Technoeconomic analysis of a methanol plant based on gasification of biomass and electrolysis of water

Methanol production process configurations based on renewable energy sources have been designed. The processes were analyzed in the thermodynamic process simulation tool DNA. The syngas used for the catalytic methanol production was produced by gasification of biomass, electrolysis of water, CO₂ from post-combustion capture and autothermal reforming of natural gas or biogas. Underground gas storage of hydrogen and oxygen was used in connection with the electrolysis to enable the electrolyser to follow the variations in the power produced by renewables. Six plant configurations, each with a different syngas production method, were compared. The plants achieve methanol exergy efficiencies of 59–72%, the best from a configuration incorporating autothermal reforming of biogas and electrolysis of water for syngas production. The different processes in the plants are highly heat integrated, and the low-temperature waste heat is used for district heat production. This results in high total energy efficiencies (∼90%) for the plants. The specific methanol costs for the six plants are in the range 11.8–25.3 €/GJ_exergy. The lowest cost is obtained by a plant using electrolysis of water, gasification of biomass and autothermal reforming of natural gas for syngas production.     

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.     

CO2 emission balances for different black liquor gasification biorefinery concepts for production of electricity or second-generation liquid biofuels

Black liquor gasification (BLG) is currently being developed as an alternative technology for energy and chemical recovery at chemical pulp mills. This study examines how different assumptions regarding systems surrounding the pulp mill affect the CO₂ emission balances for different BLG concepts. The syngas from the gasification process can be used for different applications; this study considers production of renewable motor fuels and electricity generation. Both a market pulp mill and an integrated pulp and paper mill are considered as host mill for the BLG plant. Furthermore, the consequences of limited availability of biomass are shown, i.e., increasing the use of biomass in a mill is not necessarily CO₂-neutral. The results show that the potential to reduce CO₂ emissions by introducing BLG is generally much higher for a market pulp mill than for an integrated pulp and paper mill. Electricity generation from the syngas is favoured when assuming high grid electricity CO₂ emissions where as motor fuel production is favoured when assuming low grid electricity CO₂ emissions. When considering the consequences of limited availability of biomass, the CO₂ emission balances are strongly affected, in some cases changing the results from a decrease to an increase of the CO₂ emissions.     

Sorbent enhanced hydrogen production from steam gasification of coal integrated with CO2 capture

In this work, CO₂ capture and H₂ production during the steam gasification of coal integrated with CO₂ capture sorbent were investigated using a horizontal fixed bed reactor at atmospheric pressure. Four different temperatures (650, 675, 700, and 750 °C) and three sorbent-to-carbon ratios ([Ca]/[C] = 0, 1, 2) were studied. In the absence of sorbent, the maximum molar fraction of H₂ (64.6%) and conversion of coal (71.3%) were exhibited at the highest temperature (750 °C). The experimental results verified that the presence of sorbent in the steam gasification of coal enhanced the molar fraction of H₂ to more than 80%, with almost all CO₂ was fixed into the sorbent structure, and carbon monoxide (CO) was converted to H₂ and CO₂ through the water gas shift reaction. The steam gasification of coal integrated with CO₂ capture largely depended on the reaction temperature and exhibited optimal conditions at 675 °C. The maximum molar fraction of H₂ (81.7%) and minimum CO₂ concentration (almost 0%) were obtained at 675 °C and a sorbent-to-carbon ratio of 2.     

Technoeconomic assessment of China’s indirect coal liquefaction projects with different CO2 capture alternatives

ICL (Indirect coal liquefaction), an alternative fuel-supplying technology, has drawn much attention and caused considerable debate in China’s energy sector. The hurdles to its development include the high risk of investment into large-scale installations, the high CO₂ emissions and water resource consumption. A comprehensive assessment of ICL is urgently needed. This study provides an economic assessment and a technical analysis based on process simulations. To address the future challenge of curbing CO₂ emissions, three absorption methods are compared for capturing the CO₂ released from the ICL process: DMC (a novel absorbent), MEA and Rectisol. The comparative results suggest that physical absorbents, represented by Rectisol and DMC, have a remarkable advantage over chemical absorption processes, represented by MEA. The Rectisol process costs the least, while the DMC process is close to the same level. As a novel absorbent, DMC has the potential to be widely used in the future. The economic analysis of ICL predicted a high capital cost of over 35 billion yuan and an overall product cost of approximately 3800 yuan/ton for the baseline. In addition, via a sensitivity analysis, coal price, electricity price and capacity factor were identified as the three most influential factors affecting the overall product cost.     

