Techno-economic assessment of a chemical looping splitting system for H2 and CO Co-generation

The natural gas(NG)reforming is currently one of the low-cost methods for hydrogen production.However,the mixture of H2 and CO_(2) in the produced gas inevitably includes CO_(2) and necessitates the costly CO_(2) separation.In this work,a novel double chemical looping involving both combustion(CLC)and sorption-enhanced reforming(SE-CLR)was proposed towards the co-production of H2 and CO(CLC-SECLRHC)in two separated streams.CLC provides reactant CO_(2) and energy to feed SECLRHC,which generates hydrogen in a higher purity,as well as the calcium cycle to generate CO in a higher purity.Techno-economic assessment of the proposed system was conducted to evaluate its efficiency and economic competitiveness.Studies revealed that the optimal molar ratios of oxygen carrier(OC)/NG and steam/NG for reforming were recommended to be 1.7 and 1.0,respectively.The heat integration within CLC and SECLRHC units can be achieved by circulating hot OCs.The desired temperatures of fuel reactor(FR)and reforming reactor(RR)should be 850
C and 600
C,respectively.The heat coupling between CLC and SECLRHC units can be realized via a jacket-type reactor,and the NG split ratio for reforming and combustion was 0.53:0.47.Under the optimal conditions,the H2 purity,the H2 yield and the CH4 conversion efficiency were 98.76%,2.31 mol mol-1 and 97.96%,respectively.The carbon and hydrogen utilization efficiency respectively were 58.60% and 72.45%in terms of the total hydrogen in both steam and NG.The exergy efficiency of the overall process reached 70.28%.In terms of the conventional plant capacity(75 × 103 t y^(-1))and current raw materials price(2500$t^(-1)),the payback period can be 6.2 years and the IRR would be 11.5,demonstrating an economically feasible and risk resistant capability.

Efficient hydrogen production through the chemical looping redox cycle of YSZ supported iron oxides

The chemical looping process,where an oxygen carrier is reduced and oxidized in a cyclic manner,offers a promising option for hydrogen production through splitting water because of the much higher water splitting efficiency than solar electrocatalytic and photocatalytic process.A typical oxygen carrier has to comprise a significant amount of inert support,to maintain stability in multiple redox cycles,thereby resulting in a trade-off between the reaction reactivity and stability.Herein,we proposed the use of ion-conductive yttria-stabilized zirconia(YSZ)support Fe_(2)O_(3)to prepare oxygen carriers materials.The obtained Fe_(2)O_(3)/YSZ composites showed high reactivity and stability.Particularly,Fe_(2)O_(3)/YSZ-20(oxygen storage capacity,24.13%)exhibited high hydrogen yield of~10.30 mmol g^(-1) and hydrogen production rate of~0.66 mmol g^(-1) min^(-1) which was twice as high as that of Fe_(2)O_(3)/Al_(2)O_(3).Further,the transient pulse test indicated that active oxygen diffusion was the ratelimiting step during the redox process.The electrochemical impedance spectroscopy(EIS)measurement revealed that the YSZ support addition facilitated oxygen diffusion of materials,which contributed to the improved hydrogen production performance.The support effect obtained in this work provides a potentially efficient route for the modification of oxygen carrier materials.

