Integrated fossil fuel and solar thermal systems for hydrogen production and CO2 mitigation

In most current fossil-based hydrogen production methods, the thermal energy required by the endothermic processes of hydrogen production cycles is supplied by the combustion of a portion of the same fossil fuel feedstock. This increases the fossil fuel consumption and greenhouse gas emissions. This paper analyzes the thermodynamics of several typical fossil fuel-based hydrogen production methods such as steam methane reforming, coal gasification, methane dissociation, and off-gas reforming, to quantify the potential savings of fossil fuels and CO₂ emissions associated with the thermal energy requirement. Then matching the heat quality and quantity by solar thermal energy for different processes is examined. It is concluded that steam generation and superheating by solar energy for the supply of gaseous reactants to the hydrogen production cycles is particularly attractive due to the engineering maturity and simplicity. It is also concluded that steam-methane reforming may have fewer engineering challenges because of its single-phase reaction, if the endothermic reaction enthalpy of syngas production step (CO and H₂) of coal gasification and steam methane reforming is provided by solar thermal energy. Various solar thermal energy based reactors are discussed for different types of production cycles as well.     

Integrated energy systems based on cascade utilization of energy

Focusing on the traditional principle of physical energy utilization, new integration concepts for combined cooling, heating and power (CCHP) system were identified, and corresponding systems were investigated. Furthermore, the principle of cascade utilization of both chemical and physical energy in energy systems with the integration of chemical processes and thermal cycles was introduced, along with a general equation describing the interrelationship among energy levels of substance, Gibbs free energy of chemical reaction and physical energy. On the basis of this principle, a polygeneration system for power and liquid fuel (methanol) production has been presented and investigated. This system innovatively integrates a fresh gas preparation subsystem without composition adjustment process (NA) and a methanol synthesis subsystem with partial-recycle scheme (PR). Meanwhile, a multi-functional energy system (MES) that consumes coal and natural gas as fuels simultaneously, and co-generates methanol and power, has been presented. In the MES, coal and natural gas are utilized synthetically based on the method of dual-fuel reforming, which integrates methane/steam reforming and coal combustion. Compared with conventional energy systems that do not consider cascade utilization of chemical energy, both of these systems provide superior performance, whose energy saving ratio can be as high as 10%–15%. With special attention paid to chemical energy utilization, the integration features of these two systems have been revealed, and the important role that the principle of cascade utilization of both chemical and physical energy plays in system integration has been identified.     

应用天然气重整技术的新型动力系统开拓研究

总结概述应用天然气重整反应技术的新型动力系统开拓研究,包括燃料电池及联合循环系统、化学回热燃气轮机循环、太阳能一天然气互补动力系统以及天然气／煤双燃料综合动力系统等。分析归纳天然气蒸汽重整在动力系统应用的新方式,侧重论述天然气蒸汽重整在相关新系统集成中新应用的功能与机理,还分析揭示新系统的特性与性能。     

Effect of supplementary firing options on cycle performance and CO2 emissions of an IGCC power generation system

Supplementary firing is adopted in combined‐cycle power plants to reheat low‐temperature gas turbine exhaust before entering into the heat recovery steam generator. In an effort to identify suitable supplementary firing options in an integrated gasification combined‐cycle (IGCC) power plant configuration, so as to use coal effectively, the performance is compared for three different supplementary firing options. The comparison identifies the better of the supplementary firing options based on higher efficiency and work output per unit mass of coal and lower CO₂ emissions. The three supplementary firing options with the corresponding fuel used for the supplementary firing are: (i) partial gasification with char, (ii) full gasification with coal and (iii) full gasification with syngas. The performance of the IGCC system with these three options is compared with an option of the IGCC system without supplementary firing. Each supplementary firing option also involves pre‐heating of the air entering the gas turbine combustion chamber in the gas cycle and reheating of the low‐pressure steam in the steam cycle. The effects on coal consumption and CO₂ emissions are analysed by varying the operating conditions such as pressure ratio, gas turbine inlet temperature, air pre‐heat and supplementary firing temperature. The results indicate that more work output is produced per unit mass of coal when there is no supplementary firing. Among the supplementary firing options, the full gasification with syngas option produces the highest work output per unit mass of coal, and the partial gasification with char option emits the lowest amount of CO₂ per unit mass of coal. Based on the analysis, the most advantageous option for low specific coal consumption and CO₂ emissions is the supplementary firing case having full gasification with syngas as the fuel. Copyright © 2008 John Wiley & Sons, Ltd.     

