High quality syngas production from pressurized K2CO3 catalytic coal gasification with in-situ CO2 capture

The enhanced K-catalytic coal gasification by CO₂ sorption reaction (EKcSG) was proposed to produce syngas with high content of H₂ and CH₄ and perform in-situ CO₂ capture. CO₂ is reduced dramatically with the introduction of the CaO into the reactor under typical K-catalytic coal gasification condition (3.5 MPa, 700 °C). The carbonation reaction of CaO can promote the syngas production by improving the equilibrium of the water-gas shift reaction and supplying heat for coal gasification reaction. In the presence of the CaO sorbent (Ca/C = 0.5), the CO₂ concentration in the product gas decreased from 25.61% to 12.80% compared with that without CaO. Correspondingly, the total concentration of H₂ and CH₄ is improved from 65.61% to 82.99% and the carbon conversion reached above 95%. The effect of Ca/C ratio and reaction temperature was investigated during the EKcSG process. It is considered that Ca/C ratio of 0.5 is the best proportion in terms of carbon conversion and CO₂ absorption in our experimental conditions.     

Fuel saving, carbon dioxide emission avoidance, and syngas production by tri-reforming of flue gases from coal- and gas-fired power stations, and by the carbothermic reduction of iron oxide

Flue gases from coal, gas, or oil-fired power stations, as well as from several heavy industries, such as the production of iron, lime and cement, are major anthropogenic sources of global CO₂ emissions. The newly proposed process for syngas production based on the tri-reforming of such flue gases with natural gas could be an important route for CO₂ emission avoidance. In addition, by combining the carbothermic reduction of iron oxide with the partial oxidation of the carbon source, an overall thermoneutral process can be designed for the co-production of iron and syngas rich in CO. Water-gas shift (WGS) of CO to H₂ enables the production of useful syngas. The reaction process heat, or the conditions for thermoneutrality, are derived by thermochemical equilibrium calculations. The thermodynamic constraints are determined for the production of syngas suitable for methanol, hydrogen, or ammonia synthesis. The environmental and economic consequences are assessed for large-scale commercial production of these chemical commodities. Preliminary evaluations with natural gas, coke, or coal as carbon source indicate that such combined processes should be economically competitive, as well as promising significant fuel saving and CO₂ emission avoidance. The production of ammonia in the above processes seems particularly attractive, as it consumes the nitrogen in the flue gases.     

Hydrogen production from coal gasification for effective downstream CO2 capture

The coal gasification process is used in commercial production of synthetic gas as a means toward clean use of coal. The conversion of solid coal into a gaseous phase creates opportunities to produce more energy forms than electricity (which is the case in coal combustion systems) and to separate CO₂ in an effective manner for sequestration. The current work compares the energy and exergy efficiencies of an integrated coal-gasification combined-cycle power generation system with that of coal gasification-based hydrogen production system which uses water-gas shift and membrane reactors. Results suggest that the syngas-to-hydrogen (H₂) system offers 35% higher energy and 17% higher exergy efficiencies than the syngas-to-electricity (IGCC) system. The specific CO₂ emission from the hydrogen system was 5% lower than IGCC system. The Brayton cycle in the IGCC system draws much nitrogen after combustion along with CO₂. Thus CO₂ capture and compression become difficult due to the large volume of gases involved, unlike the hydrogen system which has 80% less nitrogen in its exhaust stream. The extra electrical power consumption for compressing the exhaust gases to store CO₂ is above 70% for the IGCC system but is only 4.5% for the H₂ system. Overall the syngas-to-hydrogen system appears advantageous to the IGCC system based on the current analysis.     

A novel approach for treatment of CO2 from fossil fired power plants. Part B: The energy suitability of integrated tri-reforming power plants (ITRPPs) for methanol production

In Part A of this two-paper work, a novel approach for treatment of CO₂ from fossil fired power plants was studied. 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 industries for production of chemicals (methanol, DME, ammonia and urea, etc.). In particular, 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 fact, the methanol can be used in DMFC (Direct Methanol Fuel Cell) or as fuel for on-board reforming to produce hydrogen for PEMFC (Proton Exchange Membrane Fuel Cell).     

