Polygeneration of hydrogen and power based on coal gasification integrated with a dual chemical looping process: Thermodynamic investigation

This paper assesses, from a thermodynamic perspective, the conversion of coal to power and hydrogen through gasification simultaneously with a dual chemical looping processes, namely chemical looping air separation (CLAS) and water–gas shift with calcium looping CO₂ absorption (WGS-CaL). CLAS offers an advantage over other mature technologies in that it can significantly reduce its capital cost. WGS-CaL is an efficient method for hydrogen production and CO₂ capture. The three major factors, oxygen to coal (O/C), steam to coal (S/C) and CaO to coal (Ca/C) were analyzed. Moreover, the comparisons of this suggested process and the traditional processes including integrated gasification combined cycle (IGCC), integrated gasification combined cycle with carbon capture and storage (IGCC-CCS) and integrated gasification combined cycle with calcium-based chemical looping (IGCC-CaL) were discussed. And, the exergy destruction analysis of this suggested process has also been calculated.     

Carbon-negative syngas production: A comprehensive assessment of biomass pyrolysis coupling chemical looping reforming

This article introduces a pyrolysis chemical looping reforming (PCLR) process that produces carbon-negative syngas in autothermal operation. To enhance the system's carbon negativity, a process configuration with oxygen carrier two-stage regeneration is adopted, enabling internal CO₂ utilization. The PCLR process is systematically evaluated and compared to chemical looping gasification and steam gasification processes in the process performance, energy efficiency, and environmental impact using a process model. Results reveal significant improvements over chemical looping gasification, including 69%, 45%, and 4% improvement in syngas yield, energy efficiency, and environmental benefit. Process analysis demonstrates that decoupling volatile reforming from pyrolysis and combustion enhances syngas quality, energy efficiency, and process flexibility. While the two-stage regeneration sacrifices syngas production, it contributes to a 4% increase in carbon negativity and a 15% reduction in carbon emissions. Thus, the PCLR process effectively overcomes the limitations of chemical looping gasification systems and exhibits excellent process intensification performance.     

Biomass Gasification Integrated with Chemical Looping System for Hydrogen and Power. Coproduction Process – Thermodynamic and Techno‐Economic Assessment

Three biomass gasification‐based hydrogen and power coproduction processes are modeled with Aspen Plus. Case 1 is the conventional biomass gasification coupled with a shift reactor, cases 2 and 3 involve integration of biomass gasification with iron‐based and calcium‐based chemical looping systems. The effects of important process parameters on the performance indicators such as hydrogen yield and efficiencies are evaluated by sensitivity analyses. These parameters include gasification temperature, molar ratios of steam to biomass in the gasifier, Fe₂O₃ to syngas in the fuel reactor, Fe/FeO to steam in the steam reactor, CaO to CO, and steam to CO in the carbonator. The energy and exergy balance distributions for the above three cases are comprehensively discussed and compared. Furthermore, techno‐economic assessments are performed to evaluate the three cases in terms of capital cost, operating cost, and leveled cost of energy.     

A comparative simulation study of power generation plants involving chemical looping combustion systems

This work presents a simulation study on both energy and economics of power generation plants with inherent CO₂ capture based on chemical looping combustion technologies. Combustion systems considered include a conventional chemical looping system and two extended three-reactor alternatives (exCLC and CLC3) for simultaneous hydrogen production. The power generation cycles include a combined cycle with steam injected gas turbines, a humid air turbine cycle and a simple steam cycle. Two oxygen carriers are considered in our study, iron and nickel. We further analyze the effect of the pressure reaction and the turbine inlet temperature on the plant efficiency. Results show that plant efficiencies as high as 54% are achieved by the chemical looping based systems with competitive costs. That value is well above the efficiency of 46% obtained by a conventional natural gas combined cycle system under the same conditions and simulation assumptions.     

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 MW·h 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 900 °C, 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.     