以甲烷重整方式利用气化煤气显热的甲醇-电多联产系统

根据"温度对口,组分合适"的原则,提出了一种以甲烷重整来利用煤气显热的多联产系统,可用于煤/天然气、煤/焦炉煤气双燃料系统.该系统利用气化炉出口的高温煤气显热作为甲烷/水蒸汽重整的反应热,把煤气的热能转变为合成气的化学能进行回收,使天然气和焦炉煤气重整后的富氢气体与富碳的气化煤气可按化工生产要求灵活调配.计算结果表明,相比于单产系统,双燃料系统效率最少可提高约1.5%.     

Integrated solar combined cycle system with steam methane reforming: Thermodynamic analysis

The present paper considers an integrated solar combined cycle system (ISCCS) with an utilization of solar energy for steam methane reforming. The overall efficiency was compared with the efficiency of an integrated solar combined cycle system with the utilization of solar energy for steam generation for a steam turbine cycle. Utilization of solar energy for steam methane reforming gives the increase in an overall efficiency up to 3.5%. If water that used for steam methane reforming will be condensed from the exhaust gases, the overall efficiency of ISCCS with steam methane reforming will increase up to 6.2% and 8.9% for β = 1.0 and β = 2.0, respectively, in comparison with ISCCS where solar energy is utilized for generation of steam in steam turbine cycle. The Sankey diagrams were compiled based on the energy balance. Utilization of solar energy for steam methane reforming increases the share of power of a gas turbine cycle: two-thirds are in a gas turbine cycle, and one-third is in a steam turbine cycle. In parallel, if solar energy is used for steam generation for a steam turbine cycle, than the shares of power from a gas and steam turbine are almost equal.     

A proposal for a novel multi-functional energy system for the production of hydrogen and power

A novel multi-functional energy system with two kinds of fuels (coal and natural gas) and two kinds of products (hydrogen and electricity) is proposed. The proposed system takes advantage of the complementary properties of coal and natural gas by integrating natural gas/steam reforming together with the combustion of coal. Coal is indirectly gasified by combustion so that the need for an air separation unit is eliminated. At the same time, a part of superior natural gas fuel, which is burnt in the reformer, is replaced with inferior coal fuel. Hence, energy utilization is improved effectively. In addition, the novel system is investigated by means of the EUD (energy-utilization diagram) methodology and then compared with the reference system, which is composed of four conventional systems. As a result, the thermal efficiency of the new system may be expected to reach 75%. Moreover, a comparison with the reference system shows that the proposed system provides a 10% energy savings. The promising result obtained here provides an attractive option for an effective utilization of coal and natural gas.     

Thermochemical waste‐heat recuperation by steam methane reforming with flue gas addition

The process flow schematic of fuel‐consuming equipment with thermochemical waste‐heat recuperation by steam methane reforming with an addition of flue gas to the reaction mixture is suggested. The advantages of such a thermochemical recuperation (TCR) system compared with the TCR system by steam methane reforming are shown and justified. Based on the first law energy analysis, the heat inputs and outputs of the TCR system were determined. To determine the exhaust gases heat transformed into chemical energy of a new synthetic fuel, the thermodynamic analysis by minimizing Gibbs energy via Aspen HYSYS was performed. It was found that with an increase in the mole fraction of combustion products in the reaction mixture, the enthalpy of the methane reforming reaction increases, especially noticeable at the temperature range above 1000 K. Based on the heat, balance of the TCR system was established that the addition of combustion products to the reaction mixture has the following effects: reducing the heat input for steam production in a steam generator; reduction of the steam generator size because of the need to produce a smaller amount of steam in comparison with TCR by pure steam methane reforming; and reducing the amount of heat transferred through the wall of the reformer and, as a consequence, reduction in size of the reformer.     