Co-production system of hydrogen and electricity based on coal partial gasification with CO2 capture

To solve the problems of high cost and low efficiency of conventional co-production system of hydrogen and electricity with low hydrogen-to-electricity ratio, a novel co-production system based on coal partial gasification with CO₂ capture is proposed and thermodynamically analyzed. The new system integrates the conceptions of cascade conversion of coal and cascade utilization of syngas to realize the system with high efficiency, low cost, environmental friendliness and flexible hydrogen-to-electricity ratio. The performance of the new system is evaluated by an Aspen Plus model and effects of the operating conditions are also studied. It is found that the system with capturing CO₂ of 59.7% and hydrogen-to-electricity ratio of 4.76 holds a high exergy efficiency of 54.3% when the carbon conversion ratio of the pressurized fluidized bed (PFB) gasifier is equal to 0.7. The carbon conversion ratio of the PFB gasifier is a dominant factor to decide the performance of system. In comparison with the series-type co-production system, the parallel-type co-production system and separate production system, the new system proposed in this study has exergy-saving efficiency of 17.7%, 15.1% and 8.9%, respectively.     

Boiling coal in water: Hydrogen production and power generation system with zero net CO2 emission based on coal and supercritical water gasification

Coal is the single most important fuel for power generation today. Nowadays, most coal is consumed by means of “burning coal in air” and pollutants such as NO_x, SO_x, CO₂, PM2.5 etc. are inevitably formed and mixed with excessive amount of inner gases, so the pollutant emission reduction system is complicated and the cost is high. IGCC is promising because coal is gasified before utilization. However, the coal gasifier mostly operates in gas environments, so special equipments are needed for the purification of the raw gas and CO₂ emission reduction. Coal and supercritical water gasification process is another promising way to convert coal efficiently and cleanly to H₂ and pure CO₂. The gasification process is referred to as “boiling coal in water” and pollutants containing S and N deposit as solid residual and can be discharged from the gasifier. A novel thermodynamics cycle power generation system was proposed by us in State Key Laboratory of Multiphase Flow in Power Engineering (SKLMFPE) of Xi'an jiaotong University (XJTU), which is based on coal and supercritical water gasification and multi-staged steam turbine reheated by hydrogen combustion. It is characterized by its high coal-electricity efficiency, zero net CO₂ emission and no pollutants. A series of experimental devices from quartz tube system to a pilot scale have been established to realize the complete gasification of coal in SKLMFPE. It proved the prospects of coal and supercritical water gasification process and the novel thermodynamics cycle power generation system.     

Synthesis gas production in the combined CO2 reforming with partial oxidation of methane over Ce-promoted Ni/SiO2 catalysts

A series of nickel-based catalyst supported on silica (Ni/SiO₂) with different loading of Ce/Ni (molar ratio ranging from 0.17 to 0.84) were prepared using conventional co-impregnation method and were applied to synthesis gas production in the combination of CO₂ reforming with partial oxidation of methane. Among the cerium-containing catalysts, the cerium-rich ones exhibited the higher activity and stability than the cerium-low ones. The temperature-programmed reduction (TPR) and UV–vis diffuse reflectance spectroscopy (UV–vis DRS) analysis revealed that the addition of CeO₂ reduced the chemical interaction between Ni and support, resulting in an increase in reducibility and dispersion of Ni. Over NiCe-x/SiO₂ (x = 0.17, 0.50, 0.67, 0.84) catalysts, the reduction peak in TPR profiles shifted to the higher temperature with increasing Ce/Ni molar ratio, which was attributed to the smaller metallic nickel size of the reduced catalysts. The transmission electron microscopy (TEM) and X-ray diffraction (XRD) for the post-reaction catalysts confirmed that the promoter retained the metallic nickel species and prevented the metal particle growth at high reaction temperature. The NiCe-0.84/SiO₂ catalyst with small Ni particle size exhibited the stable activity with the constant H₂/CO molar ratio of 1.2 during 6-h reaction in the combination of CO₂ reforming with partial oxidation of methane at 850 °C and atmospheric pressure.     