Effect of Gasifying Medium on the Coal Chemical Looping Gasification with CaSO4 as Oxygen Carrier

The chemical looping gasification uses an oxygen carrier for solid fuel gasification by supplying insufficient lattice oxygen. The effect of gasifying medium on the coal chemical looping gasification with CaSO₄ as oxygen carrier is investigated in this paper. The thermodynamical analysis indicates that the addition of steam and CO₂ into the system can reduce the reaction temperature, at which the concentration of syngas reaches its maximum value. Experimental result in thermogravimetric analyzer and a fixed-bed reactor shows that the mixture sample goes through three stages, drying stage, pyrolysis stage and chemical looping gasification stage, with the temperature for three different gaseous media. The peak fitting and isoconversional methods are used to determine the reaction mechanism of the complex reactions in the chemical looping gasification process. It demonstrates that the gasifying medium (steam or CO₂) boosts the chemical looping process by reducing the activation energy in the overall reaction and gasification reactions of coal char. However, the mechanism using steam as the gasifying medium differs from that using CO₂. With steam as the gasifying medium, parallel reactions occur in the beginning stage, followed by a limiting stage shifting from a kinetic to a diffusion regime. It is opposite to the reaction mechanism with CO₂ as the gasifying medium.     

Low temperature gasification using lattice oxygen

Low temperature pyrolysis and gasification has been investigated based on the chemical looping combustion (CLC), where insufficient amount of lattice oxygen was reacted with hydrocarbons. Metal oxides such as nickel oxide, iron oxide and titanium oxide were used as lattice oxygen source and were coated on silica gel or porous aluminum. Single column reactor was used for experiments and 36.1 mmol of polyethylene was dropped to the column whose temperature was ranged from 693 to 1073 K. For the pyrolysis, hydrogen yield was 100% of polyethylene contained hydrogen, while methane, CO and CO₂ were minor products and almost half of the supplied carbon was deposited on the particle surface. On the other hand, for the steam gasification, 2-3 mol of the hydrogen was generated from 1 mol of carbon and almost no carbon deposition was observed. It is found that no wax and heavy tar was observed in the exhaust. Therefore, the lattice oxygen was able to be applied to the low temperature gasification of hydrocarbons.     

Feasibility of a Co Oxygen Carrier for Chemical Looping Air Separation: Thermodynamics and Kinetics

Chemical looping air separation (CLAS) is based on the chemical looping principle: oxygen carriers release oxygen to carrier gas in a reduction reactor and absorb oxygen from air in an oxidation reactor. High oxygen transport capacity, high reactivity in reduction and oxidation reactions, and resistance to attrition and agglomeration are some of the criteria that feasible oxygen carrier materials should fulfill. Thermodynamic analysis was applied to prove the potential of Co₃O₄ as oxygen carrier. ZrO₂ served as binder to improve the anti‐sintering property and reactivity. Kinetic experiments were performed to determine the reaction rate and conversion of the oxygen carrier. Stability and durability of the oxygen carrier were characterized before and after cyclic experiments. The Co/Zr oxygen carrier proved to be a suitable candidate for the CLAS process.     

Simulation of a calcium looping CO2 capture process for pressurized fluidized bed combustion

The Canadian regulations on carbon dioxide emissions from power plants aim to lower the emissions from coal-fired units down to those of natural gas combined cycle (NGCC) units. Since coal is significantly more carbon intensive than natural gas, coal-fired plants must operate at higher net efficiencies and implement carbon capture to meet the new regulations. Calcium looping (CaL) is a promising post-combustion carbon capture (PCC) technology that, unlike other capture processes, generates additional power. By capturing carbon dioxide at elevated temperatures, the energy penalty that carbon capture technologies inherently impose on power plant efficiencies is significantly reduced. In this work, the CO₂ capture performance of a calcium-based sorbent is determined via thermogravimetric analysis under relatively high carbonation and low calcination temperatures. The results are used in an aspenONE™ simulation of a CaL process applied to a pressurized fluidized bed combustion (PFBC) system at thermodynamic equilibrium. The combustion of both natural gas and coal are considered for sorbent calcination in the CaL process. A sensitivity analysis on several process parameters, including sorbent feed rate and carbonator operating pressure, is undertaken. The energy penalty associated with the capture process ranges from 6.8–11.8 percentage points depending on fuel selection and operating conditions. The use of natural gas results in lower energy penalties and solids circulation rates, while operating the carbonator at 202 kPa(a) results in the lowest penalties and drops the solids circulations rates to below 1000 kg/s.     

