氢气纯度会随着循环次数增多有所下降。     

运行参数对甲醇重整制氢的热力学特性影响研究

针对以氢气为燃料的动力系统运行条件需求,构建了甲醇重整反应热力学和化学平衡反应体系,以某功率型号燃料电池/燃气轮机(Solid Oxide Fuel Cell/Gas Turbine,SOFC/GT)混合动力系统为研究对象,分析其额定工况、变工况运行时,温度、水碳比和压力对各重整产物分布及产氢率的影响.结果 表明:额定...     

催化剂Ni/CeO2-ZrO2催化生物油水溶性组分重整制氢

利用固定床反应器对一系列自制催化剂Ni/CeO2-ZrO2和商业镍基催化剂Z417在生物油水溶性组分重整制氢反应中的催化性能进行考察,研究了活性金属Ni的负载量、反应温度、水油比对催化剂活性的影响.实验结果表明:Ni负载量为12wt％的催化剂Ni/CeO2-ZrO2在生物油水溶性组分重整制氢反应中表现出最佳催化活性,当反应温度为800C和水油比为4.9时,氢产率达到最大值67.8％,氢的选择性较高,为61.8％.     

生物质合成气强化重整提质制取氢气的热力学分析

针对生物质气化技术存在的制氢效率低、焦油含量高等问题,文章提出了一种生物质合成气强化重整提质工艺,并应用HSC Chemistry软件对该工艺进行了热力学分析;研究了反应温度、S/C以及CaO/C对H2放大率、提质产气各组分浓度等指标的影响.研究结果表明:经过强化重整提质,生物质合成气中焦油组分可全部裂解;吸附剂CaO...     

生物油水蒸气催化重整制氢研究进展

氢气作为一种环境友好的清洁能源,人们对它的关注度越来越高。生物油水蒸气催化重整制氢是未来制氢的一种可行性方案。本文综述了近年来生物油水蒸气重整制氢的研究进展。主要从重整制氢反应机理、热力学分析、催化重整催化剂、代表性的重整反应器方面进行讨论,指出催化重整中的主要问题是碳沉积导致催化剂失活。研制高活性、高稳定性、高选择性的催化剂是生物油催化重整制氢的关键。     

生物油制氢中CO2吸收剂改性研究

在耦合CO2吸收剂的生物油水蒸气重整反应中,通过在白云石中添加碱金属钾元素提高吸收剂的性能,进而提高H2产率与产气中的H2含量.研究表明:添加K2CO3的白云石经煅烧后制成的吸收剂有效促进了重整反应的进行,其中添加2％ K2CO3的白云石在煅烧后反应效果最好,H2产率提高20％以上.在添加2％ K2CO3基础上,进一步研究得到:在不同的水油比实验中,水蒸气重整反应最佳水油比从7.5降低到4.7;在不同的重整反应温度下,添加钾元素的煅烧白云石吸收剂在600℃下吸收效果最佳.     

生物油在流化床反应器中催化重整制氢研究

主要考察了温度、水碳比、质量空速对流化床生物油催化重整制氢的影响.研究表明,在实验范围内,较适宜的温度为750℃,水碳比为17～18,质量空速为0.4h-1.在此实验条件下,得到了最高的氢气产率56％、潜在氢气产率62.5％和碳元素选择性84.5％.另外,通过XRD及SEM研究表明,实验中催化剂失活的主要原因是镍金属晶粒在载体表面的烧结长大造成的.     