Hydrogen production from fossil fuels with carbon capture and storage based on chemical looping systems

This paper analyzes innovative processes for producing hydrogen from fossil fuels conversion (natural gas, coal, lignite) based on chemical looping techniques, allowing intrinsic CO₂ capture. This paper evaluates in details the iron-based chemical looping system used for hydrogen production in conjunction with natural gas and syngas produced from coal and lignite gasification. The paper assesses the potential applications of natural gas and syngas chemical looping combustion systems to generate hydrogen. Investigated plant concepts with natural gas and syngas-based chemical looping method produce 500 MW hydrogen (based on lower heating value) covering ancillary power consumption with an almost total decarbonisation rate of the fossil fuels used.The paper presents in details the plant concepts and the methodology used to evaluate the performances using critical design factors like: gasifier feeding system (various fuel transport gases), heat and power integration analysis, potential ways to increase the overall energy efficiency (e.g. steam integration of chemical looping unit into the combined cycle), hydrogen and carbon dioxide quality specifications considering the use of hydrogen in transport (fuel cells) and carbon dioxide storage in geological formation or used for EOR.     

Thermal design of methane steam reformer with low-temperature non-reactive heat source for high efficiency engine-hybrid stationary fuel cell system

In hybrid fuel cell systems, the fuel-lean anode-off gas is very useful to improve the system efficiency via additional power generation or utilization of thermal energy for heating up of auxiliary devices. In this study, the thermal energy of the hybrid systems is firstly utilized in homogeneous charge combustion engine for additional power and is then supplied to heat up the external reformer. Different from other hybrid fuel cell systems, it is very difficult to utilize heat energy of exhausted gas from engine due to its low temperature characteristics. This study is concentrated on the computation analysis of external methane steam reformers with engine out exhausted gases. Computational model is validated with experiment and parametric study is conducted. Results show that the temperature uniformity of the longitudinal and radial directions is crucial for the methane conversion efficiency. Additionally, the methane conversion rate also depends on the performance of tube-side heat transfer. When the total methane flow is fixed, the methane conversion rate shows trade-off with increasing steam-to-carbon ratio (SCR). Finally, the sensitivity study shows that heat transfer area and reactor length are dominant parameters for steam reforming with engine out exhausted gases.     

A novel approach for treatment of CO2 from fossil fired power plants,Part A: The integrated systems ITRPP

The environmental issues, due to the global warming caused by the rising concentration of greenhouse gases in the atmosphere, require new strategies aimed to increase power plants efficiencies and to reduce CO₂ emissions.This two-paper work focuses on a different approach for capture and reduction of CO₂ from flue gases of fossil fired power plant, with respect to conventional post-combustion technologies. This approach consists of flue gases utilization as co-reactants in a catalytic process, the tri-reforming process, to generate a synthesis gas suitable in chemical and energy industries (methanol, DME, etc.). In fact, the further conversion of syngas to a transportation fuel, such as methanol, is an attractive solution to introduce near zero-emission technologies (i.e. fuel cells) in vehicular applications.In this Part A, integrated systems for co-generation of electrical power and synthesis gas useful for methanol production have been defined and their performance has been investigated considering different flue gases compositions. In Part B, in order to verify the environmental advantages and energy suitability of these systems, their comparison with conventional technology for methanol production is carried out.The integrated systems (ITRPP, Integrated Tri-Reforming Power Plant) consist of a power island, based on a thermal power plant, and a methane tri-reforming island in which the power plants' exhausts react with methane to produce a synthesis gas used for methanol synthesis. As power island, a steam turbine power plant fuelled with coal and a gas turbine combined cycle fuelled with natural gas have been considered.The energy and environmental analysis of ITRPP systems (ITRPP-SC and ITRPP-CC) has been carried out by using thermochemical and thermodynamic models which have allowed to calculate the syngas composition, to define the energy and mass balances and to estimate the CO₂ emissions for each ITRPP configuration.The repowering of the base power plants (steam turbine power plant and gas turbine combine cycle) is very high because of the large amount of steam produced in the tri-reforming island (in the ITRPP-SC is about of 64%, while in the ITRPP-CC is about of 105%).The reduction in the CO₂ emissions has been estimated in 83% (15.4 vs. 93.4 kg/GJ_Fuelinput) and 84% (8.9 vs. 56.2 kg/GJ_Fuelinput) for the ITRPP-SC and ITRPP-CC respectively.     