Multiphase CFD Modeling for a Chemical Looping Combustion Process (Fuel Reactor)

There are growing concerns about increasing emissions of greenhouse gases and a looming global warming crisis. CO₂ is a greenhouse gas that affects the climate of the earth. Fossil fuel consumption is the major source of anthropogenic CO₂ emissions. Chemical looping combustion (CLC) has been suggested as an energy‐efficient method for the capture of carbon dioxide from combustion. A chemical‐looping combustion system consists of a fuel reactor and an air reactor. The air reactor consists of a conventional circulating fluidized bed and the fuel reactor is a bubbling fluidized bed. The basic principle involves avoiding direct contact of air and fuel during the combustion. The oxygen is transferred by the oxygen carrier from the air to the fuel. The water in combustion products can be easily removed by condensation and pure carbon dioxide is obtained without any loss of energy for separation. With the improvement of numerical methods and more advanced hardware technology, the time required to run CFD (computational fluid dynamic) codes is decreasing. Hence, multiphase CFD‐based models for dealing with complex gas‐solid hydrodynamics and chemical reactions are becoming more accessible. To date, there are no reports in the literature concerning mathematical modeling of chemical‐looping combustion using FLUENT. In this work, the reaction kinetics models of the (CaSO₄ + H₂) fuel reactor is developed by means of the commercial code FLUENT. The effects of particle diameter, gas flow rate and bed temperature on chemical looping combustion performance are also studied. The results show that the high bed temperature, low gas flow rate and small particle size could enhance the CLC performance.     

基于化学链制氧的煤气化集成系统工艺参数分析

利用化学链制氧（chemical looping air separation,CLAS）取代传统空气分离制氧技术,提出了基于化学链制氧的煤气化集成系统。以Mn2O3/Mn3O4为氧载体,依据Gibbs自由能最小化原理,利用Aspen Plus对该集成系统进行模拟研究。结果表明,当还原温度高于840℃时,还原程度和粗煤气温度不随还原温度增加而发生明显变化,H2、CO和CH4流量及含量变化趋势较平缓,冷煤气效率为80%左右;随CO2循环比增大,水蒸气用量逐渐减少,粗煤气中H2流量和含量降低,CO流量和含量升高,CH4流量和含量基本不变,冷煤气效率升高,粗煤气温度降低。气化压力变化对粗煤气中H2、CO和CH4流量和含量无明显影响,气化压力升高会降低冷煤气效率,提高粗煤气温度。     

Simulation and thermodynamic analysis of chemical looping reforming and CO2 enhanced chemical looping reforming

The production of hydrogen from methane via two chemical looping reforming (CLR) processes was simulated and thermodynamically analysed, one process being the conventional CLR process, the other being a CO₂ sorption enhanced process. The aim of the work was to identify suitable operating conditions for obtaining an optimum hydrogen gas purity and yield, whilst operating auto-thermally, at atmospheric pressure and with no carbon formation. In both simulations, the reactors were simulated using the Gibbs minimisation technique. NiO was used as the oxygen storing species, whilst CaO was used as the CO₂ adsorbent.     

Hydrodynamic analysis of a 10 kWth Calcium Looping Dual Fluidized Bed for post-combustion CO2 capture