Enhanced hydrogen-rich gas production from steam gasification of coal in a pressurized fluidized bed with CaO as a CO2 sorbent

Steam gasification of a typical Chinese bituminous coal for hydrogen production in a lab-scale pressurized bubbling fluidized bed with CaO as CO₂ sorbent was performed over a pressure range of ambient pressure to 4 bar. The compositions of the product gases were analyzed and correlated to the gasification operating variables that affecting H₂ production, such as pressure (P), mole ratio of steam to carbon ([H₂O]/[C]), mole ratio of CaO to carbon ([CaO]/[C]) and temperature (T). The experimental results indicated that the H₂ concentration was enhanced by raising the temperature, pressure and [H₂O]/[C] under the circumstances we observed. With the presence of CaO sorbent, CO₂ in the production gas was absorbed and converted to solid CaCO₃, thus shifting the steam reforming of hydrocarbons and water gas shift reaction beyond the equilibrium restrictions and enhancing the H₂ concentration. H₂ concentration was up to 78 vol% (dry basis) under a condition of 750 °C, 4 bar, [Ca]/[C] = 1 and [H₂O]/[C] = 2, while CO₂ (2.7 vol%) was almost in-situ captured by the CaO sorbent. This study demonstrated that CaO could be used as a substantially excellent CO₂ sorbent for the pressurized steam gasification of bituminous coal. For the gasification process with the presence of CaO, H₂-rich syngas was yielded at far lower temperatures and pressures in comparison to the commercialized coal gasification technologies. SEM/EDX and gas sorption analyses of solid residues sampled after the gasification showed that the pore structure of the sorbent was recovered after the steam gasification process, which was attributed to the formation of Ca(OH)₂. Additionally, a coal-CaO–H₂O system was simulated with using Aspen Plus software. Calculation results showed that higher temperatures and pressures favor the H₂ production within a certain range.     

The influence of membrane CO2 separation on the efficiency of a coal-fired power plant

In this paper, the influence of membrane separation of CO₂ from flue gases and the impacts of the whole CCS process (CO₂ separation and compression) on the performance of a coal-fired power plant are studied. First, the effects of the characteristics of the membrane (selectivity and permeability) and the parameters of the process (feed and permeate pressure) on two indices, CO₂ recovery rate and CO₂ purity are analysed. Next, a method for determining the minimum power loss and efficiency loss of the power plant as a function of these calculated indices is described. Then, the power requirements and efficiency loss (up to 15.4 percentage points) because of the CCS installation are calculated. A method for reducing these losses through the integration of the CCS installation with the power plant is also proposed. The main aims of the integration are heat exchange between media and a decrease in the CO₂ temperature before compression. Implementing this process can result in a significant reduction of the efficiency loss by 8 percentage points.     

Coal gasification in CO2 atmosphere and its kinetics since 1948: A brief review

Numerous coal gasification studies have been found in the literature those employed various kinds of gasifying agents such as steam and carbon dioxide. These studies are featured with wide variations in the parametric conditions and the usage of equipments. Steam is frequently employed as a gasifying agent, however, in several studies carbon dioxide has also been used as a gasifying agent either pure or in combination with other gasifying agents (H₂O, O₂, CO, H₂). This paper is a brief review of the coal gasification with CO₂ as a diluent. Different factors were studied over the coal gasification with CO₂ such as coal rank, pressure, temperature, gas composition, catalyst and the minerals present inside the coal, heating rate, particle size, and diverse reactor types. It also deals with the application of the gas-solid models developed in the literature and the combustion and gasification mechanisms for O₂/CO₂ streams. Moreover, it reviews the kinetics and the reaction rate equations (Arrhenius and Langmuir-Hinshelwood types) for coal-char gasification both in the reaction kinetic control region (low temperature) and the diffusion control region (high temperature) and at both low and high pressures.     