Thermodynamic analysis of hydrogen production via sorption-enhanced steam methane reforming in a new class of variable volume batch-membrane reactor

Combined reaction–separation processes are a widely explored method to produce hydrogen from endothermic steam reforming of hydrocarbon feedstock at a reduced reaction temperature and with fewer unit operation steps, both of which are key requirements for energy efficient, distributed hydrogen production. This work introduces a new class of variable volume batch reactors for production of hydrogen from catalytic steam reforming of methane that operates in a cycle similar to that of an internal combustion engine. It incorporates a CO₂ adsorbent and a selectively permeable hydrogen membrane for in situ removal of the two major products of the reversible steam methane reforming reaction. Thermodynamic analysis is employed to define an envelope of ideal reactor performance and to explore the tradeoff between thermal efficiency and hydrogen yield density with respect to critical operating parameters, including sorbent mass, steam to methane ratio and fraction of product gas recycled. Particular attention is paid to contrasting the variable volume batch-membrane reactor approach to a conventional fixed bed reaction–separation approach. The results indicates that the proposed reactor is a viable option for low temperature distributed production of hydrogen from methane, the primary component of natural gas feedstock, motivating a detailed study of reaction/adsorption kinetics and heat/mass transfer effects.     

天然气转化生产合成氨尿素的节能减排CO2新工艺

天然气三一段纯氧转化制合成气新工艺中,外加热蒸汽转化工艺段承担10%～15%的CH4负荷,用于为开车和保障自热部分氧化提供较高温度的一段转化气（〉650℃）;其余85%～90%的CH4负荷由换热转化工艺段和二段炉纯氧自热转化工艺段承担。所用的换热转化工艺,将传统的两段蒸汽转化工艺加热用的占天然气总耗量1/5～1/4的燃料天然气省下用作原料,从而使每吨合成氨的天然气耗量从传统的两段蒸汽转化的1000m^3（标准）降到800～850m^3（标准）。三一段纯氧转化制合成气新工艺比传统一段外加热蒸汽转化工艺可减少85%～90%的燃料气,同时降低相应的CO2排放。从开车到投产所需的时间为6～8d,大大缩短了开车周期。介绍了用该新工艺对我国天然气生产合成氨装置进行扩建改造的工程设计方案,以及天然气三一段转化等压一次变换制氨联产尿素的生产设计方案。     

Integration of underground coal gasification with a solid oxide fuel cell system for clean coal utilization

Underground coal gasification (UCG) is a promising clean coal technology. Typically, the syngas obtained from UCG is used for power generation via the steam turbine route. In the present paper, we consider UCG as a hydrogen generator and investigate the possibility of coupling it with a solid oxide fuel cell (SOFC) to generate electrical power directly. We show, through analysis, that integration with SOFC gives two specific advantages. Firstly, because of the high operating temperature of the SOFC, its anode exhaust can be used to produce steam required for the operation of UCG as well as for the reforming of the syngas for the SOFC. Secondly, the SOFC serves as a selective absorber of oxygen from air which paves the way for an efficient system of a carbon-neutral electrical power generation from underground coal. Thermodynamic analysis of the integrated system shows considerable improvement in the net thermal efficiency over that of a conventional combined cycle plant.     