Hydrogen production via chemical looping reforming of coke oven gas

Coke oven gas(COG)is one of the most important by-products in steel industry,and the conversion of COG to value-added products has attracted much attention from both economic and environmental views.In this work,we use the chemical looping reforming technology to produce pure H_(2) from COG.A series of La1-xSrxFeO_(3)(x?0,0.2,0.3,0.4,0.5,0.6)perovskite oxides were prepared as oxygen carriers for this purpose.The reduction behaviors of La1-xSrxFeO_(3) perovskite by different reducing gases(H_(2),CO,CH4 and the mixed gases)are investigated to discuss the competition effect of different components in COG for reacting with the oxygen carriers.The results show that reduction temperatures of H_(2) and CO are much lower than that of CH4,and high temperatures(>800℃)are requested for selective oxidation of methane to syngas.The co-existence of CO and H_(2) shows weak effect on the equilibrium of methane conversion at high temperatures,but the oxidation of methane to syngas can inhibit the consumption of CO and H_(2).The doping of suitable amounts of Sr in LaFeO_(3) perovskite(e.g.,La0.5Sr0.5FeO_(3))significantly promotes the activity for selective oxidation of methane to syngas and inhibits the formation of carbon deposition,obtaining both high methane conversion in the COG oxidation step and high hydrogen yield in the water splitting step.The La0.5Sr0.5FeO_(3) shows the highest methane conversion(67.82%),hydrogen yield(3.34 mmol g^(-1))and hydrogen purity(99.85%).The hydrogen yield in water splitting step is treble as high as the hydrogen consumption in reduction step.These results reveal that chemical looping reforming of COG to produce pure H_(2) is feasible,and an O_(2)-assistant chemical looping reforming process can further improves the redox stability of oxygen carrier.

Energy and economic analysis of a hydrogen and ammonia co-generation system based on double chemical looping

In this work,a model of hydrogen production by double chemical looping is introduced.The efficiency benefit obtained was investigated.The chemical looping hydrogen generation unit is connected in series to the downstream of a chemical looping gasification unit as an additional system for 100 MWh coal gasification,with the function of supplementary combustion to produce hydrogen.Using Aspen Plus software for process simulation,the production of H_(2) and N_(2) in the series system is higher than that in the independent Chemical looping gasification and Chemical looping hydrogen generation systems,and the production of hydrogen is approximately 25.63%and 12.90%higher,respectively;The study found that when the gasification temperature is 900C,steam-carbon ratio is 0.84 and oxygen-carbon ratio is 1.5,the hydrogen production rate of the system was the maximum.At the same time,through heat exchange between logistics,high-pressure steam at 8.010×10^(4) kg·h^(-1) and medium-pressure steam at 1.101×10^(4) kg·h^(-1) are generated,and utility consumption is reduced by 61.58%,with utility costs decreasing by 48.69%.An economic estimation study found that the production cost of ammonia is 108.66 USD(t NH_(3))^(-1).Finally,cost of equipment is the main factors influencing ammonia production cost were proposed by sensitivity analysis.

Earth abundant spinel for hydrogen production in a chemical looping scheme at 550℃

Operating chemical looping process at mid-temperatures(550–750℃)presents exciting potential for the stable production of hydrogen.However,the reactivity of oxygen carriers is compromised by the detrimental effect of the relatively low temperatures on the redox kinetics.Although the reactivity at mid-temperature can be improved by the addition of noble metals,the high cost of these noble metal containing materials significantly hindered their scalable applications.In the current work,we propose to incorporate earth-abundant metals into the ironbased spinel for hydrogen production in a chemical looping scheme at mid-temperatures.Mn0.2Co0.4Fe2.4O4 shows a high hydrogen production performance at the average rate of~0.62 mmol g^(-1) min^(-1) and a hydrogen yield of~9.29 mmol g^(-1) with satisfactory stability over 20 cycles at 550℃.The mechanism studies manifest that the enhanced hydrogen production performance is a result of the improved oxygen-ion conductivity to enhance reduction reaction and high reactivity of reduced samples with steam.The performance of the oxygen carriers in this work is comparable to those noble-metal containing materials,enabling their potential for industrial applications.

Sorption-enhanced chemical looping oxidative steam reforming of methanol for on-board hydrogen supply

Hydrogen is an indispensable energy carrier for the sustainable development of human society.Nevertheless,its storage,transportation,and in situ generation still face significant challenges.Methanol can be used as an intermediate carrier for hydrogen supplies,providing hydrogen energy through instant methanol conversion.In this study,a sorption-enhanced,chemical-looping,oxidative steam methanol-reforming(SECLOSRM)process is proposed using CuO–MgO for the on-board hydrogen supply,which could be a promising method for safe and efficient hydrogen production.Aspen Plus software was used for feasibility verification and parameter optimization of the SECL-OSRM process.The effects of CuO/CH_(3)OH,MgO/CH_(3)OH,and H_(2)O/CH_(3)OH mole ratios and of temperature on H_(2)production rate,H utilization efficiency,CH_(3)OH conversion,CO concentration,and system heat balance are discussed thoroughly.The results indicate that the system can be operated in autothermal conditions with high-purity hydrogen(99.50 vol%)and ultra-low-concentration CO(<50 ppm)generation,which confirms the possibility of integrating low-temperature proton-exchange membrane fuel cells(LT-PEFMCs)with the SECL-OSRM process.The simulation results indicate that the CO can be modulated in a lower concentration by reducing the temperature and by improving the H_(2)O/CH_(3)OH and MgO/CH_(3)OH mole ratios.