Chemical effects of added CO2 on the extinction characteristics of H2/CO/CO2 syngas diffusion flames

Chemical effects of added CO₂ on flame extinction characteristics are numerically studied in H₂/CO syngas diffusion flames diluted with CO₂. The two representative syngas flames of 80% H₂ + 20% CO and 20% H₂ + 80% CO are inspected according to the composition of fuel mixture diluted with CO₂ and global strain rate. Particular concerns are focused on impact of chemical effects of added CO₂ on flame extinction characteristics through the comparison of the flame characteristics between well-burning flames far from extinction limit and flames at extinction. It is seen that chemical effects of added CO₂ reduce critical CO₂ mole fraction at flame extinction and thus extinguish the flame at higher flame temperature irrespective of global strain rate. This is attributed by the suppression of the reaction rate of the principal chain branching reaction through the augmented consumption of H-atom from the reaction CO₂ + H→CO + OH. As a result the overall reaction rate decreases. These chemical effects of added CO₂ are similar in both well-burning flames far from extinction limit and flames at extinction. There is a mismatching in the behaviors between critical CO₂ mole fraction and maximum flame temperature at extinction. This anomalous phenomenon is also discussed in detail.     

Iron and nickel doped alkaline-earth catalysts for biomass gasification with simultaneous tar reformation and CO2 capture

The tar reforming catalytic activity of iron and nickel based catalysts supported on alkaline-earth oxides CaO, MgO and calcined dolomite [a (CaMg)O solid solution] has been investigated in a fixed bed reactor operating at temperatures ranging from 650 to 850 °C; toluene and 1-methyl naphthalene were used as model compounds for tar generated during biomass gasification. The CO₂ absorption capacities of Fe/(CaMg)O and Ni/(CaMg)O were also investigated at the lower temperature condition (650 °C) at which the sorption process is thermodynamically favoured. It was found that iron and nickel may be optimised in the substrate particles to enhance both the catalytic activity and the carbon deposition resistance during catalytic tests, at the same time reducing critical limitations on CO₂ capture capacity.     

Characteristics of cardboard and paper gasification with CO2

Evolutionary behavior of syngas chemical composition and yield have been examined for paper and cardboard at three different temperatures of 800, 900 and 1000 °C using CO₂ as the gasifying agent at constant flow rate. Specifically the evolution of syngas chemical composition with time has been investigated. Pyrolysis of the sample was dominant at the beginning of the gasification process as observed from the high initial devolatilization of the sample followed by char gasification of material to form syngas for a long period of time. Results provided the role of gasification temperature on kinetics of the CO₂ gasification process. Increase in gasification temperature provided increased conversion of the sample material to syngas. Thus the sample conversion to syngas was low at the low temperature of 800 °C while at elevated temperatures of 900 and 1000 °C substantial enhancement of the kinetics process occurred. The evolution of extensive reaction rate of carbon-monoxide was calculated. Results show that increase in temperature increased the extensive reaction rate of carbon-monoxide. The global behavior of syngas chemical composition examined at three different temperatures revealed a peak in concentration of H₂ to exhibit after few minutes into the gasification that changed with gasification temperature. At 800 °C gasification temperature peak in H₂ was displayed at 3 min into gasification while it decreased to only 2 min, approximately, at gasification temperatures of 900 and 1000 °C. The effect of reactor temperature on CO mole fraction has also been examined. Increase in the gasification temperature enhances the mole fraction of CO yields. This is attributed to the increase in forward reaction rate of the Boudouard reaction (C+CO₂2CO). The results show important role of CO₂ gas for the gasification of wastes and low grade fuels to clean syngas.     

Liquid CO2 droplet extraction from gases

Efficient mechanical separation of CO₂ from combustion effluent affects the utilization potential of high CO₂ producers such as coal. Novel mechanical separations of condensing CO₂ from gas flows need to be able to capture the small condensed droplets below the cyclone cut-off limit of 20 μm. We describe the thermodynamics, the energy costs and droplet formation of CO₂ phase separation from combustion effluent and natural gas. We report the first measurements of condensing CO₂ droplet sizes from gas. This shows that application of homogeneous condensation of CO₂ yields much smaller droplets in flue gas (N₂/CO₂) than from contaminated natural gas (CH₄/CO₂). These small droplets can only be efficiently removed at high throughputs using the novel centrifugal method we describe. Such mechanical separations are preferable to the current standard chemical methods because of the much lower environmental footprint.     