Ni/KZSM-5催化剂的生物乙醇水蒸气重整制氢催化性能

采用浸渍法制备了Ni/γ-Al_2O_3,Ni/HZSM-5和Ni/KZSM-5 3种负载型催化剂,利用XRD,XPS,BET,NH3-TPD,CO2-TPD和H2-TPR等手段对催化剂的晶相、比表面积、酸/碱性等物化特性进行了表征,并通过固定床反应器对比考察了不同载体的Ni基负载型催化剂对乙醇水蒸气重整制氢的催化性能。实验结果表明:由于HZSM-5的酸性较强,Ni/HZSM-5催化剂不能有效催化乙醇水蒸气重整制氢,主要产物为乙烯;由于KZSM-5具有一定的碱性并有较高的比表面积,Ni/KZSM-5催化剂对乙醇水蒸气重整制氢表现出了较高的催化活性,当反应温度为450℃时,乙醇转化率为100%,氢气选择性达到65.0%,且反应积碳率仅为3.0%;由于载体的碱性较弱,导致产物中含有部分乙烯,降低了氢气选择性,从而Ni/γ-Al_2O_3催化剂的活性低于Ni/KZSM-5催化剂。     

Ni、Fe负载CaO催化剂作用下生物油模化物水蒸气催化重整制氢研究

采用浸渍法制备Ni/CaO、Fe/CaO、Ni-Fe/CaO催化剂,用于生物油模化物乙酸水蒸气催化重整反应.对反应前后催化剂进行BET、H2-TPR、CO2-TPD、XRD等表征.通过比较3种催化剂重整反应性能得出Ni/CaO催化剂具有最佳性能.进一步研究在Ni/CaO催化剂参与下反应温度、水碳比(S/C)、液时空速(...     

Hydrogen production from bio-oil: A thermodynamic analysis of sorption-enhanced chemical looping steam reforming

The steam reforming of pyrolysis bio-oil is one proposed route to low carbon hydrogen production, which may be enhanced by combination with advanced steam reforming techniques. The advanced reforming of bio-oil is investigated via a thermodynamic analysis based on the minimisation of Gibbs Energy. Conventional steam reforming (C-SR) is assessed alongside sorption-enhanced steam reforming (SE-SR), chemical looping steam reforming (CLSR) and sorption-enhanced chemical looping steam reforming (SE-CLSR). The selected CO₂ sorbent is CaO(s) and oxygen transfer material (OTM) is Ni/NiO. PEFB bio-oil is modelled as a surrogate mixture and two common model compounds, acetic acid and furfural, are also considered. A process comparison highlights the advantages of sorption-enhancement and chemical looping, including improved purity and yield, and reductions in carbon deposition and process net energy balance.The operating regime of SE-CLSR is evaluated in order to assess the impact of S/C ratio, NiO/C ratio, CaO/C ratio and temperature. Autothermal operation can be achieved for S/C ratios between 1 and 3. In autothermal operation at 30 bar, S/C ratio of 2 gives a yield of 11.8 wt%, and hydrogen purity of 96.9 mol%. Alternatively, if autothermal operation is not a priority, the yield can be improved by reducing the quantity of OTM. The thermodynamic analysis highlights the role of advanced reforming techniques in enhancing the potential of bio-oil as a source of hydrogen.     

Optimization of bio-oil steam reforming process by thermodynamic analysis

A straightforward thermodynamic analysis of bio-oil steam reforming was carried out in the context of hydrogen and syngas production, employing Gibbs energy minimization method to determine equilibrium composition and global reaction heat. The bio-oil model compound was a mixture of acetic acid, phenol, and acetone. The effects of process variables, such as temperature and inlet S/C molar ratio, were investigated over a wide range of conditions. Thermodynamic analysis was performed using the software Aspen Plus v.11. It was identified the best operational conditions that could maximize syngas and further hydrogen production considering energy efficiency. The optimum production of hydrogen is 2.28 mol per carbon mole at S/C = 10 and 850 K, and syngas is 2.37 mol per carbon mole at S/C = 10 and 900 K. It has been demonstrated that the equilibrium calculations can be used to simulate these steam reforming reactions, given the catalyst's behavior.     