A thermodynamic view on the in-situ carbon dioxide reduction by biomass-derived hydrogen during calcium carbonate decomposition

In the carbonate industry,deep decarbonization strategies are necessary to effectively remediate CO_(2).These strategies mainly include both sustainable energy supplies and the conversion of CO_(2)in downstream processes.This study developed a coupled process of biomass chemical looping H2 production and reductive calcination of CaCO_(3).Firstly,a mass and energy balance of the coupled process was established in Aspen Plus.Following this,process optimization and energy integration were implemented to provide optimized operation conditions.Lastly,a life cycle assessment was carried out to assess the carbon footprint of the coupled process.Results reveal that the decomposition temperature of CaCO_(3)in an H_(2)atmosphere can be reduced to 780℃(generally around 900℃),and the conversion of CO_(2)from CaCO_(3)decomposition reached 81.33%with an H2:CO ratio of 2.49 in gaseous products.By optimizing systemic energy through heat integration,an energy efficiency of 86.30%was achieved.Additionally,the carbon footprint analysis revealed that the process with energy integration had a low global warming potential(GWP)of-2.624 kg·kg^(-1)(CO_(2)/CaO).Conclusively,this work performed a systematic analysis of introducing biomass-derived H_(2)into CaCO_(3)calcination and demonstrated the positive role of reductive calcination using green H_(2)in mitigating CO_(2)emissions within the carbonate industry.

Layered Mg-Al spinel supported Ce-Fe-Zr-O oxygen carriers for chemical looping reforming

A series of layered Mg-Al spinel supported Ce-Fe-Zr-O oxygen carriers were prepared for co-production of syngas and pure hydrogen via chemical looping steam reforming(CLSR).The presence of magnesium-aluminum layered double oxides(Mg Al-LDO)significantly increases the specific surface area of the mixed oxides,reduces the particle size of CeO2-based solid solution and promotes the dispersion of free Fe2O3.When reacting with methane,Mg Al-LDO supported oxygen carrier shows much lower temperature for methane oxidation than the pure CeFe-Zr-O sample,indicating enhanced low-temperature reactivity.Among different Ce-Fe-Zr-O(x)/Mg Al-LDO samples,the Ce-Fe-Zr-O(40 wt%)/Mg Al-LDO sample shows the best performance for the selective oxidation of methane to syngas and the H2 production by water splitting.After a long period of high temperature redox experiment,the Ce-Fe-Zr-O(40 wt%)/Mg Al-LDO oxygen carrier still shows high activity for syngas generation.The comparison on the morphology of the fresh and cycled oxygen carriers indicates that the Mg-Al spinel support still forms a stable skeleton structure with high dispersion of active components on the surface after the long-term cycling,which contributes to excellent redox stability of the Ce-Fe-Zr-O(40 wt%)/Mg Al-LDO oxygen carrier.

计及CLHG-SOFC碳捕集的多能源系统低碳优化调度

为了响应碳达峰、碳中和的发展目标,实现对能源的高效利用,减少CO_(2)的排放,多能源系统引入基于化学链制氢-固体氧化物燃料电池(CLHG-SOFC)的碳捕集技术,以实现在供电供热的同时完成对CO_(2)的捕集。首先,对CLHG-SOFC碳捕集模块的运行机理与能量流动关系进行分析,推导出其净输出功率模型和电碳特性关系。其次,建立计及基于CLHG-SOFC碳交易与碳封存成本的多能源系统低碳优化调度模型。最后,通过算例分析验证了所提模型能够在不同电碳特性运行下实现系统运行的经济性和低碳性。

