Combined Decarbonization of Electrical Energy Generation and Production of Synthetic Fuels by Renewable Energies and Fossil Fuels

Power generation from renewable energy sources and fossil fuels are integrated into one system. A combination of technologies in the form of a carbon capture utilization (CCU)-combined power station is proposed. The technology is based on energy generation from fossil fuels by a coal power plant with CO₂ recovery from exhaust gases, and pyrolysis of natural gas to hydrogen and carbon, completed by reverse water-gas shift for the conversion of CO₂ to CO, which will react with hydrogen in a Fischer-Tropsch synthesis for synthetic diesel. The carbon from the pyrolysis can replace other fossil carbon or can be sequestered. This technology offers significant CO₂ savings compared to the current state of technology and makes an environmentally friendly use of fossil fuels for electricity and fuel sectors possible.     

Response Surface Optimization of Hydrogen-Rich Syngas Production by Greenhouse Gases Reforming

The effect of process interaction and response surface optimization of hydrogen-rich syngas production by catalytic carbon dioxide (CO₂) reforming of methane (CH₄) was evaluated. The Box-Behnken design was applied to investigate the influence of CH₄ partial pressure, CO₂ partial pressure, and temperature on the hydrogen yield. The analysis of variance indicated that temperature and CH₄ partial pressure had the most significant impact on the hydrogen yield. Under optimum conditions a maximum hydrogen yield of 71.38 % was achieved. Model validation with the ideal conditions confirmed close agreement of the predicted hydrogen yields with experimental values.     

卤素负载锌-腺嘌呤骨架材料的构建及无助剂催化CO2环加成反应

富氮型金属有机骨架材料（MOFs）具有良好的CO₂捕集性能,但其CO₂催化性能常需添加带氢键或亲核基团的助催化剂。以硝酸锌-腺嘌呤-异烟酸［Zn（NO₃）₂-Ad-Int-DMF］构建稳健的骨架材料,发现其催化合成碳酸丙烯酯（PC）收率不足2%;尝试选型锌盐前体引入亲核卤素,在DMF溶剂中部分卤代锌盐不能络合结晶成MOFs,而形成的ZnI₂-Ad-Int-DMF收率提升至19.5%;溶剂由DMF调变为H₂O-DMF混合溶剂,H₂O的引入避免了卤素对金属和配体间络合的影响,使得以ZnCl₂、ZnBr₂和ZnI₂为前体均能晶化成MOFs,其热分解起始温度（Tonset,434℃）明显高于ZnI₂-Ad-Int-DMF（280℃）,而比表面积（<14 m²/g）明显小于后者（571 m²/g）,造成活性低于后者。通过CO₂吸附脉冲和UV-Vis漫反射推测I^-由于与Zn碱位的相互作用而均匀吸附于骨架上。进而,在无助剂、无溶剂工况下对CO₂环加成反应进行活性评价。温度升高显著提升PC产率,140℃下ZnI₂-Ad-Int-DMF催化产率可达98.5%,但由于吸附在骨架上的卤素在高温、溶剂环境下会脱落,造成重复性实验中活性下降,而该类MOFs在反应前后骨架保持稳定,未造成坍塌或明显孔堵塞现象。后续如能强化卤素的吸附或温和化反应条件,则具有良好的应用潜力。     

超临界CO2脱附作用调控负载纳米颗粒结晶动力学研究

依据经典成核理论和超临界领域中的结晶动力学相关模型,分析影响成核速率的主要因素及其规律。研究共溶剂辅助超临界CO₂溶解无机盐,在SBA-15介孔材料表面沉积实验的结果,发现伴随初始阶段的泄压速率逐步提升（0.05~18 MPa/min,20~14 MPa）,载体所负载的纳米颗粒的粒径逐渐减小至1.5 nm左右,与典型的晶核尺寸1 nm相接近,而担载量却出现逐渐增加的趋势。晶体的临界成核半径取为0.5 nm,通过Türk模型和Debenedetti模型计算超临界流体快速膨胀（RESS）工艺其喷嘴内的成核速率,与超临界反溶剂（SAS）群体平衡模型（PBM）的边界条件即SAS过程的初始成核速率相比较,三者的成核速率相接近,且利用快速泄压方法的沉积实验结果与按Cu担载量所估算的成核速率相接近。分析在沉积反应后的泄压阶段,超临界条件下的CO₂的脱附作用,可能成为吸附于载体表面的前驱物离子结晶的诱导因素。并且CO₂瞬时脱附量能够调控负载型纳米颗粒的成核速率,同时控制复合材料的金属担载量。为研究微观尺度下SAS过程的实现提供了实验与理论基础。     

Photocatalytic syngas synthesis from CO2 and H2O using ultrafine CeO2-decorated layered double hydroxide nanosheets under visible-light up to 600 nm