Calcium Looping (CaL) in a Dual Fluidized Bed (DFB), utilizing a carbonator and a regenerator, is a post-combustion CO₂ capture technology currently under development. At IFK, University of Stuttgart, a 10 kW_th CaL DFB system has been built consisting of a carbonator riser and a Bubbling Fluidized Bed (BFB) regenerator. A major novelty of this facility is the implementation of a cone valve to control the sorbent looping rate between the two beds. This study presents detailed results of tests conducted on a hydrodynamically scaled cold model of the 10 kW_th CaL DFB facility. The performance of the cold model was compared with CaL process boundary conditions in order to determine the suitability of the 10 kW_th CaL DFB system. The resulting qualitative conclusions regarding DFB hydrodynamics may be of aid to other DFB processes, such as Chemical Looping Combustion (CLC) and Fast Internally Circulating Fluidized Bed (FICFB) gasification. All important operational parameters of the cold model DFB system, namely the Total Solid Inventory (TSI), riser superficial velocity, loop seal aeration, BFB overpressure, cone valve opening and mean particle size were varied in order to fully characterize the DFB operation. A stable operating region, bordered by two unstable regions, has been identified for the cold model riser. The cold model riser pressure drop profile, solid fraction profile, solid flow structure and their variation with respect to operational parameters have been analyzed in order to draw conclusions regarding axial inventory allocation and gas–solid contacting which are important criteria for the CFB carbonator's CO₂ capture efficiency. Finally, empirical correlations regarding the cold model riser entrainment and the solid looping rate have been derived.     

Comparative assessment of coal fired IGCC systems with CO2 capture using physical absorption,membrane reactors and chemical looping

The integrated gasification combined cycle (IGCC) as an efficient power generation technology with lowest specific carbon dioxide emissions among coal power plants is a very good candidate for CO₂ capture resulting in low energy penalties and minimised CO₂ avoidance costs. In this paper, the techno-economic characteristics of four different capture technologies, which are built upon a conventional reference case, are studied using the chemical process simulation package “ECLIPSE”. The technology options considered are: physical absorption, water gas shift reactor membranes and two chemical looping combustion cycles (CLC), which employ single and double stage reactors. The latter system was devised to achieve a more balanced distribution of temperatures across the reactors and to counteract hot spots which lead to the agglomeration and the sintering of oxygen carriers. Despite the lowest efficiency loss among the studied systems, the economic performance of the double stage CLC was outperformed by systems employing physical absorption and water gas shift reactor membranes. Slightly higher efficiencies and lower costs were associated with systems with integrated air separation units. The estimation of the overall capital costs was carried out using a bottom-up approach. Finally, the CO₂ avoidance costs of individual technologies were calculated based on the techno-economic data.     

Hydrogen production through chemical looping using NiO/NiAl2O4 as oxygen carrier

A new autothermal route to produce hydrogen from natural gas via chemical looping technology was investigated. Tests were conducted in a micro-fixed bed reactor loaded with 200 mg of NiO/NiAl₂O₄ as oxygen carrier. Methane reacts with a nickel oxide in the absence of molecular oxygen at 800 °C for a period of time as high as 10 min. The NiO is subsequently contacted with a synthetic air stream (21% O₂ in argon) to reconstitute the surface and combust carbon deposited on the surface. Methane conversion nears completion but to minimize combustion of the hydrogen produced, the oxidation state of the carrier was maintained below 30% (where 100% represents a fully oxidized surface). Co-feeding water together with methane resulted in stable hydrogen production. Although the carbon deposition increased with time during the reduction cycle, the production rate of hydrogen remained virtually constant. A new concept is also presented where hydrogen is obtained from methane with inherent CO₂ capture in an energy neutral 3-reactors CFB process. This process combines a methane combustion step where oxygen is provided via an oxygen carrier, a steam methane reforming step catalyzed by the reduced oxygen carrier and an oxidizing step where the O-carrier is reconstituted to its original state.     

化学链空分联合化学链制氢的煤制甲醇过程参数优化与分析

我国能源结构决定了以煤为主的甲醇生产路线。传统煤制甲醇过程主要存在过程能量效率低、CO₂捕集能耗高等问题。本文提出了一种化学链空分联合化学链制氢的煤制甲醇新过程，以降低能耗、二氧化碳排放及提高能源效率。化学链空分技术的集成可以替代传统煤制甲醇过程的空气分离单元，并在一定程度上降低能耗。化学链制氢技术的集成，一方面可以替代水煤气变换装置，并且可以极大程度降低二氧化碳捕集能耗；另一方面，化学链制氢技术还可生产用于调整合成气氢与碳比的氢。本文对新过程的核心单元进行了参数优化以及全流程的模拟，基于模拟对新过程的性能进行了分析，结果表明新过程与传统的煤制甲醇过程相比，空分和二氧化碳捕集能耗分别降低了41%和89%。同时，新过程的能量效率提高了18%，二氧化碳排放量降低了45%。     