Process reconfiguration and intensification:An emerging opportunity enabling efficient carbon capture and low-cost blue hydrogen production

Low-carbon hydrogen can play a significant role in decarbonizing the world. Hydrogen is currently mainly produced from fossil sources,requiring additional CO_(2)capture to decarbonize, which energy intense and costly. In a recent Green Energy & Environment paper, Cheng and Di et al. proposed a novel integration process referred to as SECLR_(HC) to generate high-purity H_(2) by in-situ separation of H_(2)and CO without using any additional separation unit. Theoretically, the proposed process can essentially achieve the separation of C and H in gaseous fuel via a reconfigured reaction process, and thus attaining high-purity hydrogen of ~99%, as well as good carbon and hydrogen utilization rates and economic feasibility. It displays an optimistic prospect that industrial decarbonization is not necessarily expensive, as long as a suitable CCS measure can be integrated into the industrial manufacturing process.

助剂对ZnFe_(2)O_(4)氧载体化学链制氢反应性能的影响

采用溶胶-凝胶法制备不同助剂掺杂改性的ZnFe_(2)O_(4)氧载体,探究不同助剂(Sr、Ce、La和Al)对其性能的影响。化学链制氢实验在固定床反应器中进行,结果表明:添加助剂能有效提高氧载体的性能,单位质量氧载体H_(2)产量从高到低依次为La>Sr>Al>Ce,La改性的ZnFe_(2)O_(4)氧载体反应活性最高。结合X射线衍射、H_(2)-程序升温还原、吸附比表面测试法等表征手段和化学链制氢实验对掺杂助剂La的氧载体物理化学性质作进一步分析,考察不同掺杂质量分数对氧载体反应性能的影响。结果表明:添加质量分数为12%La助剂的ZnFe_(2)O_(4)在化学链制氢反应中单位H_(2)产量最高;La助剂的加入提高了氧载体的比表面积,促进氧空位的形成,加快晶格氧的迁移速率,有利于化学链制氢反应。

熔融法甲烷热裂解耦合化学链燃烧技术低碳联产工艺

目的开发以天然气为原料的熔融法甲烷热裂解耦合化学链燃烧技术联产氢气、电、碳材料新工艺。方法利用Aspen Plus对联产工艺进行建模计算,并从经济效益方面分析了技术经济可行性,以及讨论了热裂解反应甲烷转化率、热裂解反应温度和变压吸附分离效率等主要因素对系统的影响。结果在600 kmol/h进料条件下,氢气和碳材料产量分别为956 kmol/h和503 kmol/h,系统发电量为9.43 MW,CO_(2)捕集量为208 kmol/h,捕集率达到99.75%。制氢效率、制碳材料效率和产电效率分别为41.059%、31.453%和4.532%,系统总效率达到77.044%。结论提高甲烷转化率和变压吸附效率、降低热裂解反应温度有助于提高产品产量和系统总效率。

载氧体在甲烷化学链重整反应中的研究进展

甲烷化学链重整(CLRM)反应利用固体载氧体材料作为中间体,将传统甲烷重整反应分成还原和氧化两个反应,载氧体在这个过程中不断地被氧化还原,形成链式循环反应,实现了合成气或氢气的连续生产。相比传统重整反应而言,CLRM反应无须高成本的空分装置即可得到高纯度的产物。CLRM反应研究的关键在于载氧体的设计与选择,本文总结了近年来金属基载氧体(Ni、Fe、Cu、Co、Mn、Ce基)、复合型载氧体(包括钙钛矿和六铝酸盐)的最新研究进展,重点讨论了这些载氧体的组成、结构对反应性能的影响以及材料的设计与优化策略。进一步地,对载氧体的合成方法也做了总结和论述。此外,在甲烷化学链重整的工业化方面,探讨了反应器工艺流程设计的相关内容并提出了潜在问题。最后,对CLRM反应载氧体的研究现状提出了一些存在的挑战和未来的展望。