Tackling CO2 reduction in India through use of CO2 capture and storage (CCS): Prospects and challenges

CO₂ capture and storage (CCS) is not currently a priority for the Government of India (GOI) because, whilst a signatory to the UNFCCC and Kyoto Protocol, there are no existing greenhouse gas emission reduction targets and most commentators do not envisage compulsory targets for India in the post-2012 phase. The overwhelming priority for the GOI is to sustain a high level of economic growth (8%+) and provision of secure, reliable energy (especially electricity) is one of the widely recognised bottlenecks in maintaining a high growth rate. In such a supply-starved context, it is not easy to envisage adoption of CCS—which increases overall generation capacity and demand for coal without increasing actual electricity supply—as being acceptable. Anything which increases costs—even slightly—is very unlikely to happen, unless it is fully paid for by the international community. The majority viewpoint of the industry and GOI interviewees towards CCS appears to be that it is a frontier technology, which needs to be developed further in the Annex-1 countries to bring down the cost through RD&D and deployment. More RD&D is required to assess in further detail the potential for CO₂ storage in geological reservoirs in India and the international community has an important role to play in cultivating such research.     

Pre-combustion, post-combustion and oxy-combustion in thermal power plant for CO2 capture

This paper presents a summary of technical-economic studies. It allows evaluating, in the French context, the production cost of electricity derived from coal and gas power plants with the capture of CO₂, and the cost per tonne of CO₂ avoided. Three systems were studied: an Integrated Gasification Combined Cycle (IGCC), a conventional combustion of Pulverized Coal (PC) and a Natural Gas Combined Cycle (NGCC). Three main methods were envisaged for the capture of CO₂: pre-combustion, post-combustion and oxy-combustion.For the IGCC, two gasification types have been studied: a current technology based on gasification of dry coal at 27 bars (Shell or GE/Texaco radiant type) integrated into a classical combined cycle providing 320 MWe, and a future technology (planned for about 2015–2020) based on gasification of a coal–water mixture (slurry) that can be compressed to 64 bars (GE/Texaco slurry type) integrated into an advanced combined cycle (type H with steam cooling of the combustion turbine blades) producing a gross power output of 1200 MWe.     

Role of CO2 in the CH4 oxidation and H2 formation during fuel-rich combustion in O2/CO2 environments

The effect of CO₂ reactivity on CH₄ oxidation and H₂ formation in fuel-rich O₂/CO₂ combustion where the concentrations of reactants were high was studied by a CH₄ flat flame experiment, detailed chemical analysis, and a pulverized coal combustion experiment. In the CH₄ flat flame experiment, the residual CH₄ and formed H₂ in fuel-rich O₂/CO₂ combustion were significantly lower than those formed in air combustion, whereas the amount of CO formed in fuel-rich O₂/CO₂ combustion was noticeably higher than that in air. In addition to this experiment, calculations were performed using CHEMKIN-PRO. They generally agreed with the experimental results and showed that CO₂ reactivity, mainly expressed by the reaction CO₂ + H → CO + OH (R1), caused the differences between air and O₂/CO₂ combustion under fuel-rich condition. R1 was able to advance without oxygen. And, OH radicals were more active than H radicals in the hydrocarbon oxidation in the specific temperature range. It was shown that the role of CO₂ was to advance CH₄ oxidation during fuel-rich O₂/CO₂ combustion. Under fuel-rich combustion, H₂ was mainly produced when the hydrocarbon reacted with H radicals. However, the hydrocarbon also reacted with the OH radicals, leading to H₂O production. In fact, these hydrocarbon reactions were competitive. With increasing H/OH ratio, H₂ formed more easily; however, CO₂ reactivity reduced the H/OH ratio by converting H to OH. Moreover, the OH radicals reacted with H₂, whereas the H radicals did not reduce H₂. It was shown that OH radicals formed by CO₂ reactivity were not suitable for H₂ formation. As for pulverized coal combustion, the tendencies of CH₄, CO, and H₂ formation in pulverized coal combustion were almost the same as those in the CH₄ flat flame.     