Calcium looping gasification for high-concentration hydrogen production with CO2 capture in a novel compact fluidized bed: Simulation and operation requirements

The coal/CaO/steam gasification system is one of the clean coal technologies being developed for hydrogen production with inherent carbon dioxide separation. A novel reactor configuration for the system is proposed in this paper. It consists of three major counterparts: a gasifier, a riser and a regenerator. A regenerable calcium-based sorbent CaO is used to remove carbon dioxide. In the gasifier, the coal-steam gasification reaction occurs with in situ carbon dioxide removal by carbonation reaction. The removal of carbon dioxide favors the gasification and water-shift reaction equilibrium and enables the production of a hydrogen-rich gas stream. CaO is regenerated in the regenerator by burning the unreacted char with oxygen, and a pure stream of carbon dioxide is separated after a cyclone. The regenerated CaO then flows into the riser above the gasifier, and removes the carbon dioxide in the outlet gases from the gasifier and drives the water-gas shift reaction forward, further improving the hydrogen purity. In this work, the feasibility and optimum process conditions of the proposed system were described. The hydrogen purity can reach 96 vol% at a steam flow 80 mol/s and CaO recycle rate 30 mol/s when the carbon conversion rate is 0.50. Increasing the steam flow and CaO recycle rate can enhance the hydrogen yield and purity. With the rise of operation pressure from 1 bar to 10 bar, the hydrogen yield and purity decrease and methane yield increases. High pressure leads to higher calcination temperature. At 10 bar, the temperature for CaCO₃ decomposition is approximately 1100 °C, at such temperature, the sorbent is easy to deactivate. The appropriate temperatures in the gasifier and the riser are 700 and 600 °C, respectively. An analysis of heat integration is conducted. The maximum carbon conversion rate is ∼0.65. A hydrogen production efficiency of 58.5% is obtained at a carbon conversion rate 0.50, steam flow 60 mol/s and CaO recycle rate 30 mol/s, with a hydrogen purity of 93.7 vol%.     

Methane decomposition with some CO2 as co-feed: Co-production of syngas and carbon fibers/microspheres by using a hybrid of K2CO3 and coal char

Co-production of hydrogen and valuable carbonaceous materials by catalytic methane decomposition (CMD) is a promising process. However, nowadays it is still difficult for various carbon catalysts to make it. Here CMD with addition of some CO₂ as co-feed was proposed and evaluated by using a hybrid of K₂CO₃ and coal char (CC). Effect of the additional CO₂ as co-feed was investigated on methane conversion, the outlet gas composition, and the deposited carbon morphology. The results show that co-production of syngas (H₂ and CO) and carbon fibers/microspheres could be obtained along with high and stable methane (around 80%) and CO₂ conversion (up to about 100%) in the process. Stable molar ratios of H₂/CO (ranging from 0.6:1 to 5:1) as well as different carbon morphologies (amorphous, fibrous or microspherical) can be regulated and controlled by the molar ratio of CH₄/CO₂ (from 75:10 to 75:75) in the feedstock. Quantitative and qualitative analysis of the products show that there is probably a synergy between K₂CO₃ and CC during the reaction process.     

Hydrogen production with CO2 capture by coupling steam reforming of methane and chemical-looping combustion: Use of an iron-based waste product as oxygen carrier burning a PSA tail gas

In this work it is analyzed the performance of an iron waste material as oxygen carrier for a chemical-looping combustion (CLC) system. CLC is a novel combustion technology with the benefit of inherent CO₂ separation that can be used as a source of energy for the methane steam reforming process (SR). The tail gas from the PSA unit is used as fuel in the CLC system.The oxygen carrier behaviour with respect to gas combustion was evaluated in a continuous 500 W_th CLC prototype using a simulated PSA off-gas stream as fuel. Methane or syngas as fuel were also studied for comparison purposes. The oxygen carrier showed enough high oxygen transport capacity and reactivity to fully convert syngas at 880 °C. However, lower conversion of the fuel was observed with methane containing fuels. An estimated solids inventory of 1600 kg MW_th⁻¹ would be necessary to fully convert the PSA off-gas to CO₂ and H₂O. An important positive effect of the oxygen carrier-to-fuel ratio up to 1.5 and the reactor temperature on the combustion efficiency was found.A characterization of the calcined and after-used particles was carried out showing that this iron-based material can be used as oxygen carrier in a CLC plant since particles maintain their properties (reactivity, no agglomeration, high durability, etc.) after more than 111 h of continuous operation.