整体煤气化联合循环(IGCC)发电技术介绍

整体煤气化联合循环（IGCC）发电技术是煤气化和蒸汽联合循环的结合,是当今国际正在兴起的一种先进的洁净煤（CCT）发电技术,具有高效、低污染、节水、综合利用好等优点。它的原理是：煤经过气化和净化后,除去煤气中99％以上的硫化氢和接近100％的粉尘,将固体燃料转化成燃气轮机能燃用的清洁气体燃料,以驱动燃气轮机发电,再使燃气发电与蒸汽发电联合起来。     

The air membrane-ATR integrated gas turbine power cycle: A method for producing electricity with low CO2 emissions

The air membrane-auto thermal reforming (AM-ATR) gas turbine cycle combines features of the R-ATR power cycle, introduced at the University of Florence, with ceramic, air separation membranes to achieve a novel combined cycle process with fuel decarbonisation and near-zero CO₂ emissions. Within this process, the natural gas fuel is converted to H₂ and CO through the auto thermal reforming process (ATR), i.e. combined partial oxidation and steam methane reforming, within the air separation membrane reactor. In a subsequent process unit, the H₂ content of the reformed fuel is enriched by the well known CO–CO₂ shift reaction. This fuel is then sent to an amine based carbon dioxide removal unit and, finally, to two combustors: the first one is located upstream of the membrane reformer (in order to achieve the required working temperature) and the second one is downstream of the membrane to reach the desired turbine inlet temperature (TIT).The main advantage of the proposed concept over other decarbonisation processes is the coupling of the membrane and the ATR reactor. This coupling greatly reduces the mass flow of syngas with respect to the air blown ATR contained in the previously proposed R-ATR, thus lowering the size of the syngas treatment section. Furthermore, as the oxygen production is integrated at high temperatures in the power cycle, the efficiency penalty of producing oxygen is much smaller than for the traditional cryogenic oxygen separation. The main advantages over other integrated GT-membrane concepts are the lower membrane operating temperature, lower levels of required air separation at high partial pressure driving forces (leading to lower membrane surface areas) and the possibility to achieve a higher TIT with top firing without increasing CO₂ emissions. When compared to power plants with tail end CO₂ separation, the CO₂ removal process treats a gas at pressure and with a significantly higher CO₂ concentration than that of gas turbine exhausts, which allows a compact carbon dioxide removal unit with a lower energy penalty.Starting from the same basis, various configurations were considered and optimised, all of which targeted a 65 MW power output combined cycle. The efficiency level achieved is around 45% (including recompression of the separated CO₂), which is roughly 10% less than the reference GT-CC plant (without CO₂ removal). A significant part of the efficiency penalty (4.3–5.6% points) is due to the fuel reforming, whereas further penalties come from the recompression units, loss of working fluid through the expander and the steam extracted for the ATR reactor and CO₂ separation. The specific CO₂ emissions of the MCM-ATR are about 120 kg CO₂/kWh, representing 30% of the emissions without CO₂ removal. This may be reduced to 10–15% with a better design of the shift reactors and the CO₂ removal unit. Compared to other concepts with air membrane technology, such as the AZEP concept, the efficiency loss is much greater when used for fuel de-carbonisation than for previous integration options.     

Forging furnace with thermochemical waste-heat recuperation by natural gas reforming: Fuel saving and heat balance

This paper considers thermochemical recuperation (TCR) of waste-heat using natural gas reforming by steam and combustion products. Combustion products contain steam (H₂O), carbon dioxide (CO₂), and ballast nitrogen (N₂). Because endothermic chemical reactions take place, methane steam-dry reforming creates new synthetic fuel that contains valuable combustion components: hydrogen (H₂), carbon monoxide (CO), and unreformed methane (CH₄). There are several advantages to performing TCR in the industrial furnaces: high energy efficiency, high regeneration rate (rate of waste-heat recovery), and low emission of greenhouse gases (CO₂, NO_x). As will be shown, the use of TCR is significantly increasing the efficiency of industrial furnaces – it has been observed that TCR is capable of reducing fuel consumption by nearly 25%. Additionally, increased energy efficiency has a beneficial effect on the environment as it leads to a reduction in greenhouse gas emissions.     