工业副产气化学链回收氢气技术研究进展

我国的工业副产气年产量巨大,是一种重要的制氢资源。由于其高杂质含量,回收其中的H_(2)需要采用复杂的工艺且成本较高,导致副产气的利用率低。相比传统方法,化学链制氢技术只需两步或三步即可制得H_(2),为工业副产气转化为高纯H_(2)提供了一条很有前景的途径。本文针对工业副产气化学链制氢技术的研究进展,讨论了工业副产气化学链制氢工艺的技术优势,总结了不同还原气对化学链制氢过程的影响。在化学链制氢反应过程中,H_(2)的反应活性优于CO,而CH_(4)的反应过程复杂,反应温度对不同气体的反应特性影响较为显著,杂质气体N_(2)和CO_(2)会对制氢过程产生不利影响。针对载氧体,高活性和稳定性载氧体是研究的重点,设计复合型载氧体、掺杂异价元素和负载离子导体等方法是改善载氧体反应性能的重要途径。总的来讲,化学链制氢技术取得了较快的进展,也为其他化学链反应研究提供了借鉴。

Ni、Ce、Zn和Cu修饰Fe_(2)O_(3)/Al_(2)O_(3)载氧体的甲烷化学链制氢特性

以甲烷为燃料的化学链制氢是一种耦合CO_(2)捕集的高效制氢技术。在Fe_(2)O_(3)/Al_(2)O_(3)载氧体的基础上,通过浸渍法分别添加Ni、Ce、Zn和Cu形成双金属载氧体,以提高其晶格氧传递性能、制氢性能和抗积炭性能。本文通过热力学计算、材料表征和实验研究,研究了不同双金属载氧体还原阶段和制氢阶段的反应性能,获得了不同双金属载氧体晶相结构与反应活性、制氢性能间的构效关系;并针对筛选出的最佳载氧体,进一步研究了其循环反应稳定性。研究表明,Cu是最合适的金属添加剂。Cu在Fe_(2)O_(3)/Al_(2)O_(3)双金属载氧体中形成了结构稳定的尖晶石相CuFe_(2)O_(4),提高了晶格氧活性,促进了载氧体中Fe_(2)O_(3)的深度还原,同时有效抑制积炭的生成,显著提高氢气产量和纯度,其中氢气产量由245mmol/100g载氧体提高到288mmol/100g载氧体,氢气纯度由88.3%提高到95.7%。Cu修饰Fe_(2)O_(3)/Al_(2)O_(3)载氧体在循环中表现出良好的稳定性,Fe^(3+)和Cu^(2+)的迁移使其微观结构得到改善,循环反应性能得到提高。研究验证了双金属载氧体在甲烷化学链制氢反应中的可行性,研究结果为铁基载氧体的设计和筛选提供了理论和实验依据。

多层核壳结构Fe@Al-Ti载氧体化学链制氢性能研究

Fe-Al-Ti载氧体在化学链制氢工艺中具有良好的循环稳定性和抗积炭性能,但反应形成FeAl_(2)O_(4)会降低抗烧结性能和氢气产率。为抑制FeAl_(2)O_(4)的生成并进一步提升载氧体反应性能,本研究采用自组装模板燃烧法制备多层核壳结构载氧体,以TiO_(2)为介层阻隔Fe2O3与Al2O3,形成多层核壳Fe@Al-Ti载氧体,在固定床上进行化学链制氢循环,评价多层核壳结构对反应性能的影响。结果表明,Fe@Al-Ti载氧体的介层有效阻隔Fe_(2)O_(3)与Al_(2)O_(3)的接触,抑制了FeAl_(2)O_(4)形成,抗烧结性能得到进一步提升。Fe@Al-Ti载氧体在化学链制氢循环实验中无明显积炭和团聚现象,制氢能力随循环次数逐渐增加,循环稳定性较好;尤其物质的量比Al∶Ti=3.5∶1的核壳载氧体的碳转化率、制氢率和储氧量最高,分别为57.4%、75.0%和6.01 mmol/g,比非核壳Fe-Al-Ti载氧体分别增加28.4%、30.0%、26.9%。