The rational design of photocatalyst that can effectively reduce CO₂ under visible light(l>400 nm),and simultaneously precise control of the products syngas(CO/H2)ratio is highly desirable for the Fischer-Tropsch reaction.In this work,we synthesized a series of CeO₂-decorated layered double hydroxides(LDHs,Ce-x)samples for photocatalytic CO₂ reduction.It was found that the selectivity and productivity of CO and H₂ from photoreduction of CO₂ in conjunction with Ru-complex as photosensitizer performed an obvious“volcano-like”trend,with the highest point at Ce-0.15 and the CO/H₂ ratio can be widely tunable from 1/7.7 to 1/1.3.Furthermore,compared with LDH,Ce-0.15 also drove photocatalytic CO₂ to syngas under 600 nm irradiation.It implied that an optimum amount of CeO₂ modifying LDH promoted the photoreduction of CO₂ to syngas.This report gives the way to fully utilize the rare earth elements and provides a promising route to enhance the photo-response ability and charge injection efficiency of LDH-based photocatalysts in the synthesis of syngas with a tunable ratio under visible light irradiation.     

Electrolytic cell engineering and device optimization for electrosynthesis of e-biofuels via co-valorisation of bio-feedstocks and captured CO2

Utilizing CO₂ in an electro-chemical process and synthesizing value-added chemicals are amongst the few viable and scalable pathways in carbon capture and utilization technologies.CO₂ electro-reduction is also counted as one of the main options entailing less fossil fuel consumption and as a future electrical energy storage strategy.The current study aims at developing a new electrochemical platform to produce low-carbon e-biofuel through multifunctional electrosynthesis and integrated co-valorisation of biomass feedstocks with captured CO₂.In this approach,CO₂ is reduced at the cathode to produce drop-in fuels(e.g.,methanol)while value-added chemicals(e.g.,selective oxidation of alcohols,aldehydes,carboxylic acids and amines/amides)are produced at the anode.In this work,a numerical model of a continuous-flow design considering various anodic and cathodic reactions was built to determine the most techno-economically feasible configurations from the aspects of energy efficiency,environment impact and economical values.The reactor design was then optimized via parametric analysis.     

超临界CO2萃取生姜特性组分--姜油的研究

本文以超临界CO2 萃取的方法 ,研究了生姜中特性组分姜油萃取过程中工艺条件的影响 ,得到了优化的工艺 :萃取温度 5 0℃ ;萃取压力 14 4MPa ;二级高压萃取釜萃取浸泡时间 2h ;流体取样量约 5mL ;取样过程气体流速 0 3～ 0 9L/min。对所提取的姜油采用紫外光谱和气相色谱连用的分析方法 ,确定了各组分的相对含量。     

正丙醇-水-钾盐和异丙醇-水-钾盐体系液液相平衡数据的测定和理论计算

实验测定了正丙醇 水 氟化钾、异丙醇 水 氟化钾、正丙醇 水 碳酸钾、异丙醇 水 碳酸钾体系在25℃时的液液相平衡数据,当水相中氟化钾或碳酸钾浓度较高时产生的正丙醇或异丙醇富集相中含有可以忽略的盐,水富集相中含有可以忽略的正丙醇或异丙醇,因此用氟化钾或碳酸钾可以成功地分离正丙醇 水或异丙醇 水体系。采用Pitzer方程计算富水相中水的活度,用NRTL方程计算富正丙醇或异丙醇相中水的活度,将二者结合对液液相平衡数据进行理论计算。结果表明计算值与实验值符合良好,为工业上用钾盐分离正丙醇 水或异丙醇 水体系提供了数据和模型。     

氧化钙对镍基催化剂萘转化性能影响的研究

用浸渍法和共浸渍法分别制备了Ni Al2O3和Ni-Ca Al2O3催化剂,在常压连续流动固定床反应器上,研究了氧化钙对Ni Al2O3催化剂萘的转化率、CO、H2和CO2的收率以及它们的选择性的影响,比较了在Ni Al2O3和Ni-Ca Al2O3两种催化剂上萘水蒸气转化所产生的H2 CO比例大小、积炭量和有机副产物的区别。试验发现,氧化钙助剂的加入增强了Ni Al2O3催化剂的活性和抗积炭性能。     

Copper oxide catalysts supported on ceria for low-temperature CO oxidation

Copper oxide catalysts supported on ceria were prepared by wet impregnation method using finely CeO₂ nanocrystals, which was derived from alcohothermal synthesis, and copper nitrate dissolved in the distilled water. The catalytic activity of the prepared CeO₂ and CuO/CeO₂ catalysts for low-temperature CO oxidation was investigated by means of a microreactor-GC system. The samples were characterized using BET, XRD, SEM, HRTEM and TPR.