Autothermal sorption-enhanced steam reforming of bio-oil/biogas mixture and energy generation by fuel cells: Concept analysis and process simulation

A concept of sorption-enhanced steam reforming of bio-oil/biogas for electricity and heat generation by phosphoric acid fuel cells is investigated. The process is modeled using SIMSCI Pro II process simulator. Sorptive removal of the carbon dioxide from the reaction site results in low CO and _CO2${\mathrm{CO}}_2$ concentrations (<1%$<1\%$) in the reformate, as a result it can be used in the phosphoric acid fuel cell without any further fuel cleanup. High hydrogen concentration and calorific value of the reformate enable the operation of the fuel cell at a high-efficiency mode despite of the high carbon/hydrogen ratio of the bio-fuel. Addition of biogas to the reformer enables autothermal operation of the reformer, as well as significantly improves the efficiency of the process. The simulation shows that the overall efficiency of the proposed system is compatible with the efficiency of the system using “classical” steam reforming of the fuel. The process exhibits 6% lower electrical efficiency compared to the system utilizing natural gas, and 4.6% higher efficiency compared to a system using bio-oil as a fuel.     

Performance analysis and temperature gradient of solid oxide fuel cell stacks operated with bio-oil sorption-enhanced steam reforming

A high temperature gradient within a solid oxide fuel cell (SOFC) stack is considered a major challenge in SOFC operations. This study investigates the effects of the key parameters on SOFC system efficiency and temperature gradient within a SOFC stack. A 40-cell SOFC stack integrated with a bio-oil sorption-enhanced steam reformer is simulated using MATLAB and DETCHEM. When the air-to-fuel ratio and steam-to-fuel ratio increase, the stack average temperature and temperature gradient decrease. However, a decrease in the stack temperature steadily reduces the system efficiency owing to the tradeoff between the stack performance and thermal balance between heat recovered and consumed by the system. With an increase in the bio-oil flow rate, the system efficiency decreases because of the lower resident time for the electrochemical reaction. This is not, however, beneficial to the maximum temperature gradient. To minimize the temperature gradient of the SOFC stack, a decrease in the bio-oil flow rate is the most effective way. The maximum temperature gradient can be reduced to 14.6 K cm⁻¹ with the stack and system efficiency of 76.58 and 65.18%, respectively, when the SOFC system is operated at an air-to-fuel ratio of 8, steam-to-fuel ratio of 6, and bio-oil flow rate of 0.0041 mol s⁻¹.     

Towards autothermal hydrogen production by sorption-enhanced water gas shift and methanol reforming: A thermodynamic analysis

Hydrogen production by the water gas shift reaction (WGS) is equilibrium limited. In the current study, we demonstrate that the overall efficiency of the WGS can be improved by co-feeding methanol and removing CO₂ in situ. The thermodynamics of the water gas shift and methanol reforming/WGS (methanol-to-shift, MtoS) reactions for H₂ production alone and with simultaneous CO₂ adsorption (sorption-enhanced, SEWGS and SEMtoS) were studied using a non-stoichiometric approach based on the minimisation of the Gibbs free energy. A typical composition of the effluent from a steam methane reformer was used for the shift section. The effects of temperature (450–750 K), pressure (5–30 barg), steam and methanol addition, fraction of CO₂ adsorption (0–95%) and energy efficiency of the shift systems have been investigated. Adding methanol to the feed facilitates autothermal operation of the shift unit, with and without CO₂ removal, and enhances significantly the amount of H₂ produced. For a set methanol and CO input, the MtoS and SEMtoS systems show a maximum productivity of H₂ between 523 and 593 K due to the increasing limitation of the exothermic shift reaction while the endothermic methanol steam reforming is no longer limited above 593 K. The heat of adsorption of CO₂ was found to make only a small difference to the H₂ production or the autothermal conditions.     