双流化床化学链制氢反应器的数值模拟

化学链制氢技术具有能耗低、产氢纯度高、清洁高效等优势,在氢能领域越来越受到重视。化学链制氢系统中复杂的流动与传递过程限制了该技术的发展,需要开展深入的研究工作揭示化学链制氢反应器的运行特性。使用双流体模型对化学链制氢双流化床反应器进行三维数值模拟研究,考察不同操作工况和载氧体属性对系统运行的影响,揭示反应器内部压力和固相浓度分布规律,为双流化床化学链制氢装置的运行和优化提供指导。计算结果表明,随着床料量增加,提升管压力波动幅值减小,运行更加平稳;由于进料口布置形式的影响,在提升管入口段固相分布呈现较强的不对称性;当前工况下提升管入口气速为7 m/s时反应器运行最平稳,随着流化气速增加固体循环量出现剧烈波动。

煤直接化学链气化合成尿素过程建模与性能分析

本文针对传统煤制尿素过程碳利用率低及二氧化碳捕集能耗高的问题,提出了煤直接化学链气化合成尿素的新工艺。本文对新工艺关键单元进行建模、模拟和性能分析。新工艺中CO_(2)、H2和N2分别来自于化学链技术的燃烧反应器,水蒸气反应器和空气反应器,避免了高能耗的空分单元和气体分离单元,H2和N2用于合成氨,氨进一步与CO_(2)合成尿素。采用碳利用率和二氧化碳捕集能耗分析新艺的技术性能,生产成本和投资回收期分析其经济性能。结果表明煤直接化学链气化合成尿素工艺碳利用率为30.11%,相比于传统煤制尿素提高约7%,二氧化碳捕集能耗下降了97.04%。新工艺单位尿素成本相比传统工艺下降了12.18%,投资回收期缩短了4年。

Numerical Study on the Process of Chemical Looping Hydrogen Production with Multiple Circulating Fluidized Bed Reactors

Hydrogen is an attractive energy carrier due to the high conversion efficiency and low pollutant emission.Chemical looping hydrogen production(CLHP)is an available way for producing high purity hydrogen with relatively low penalty energy and CO_(2)is captured simultaneously.Three reactors are usually contained for CLHP system including air reactor(AR),fuel reactor(FR)and steam reactor(SR).In current work,we focus on the performance of CLHP system,which is the basement for operation and design.Numerical simulations are carried out for analyzing the flow behavior and the numerical structure is built according to the experimental unit constructed at Southeast University,China.Results show that the operation of L-valve influences most the solid circulating rate of system and particles pass L-valve easily with large aeration rate.Mass distribution results indicate that fuel reactor has the capacity for particles storage.Increase of gas inlet rate of steam reactor leads to more particles leave steam reactor and accumulate into fuel reactor.L-valve can prevent the gas leakage between reactors and it will be adopted for reactive unit.Combining the operation of fuel reactor and L-valve,the system can reach steady state and get the regulating ability.

Regulation of Oxygen Activity by Lattice Confinement over Ni_(x)Mg_(1-x)O Catalysts for Renewable Hydrogen Production

The chemical looping steam reforming(CLSR)of bioethanol is an energy-efficient and carbon-neutral approach of hydrogen production.This paper describes the use of a Ni_(x)Mg_(1-x)O solid solution as the oxy-gen carrier(OC)in the CLSR of bioethanol.Due to the regulation effect of Mg^(2+)in Ni_(x)Mg_(1-x)O,a three-stage reaction mechanism of the CLSR process is proposed.The surface oxygen of Ni_(x)Mg_(1-x)O initially causes complete oxidation of the ethanol.Subsequently,H_(2)O and bulk oxygen confined by Mg^(2+)react with etha-nol to form CH_(3)COO^(*)followed by H_(2) over partially reduced Ni_(x)Mg_(1-x)O.Once the bulk oxygen is con-sumed,the ethanol steam reforming process is promoted by the metallic nickel in the stage Ⅲ.As a result,Ni_(0.4)Mg_(0.6)O exhibits a high H_(2) selectivity(4.72 mol H_(2) per mole ethanol)with a low steam-to-carbon molar ratio of 1,and remains stable over 30 CLSR cycles.The design of this solid-solution OC pro-vides a versatile strategy for manipulating the chemical looping process.