Innovative Internally Circulating Reactor Concept for Chemical Looping‐Based CO2 Capture Processes: Hydrodynamic Investigation

An experimental hydrodynamic investigation has been carried out for a novel internally circulating chemical looping (ICCL) reactor concept proposed to reduce the technical complexities encountered in conventional chemical looping combustion (CLC) and reforming (CLR) technologies. The concept consists of a single reactor with internal physical separations dividing it into two sections, i.e., the fuel and air sections. The trade‐off for this reduction in process complexity is increased gas leakage between the two reactor sections, so a pseudo‐2D cold‐flow experimental unit was designed. The ICCL concept remains highly efficient in terms of CO₂ separation while ensuring significant process simplifications. The solids circulation rate also proved easy to control by adjusting the fluidization velocity ratio and the bed loading. In the light of the excellent hydrodynamic performance, the ICCL concept appears to be well‐suited for further development as a CLC/CLR reactor model.     

Chemical Looping of Manganese to Synthesize Ammonia at Atmospheric Pressure: Sodium as Promoter

Affordable synthetic ammonia (NH₃) enables the production of nearly half of the food we eat and is emerging as a renewable energy carrier. Sodium-promoted chemical looping NH₃ synthesis at atmospheric pressure using manganese (Mn) is here demonstrated. The looping process may be advantageous when inexpensive renewable hydrogen from electrolysis is available. Avoiding the high pressure of the Haber-Bosch process by chemical looping using earth-abundant materials may reduce capital cost, facilitate intermittent operation, and allow operation in geographic areas where infrastructure is less sophisticated. At this early stage, the data suggest that 0.28 m³ of a 50 % porosity solid Mn bed may suffice to produce 100 kg NH₃ per day by chemical looping, with abundant opportunities for improvement.     

Ni载体整体煤气化链式燃烧联合循环性能

本文将具有分离CO₂的链式燃烧技术与整体煤气化联合循环(IGCC)技术结合,构成整体煤气化链式燃烧联合循环系统,对系统性能进行了模拟研究。结果表明,采用德士古气化工艺、空气反应器出口温度1200℃,NiO/NiAl₂O₄作载氧体,压气机压比17、补燃后透平初温(TIT)1350℃、冷却空气量12％时,系统净效率39.61% HHV（41.55%LHV）,CO₂排放量126 g·kW^-1·h^-1。补燃温度1350℃,空气反应器温度由1000℃升高到1200℃,CO₂的回收率提高约23％,系统效率由40.3%降低到39.61％;补燃温度由1200℃提高到1500℃,系统净效率由37.4%增加到40.8%,CO₂的排放量从3g·kW^-1·h^-1增加到202 g·kW^-1·h^-1;补燃温度一定,压比增大,系统比功减小,CO₂排放量增加,效率先增大后减小,存在最佳压比.     

Physical mixtures as simple and efficient alternative to alloy carriers in chemical looping processes

Chemical looping combustion is a clean combustion technology for fossil or renewable fuels. In a previous demonstration, chemical looping was applied to CO₂ activation via reduction to CO with concurrent production of synthesis gas (CO + H₂) from CH₄ via rationally designed Fe‐Ni alloys. Here, it is demonstrated that that a simple physical mixture can even outperform the equivalent alloy based on an intricate gas phase mediated coupling between the two metals: Ni cracks methane to carbon and H₂. The latter then reduces iron oxide carrier, forming steam, which gasifies the carbon deposits on Ni to produce a mixture of CO + H₂, thus regenerating the active Ni surface. It was suggested that the principle demonstrated here—the gas phase‐mediated coupling of two solid reactants with distinct functionalities—should be applicable broadly toward oxidation reactions and hence opens a new avenue for rational design of chemical looping processes. © 2016 American Institute of Chemical Engineers AIChE J, 63: 51–59, 2017