Optimization of two bio-oil steam reforming processes for hydrogen production based on thermodynamic analysis

Thermodynamics of hydrogen production from conventional steam reforming (C-SR) and sorption-enhanced steam reforming (SE-SR) of bio-oil was performed under different conditions including reforming temperature, S/C ratio (the mole ratio of steam to carbon in the bio-oil), operating pressure and CaO/C ratio (the mole ratio of CaO to carbon in the bio-oil). Increasing temperature and S/C ratio, and decreasing the operating pressure were favorable to improve the hydrogen yield. Compared to C-SR, SE-SR had the significant advantage of higher hydrogen yield at lower desirable temperature, and showed a significant suppression for carbon formation. However excess CaO (CaO/C > 1) almost had no additional contribution to hydrogen production. Aimed to achieve the maximum utilization of bio-oil with as little energy consumption as possible, the influences of temperature and S/C ratio on the reforming performance (energy requirements and bio-oil consumption per unit volume of hydrogen produced, Q_D/H2 (kJ/Nm³) and Y_Bio-oil/H2 (kg/Nm³)) were comprehensively evaluated using matrix analysis while ensuring the highest hydrogen yield as possible. The optimal operating parameters were confirmed at 650 °C, S/C = 2 for C-SR; and 550 °C, S/C = 2 for SE-SR. Under their respective optimal conditions, the Y_Bio-oil/H2 of SE-SR is significant decreased, by 18.50% compared to that of C-SR, although the Q_D/H2 was slightly increased, just by 7.55%.     

Assessment of sorption-enhanced crude glycerol steam reforming process via CFD simulation

The sorption-enhanced glycerol reforming performance in a fluidized bed reactor is numerically studied with CaO and Li₄SiO₄ as CO₂ sorbents, where the multi-fluid model with the kinetic theory of granular flow is employed to carry out three-dimensional simulations. The ethanol is treated as the impurity in the crude glycerol and its effect on the reforming performance is evaluated. It is found that the hydrogen yield is higher using the crude glycerol with the ethanol owing to a greater reaction rate of the ethanol. An increase of the temperature is beneficial to the glycerol conversion and hydrogen production. Meanwhile, the enhancing effect on the reforming performance of CaO and Li₄SiO₄ is compared. The result demonstrates that the enhancing reforming effect of the Li₄SiO₄-based sorbent is similar to that of the CaO-based sorbent. At a high temperature, the CaO-based sorbent has a better performance.     

Comparative techno-economic analysis of biohydrogen production via bio-oil gasification and bio-oil reforming

This paper evaluates the economic feasibility of biohydrogen production via two bio-oil processing pathways: bio-oil gasification and bio-oil reforming. Both pathways employ fast pyrolysis to produce bio-oil from biomass stock. The two pathways are modeled using Aspen Plus^® for a 2000 t d⁻¹ facility. Equipment sizing and cost calculations are based on Aspen Economic Evaluation® software. Biohydrogen production capacity at the facility is 147 t d⁻¹ for the bio-oil gasification pathway and 160 t d⁻¹ for the bio-oil reforming pathway. The biomass-to-fuel energy efficiencies are 47% and 84% for the bio-oil gasification and bio-oil reforming pathways, respectively. Total capital investment (TCI) is 435 million dollars for the bio-oil gasification pathway and is 333 million dollars for the bio-oil reforming pathway. Internal rates of return (IRR) are 8.4% and 18.6% for facilities employing the bio-oil gasification and bio-oil reforming pathways, respectively. Sensitivity analysis demonstrates that biohydrogen price, biohydrogen yield, fixed capital investment (FCI), bio-oil yield, and biomass cost have the greatest impacts on facility IRR. Monte-Carlo analysis shows that bio-oil reforming is more economically attractive than bio-oil gasification for biohydrogen production.     

Catalytic steam reforming of bio-oil

Hydrogen and synthesis gas can be produced in an environmentally friendly and sustainable way through steam reforming (SR) of bio-oil and this review presents the state-of-the-art of SR of bio-oil and model compounds hereof. The possible reactions, which can occur in the SR process and the influence of operating conditions will be presented along with the catalysts and processes investigated in the literature.