Two novel oxy-fuel power cycles integrated with natural gas reforming and CO2 capture

Two novel system configurations were proposed for oxy-fuel natural gas turbine systems with integrated steam reforming and CO₂ capture and separation. The steam reforming heat is obtained from the available turbine exhaust heat, and the produced syngas is used as fuel with oxygen as the oxidizer. Internal combustion is used, which allows a very high heat input temperature. Moreover, the turbine working fluid can expand down to a vacuum, producing an overall high-pressure ratio. Particular attention was focused on the integration of the turbine exhaust heat recovery with both reforming and steam generation processes, in ways that reduce the heat transfer-related exergy destruction. The systems were thermodynamically simulated, predicting a net energy efficiency of 50–52% (with consideration of the energy needed for oxygen separation), which is higher than the Graz cycle energy efficiency by more than 2 percentage points. The improvement is attributed primarily to a decrease of the exergy change in the combustion and steam generation processes that these novel systems offer. The systems can attain a nearly 100% CO₂ capture.     

Life cycle environmental impact comparison of solid oxide fuel cells fueled by natural gas,hydrogen, ammonia and methanol for combined heat and power generation

This study aims to provide a comprehensive environmental life cycle assessment of heat and power production through solid oxide fuel cells (SOFCs) fueled by various chemical feeds namely; natural gas, hydrogen, ammonia and methanol. The life cycle assessment (LCA) includes the complete phases from raw material extraction or chemical fuel synthesis to consumption in the electrochemical reaction as a cradle-to-grave approach. The LCA study is performed using GaBi software, where the selected impact assessment methodology is ReCiPe 1.08. The selected environmental impact categories are climate change, fossil depletion, human toxicity, water depletion, particulate matter formation, and photochemical oxidant formation. The production pathways of the feed gases are selected based on the mature technologies as well as emerging water electrolysis via wind electricity. Natural gas is extracted from the wells and processed in the processing plant to be fed to SOFC. Hydrogen is generated by steam methane reforming method using the natural gas in the plant. Methanol is also produced by steam methane reforming and methanol synthesis reaction. Ammonia is synthesized using the hydrogen obtained from steam methane reforming and combined with nitrogen from air in a Haber-Bosch plant. Both hydrogen and ammonia are also produced via wind energy-driven decentralized electrolysis in order to emphasize the cleaner fuel production. The results of this study show that feeding SOFC systems with carbon-free fuels eliminates the greenhouse gas emissions during operation, however additional steps required for natural gas to hydrogen, ammonia and methanol conversion, make the complete process more environmentally problematic. However, if hydrogen and ammonia are produced from renewable sources such as wind-based electricity, the environmental impacts reduce significantly, yielding about 0.05 and 0.16 kg CO₂ eq., respectively, per kWh electricity generation from SOFC.     

Solar thermal power cycle with integration of methanol decomposition and middle-temperature solar thermal energy

In this paper, we have proposed a new solar thermal power cycle which integrates methanol decomposition and middle-temperature solar thermal energy, and investigated its features based on the principle of the cascade utilization of chemical exergy. Also, the methanol decomposition with a catalyst was experimentally studied at temperatures of 150–300 °C and under atmospheric pressure. The chemical energy released by methanol fuel in this cycle consisted of two successive processes: solar energy drives the thermal decomposition of methanol in a solar receiver-reactor, and the syngas of resulting products is combusted with air, namely, indirect combustion after methanol decomposition. As a result, the net solar-to-electric efficiency of the proposed cycle could be 35% at the collector temperature of 220 °C and the turbine inlet temperature of 1300 °C, and the exergy loss in the indirect combustion of methanol was about 7% points lower than that in the direct combustion of methanol. The promising results obtained in this study indicated that this new solar thermal power cycle could make significant improvements both in the efficient use of the chemical energy of clean synthetic fuel and in the middle-temperature solar thermal energy in a power system.