Laminar burning velocities and flame stability analysis of H2/CO/air mixtures with dilution of N2 and CO2

Experimental measurement of the laminar burning velocities of H₂/CO/air mixtures and equimolar H₂/CO mixtures diluted with N₂ and CO₂ up to 60% and 20% by volume, respectively, were conducted at different equivalence ratios and conditions near to the sea level, 0.95 atm and 303 ± 2 K. Flames were generated using contoured slot-type nozzle burners and Schlieren images were used to determine the laminar burning velocity with the angle method. Numerical calculations were also conducted using the most recent detailed reaction mechanisms for comparison with the present experimental results. Additionally, a study was conducted to analyze the flame stability phenomenology that was found in the present experiments. The increase in the N₂ and CO₂ dilution fractions considerably reduced the laminar burning velocity due to the decrease in heat release and increase in heat capacity. At the same dilution fractions this effect was higher for the case of CO₂ due to its higher heat capacity and dissociation effects during combustion. Flame instabilities were observed at lean conditions. While the presence of CO in the fuel mixture tends to stabilize the flame, H₂ has a destabilizing effect which is the most dominant. A higher N₂ and CO₂ dilution fraction increased the range of equivalence ratios where unstable flames were obtained due to the increase in the thermal-diffusive instabilities.     

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.     

The thermodynamic analysis of two-step conversions of CO2/H2O for syngas production by ceria

Due to the challenges of demands on alternative fuels and CO₂ emission, the conversion of CO₂ has become a hot spot. Among various methods, two-step conversion of CO₂ with catalyst ceria (cerium oxide, CeO₂) appears to be a promising way. Solar energy is commonly employed to drive the conversion systems. This article proposes a solar-driven system with fluidized bed reactors (FBR) for CO₂/H₂O conversions. N₂ is used as the gas of the heat carrier. The products of CO/H₂ could be further used for syngas. To evaluate the capability of the system for exporting work, the system was analysed on the basis of the Second Law of Thermodynamics and the reaction mechanism of ceria. Heat transfer barriers in practical situations were considered. The lowest solar to chemical efficiency is 4.86% for CO₂ conversion, and can be enhanced to 43.2% by recuperating waste heat, raising the N₂ temperature, and increasing the concentration ratio. The analysis shows that the method is a promising approach for CO₂/H₂O conversion to produce syngas as an alternative fuel.     

Catalytic conversion of CH4 and CO2 to synthesis gas on Ni/SiO2 catalysts containing Gd2O3 promoter

A series of Ni/SiO₂ catalysts containing different amounts of Gd₂O₃ promoter was prepared, characterized by H₂-adsorption and XRD, and used for carbon dioxide reforming of methane (CRM) and methane autothermal reforming with CO₂ + O₂ (MATR) in a fluidized-bed reactor. The results of pulse surface reactions showed that Ni/SiO₂ catalysts containing Gd₂O₃ promoter could increase the activity for CH₄ decomposition, and Raman analysis confirmed that reactive carbon species mainly formed on the Ni/SiO₂ catalysts containing Gd₂O₃ promoter. In this work, it was found that methane activation and reforming reactions proceeded according to different mechanisms after Gd₂O₃ addition due to the formation of carbonate species. In addition, Ni/SiO₂ catalysts containing Gd₂O₃ promoter demonstrated higher activity and stability in both CRM and MATR reactions in a fluidized bed reactor than Ni/SiO₂ catalysts without Gd₂O₃ even at a higher space velocity.     

Impacts of equations of state (EOS) and impurities on the volume calculation of CO2 mixtures in the applications of CO2 capture and storage (CCS) processes

Volume property is the necessary thermodynamic property in the design and operation of the CO₂ capture and storage system (CCS). Because of their simple structures, cubic equations of state (EOS) are preferable to be applied in predicting volumes for engineering applications. This paper evaluates the reliabilities of seven cubic EOS, including PR, PT, RK, SRK, MPR, MSRK and ISRK for predicting volumes of binary CO₂ mixtures containing CH₄, H₂S, SO₂, Ar and N₂, based on the comparisons with the collected experimental data. Results show that for calculations on the volume properties of binary CO₂ mixtures, PR and PT are generally superior to others for all of the studied mixtures. In addition, it was found that the binary interaction parameter has clear effects on the calculating accuracy of an EOS in the volume calculations of CO₂ mixtures. In order to improve the accuracy, k_ij was calibrated for all of the EOS regarding the gas and liquid phases of all the studied binary CO₂ mixtures, respectively.