Gasification of Microalgae Using Supercritical Water and the Potential of Effluent Recycling

The gasification of microalgae in supercritical water was investigated in this work. The product gas contained mainly H₂, CO₂, CH₄, and C₂H₆. Operation at high temperatures and lower biomass concentrations resulted in the highest carbon gasification efficiency and the lowest total organic carbon levels in the residual water. Due to its content of inorganic nutrients, the residual water was applied as cultivation medium for microalgae. However, algal growth in the untreated residual water was inhibited by the existence of potentially toxic substances evolved from gasification. Upon treatment by activated carbon filtration and ultraviolet light degradation, these substances were eliminated and cultivation in the residual water was possible. The major fraction of inorganic residues from gasification was recovered by means of water purging, increasing the potential of nutrient recycling for cultivation.     

Catalysis of gasification of coal-derived cokes and chars

Calcium is the most important in-situ catalyst for gasification of US coal chars in O₂, CO₂ and H₂O. It is a poor catalyst for gasification of chars by H₂. Potassium and sodium added to low-rank coals by ion exchange and high-rank coals by impregnation are excellent catalysts for char gasification in O₂, CO₂ and H₂O. Carbon monoxide inhibits catalysis of the CH₂O reaction by calcium, potassium and sodium; H₂ inhibits catalysis by calcium. Thus injection of synthesis gas into the gasifier will inhibit the CH₂O reaction. Iron is not an important catalyst for the gasification of chars in O₂, CO₂ and H₂O, because it is invariably in the oxidized state. Carbon monoxide disproportionates to deposit carbon from a dry synthesis gas mixture (3 vol H₂ + 1 vol CO) over potassium-, sodium- and iron-loaded lignite char and a raw bituminous coal char, high in pyrite, at 1123 K and 0.1 MPa pressure. The carbon is highly reactive, with the injection of 2.7 kPa H₂O to the synthesis gas resulting in net carbon gasification. The effect of traces of sulphur in the gas stream on catalysis of gasification or carbon-forming reactions by calcium, potassium, or sodium is not well understood at present. Traces of sulphur do, however, inhibit catalysis by iron.     

Air blown partial gasification of coal in a pilot plant pressurized spout-fluid bed reactor

The advanced high efficiency cycles are all based on gas turbine technology, so coal gasification is the heart of the process. A 2 MW_th spout-fluid bed gasifier has been constructed to study the partial gasification performance of a high ash Chinese coal. This paper presents the results of pilot plant partial gasification tests carried out at 0.5 MPa pressure and temperatures within the range of 950–980 °C in order to assess the technical feasibility of the raw gas and residual char generated from the gasifiier for use in the gas turbine based power plant. The results indicate that the gasification process at a higher temperature is better as far as carbon conversion, gas yield and cold gas efficiency are concerned. Increasing steam to coal ratio from 0.32 to 0.45 favors the water–gas and water–gas shift reactions that causes hydrogen content in the raw gas to rise. Coal gasification at a higher bed height shows advantages in gas quality, carbon conversion, gas yield and cold gas efficiency. The gas heating value data obtained from the deep-bed-height displays only 6–12% lower than the calculated value on the basis of Gibbs free energy minimization. The char residue shows high combustion reactivity and more than 99% combustion efficiency can be achieved.     

Three‐stage well‐mixed reactor model for a pressurized coal gasifier

Three Canadian coals of different rank were gasified with air‐steam mixtures in a 0.1 m diameter spouted bed reactor at pressures to 292 kPa, average bed temperatures varying between 840 and 960°C, and steam‐to‐coal feed ratios between 0.0 and 2.88. In order to analyze gasifier performance and correlate data, a three‐stage model has been developed incorporating instantaneous devolatilization of coal, instantaneous combustion of carbon at the bottom of the bed, and steam/carbon gasification and water gas shift reaction in a single well mixed isothermal stage. The capture of H₂S by limestone sorbent injection is also treated. The effects of various assumptions and model parameters on the predictions were investigated. The present model indicates that gasifier performance is mainly controlled by the fast coal devolatilization and char combustion reactions, and the contribution to carbon conversion of the slow char gasification reactions is comparatively small. The incorporation of tar decomposition into the model provides significantly closer predictions of experimental gas composition than is obtained otherwise.     

Gasification of western canadian lignite coals

Samples of a typical Estevan lignite coal (empirical formula CH_0.81 O_0.25 N_0.01 S_0.003) with a heating value of 16.713 MJ/kg were gasified with air only and air/steam mixtures at near atmospheric and high pressures up to 6 MPa. The carbon content of ash/char residues of the gasification reactions varied from 1.2% for air/steam reactions and was in the 16-53% range for reactions using air only, For all experiments the end point was clearly indicated by a rapid change in oxygen concentration in the gas samples. Plots of the fractional conversion of carbon as a function of time, showed high initial reaction rates as the volatile matter in coal is gasified. The rates diminish as the carbon is being consumed. The heating values for the gas samples collected during each run showed a large correlation with the methane content of the sample.     

Experiment and mathematical modeling of a bench-scale circulating fluidized bed gasifier

The gasification of two different coals and chars with CO₂ and CO₂/O₂ mixture in a 48-mm-i.d. circulating fluidized bed (CFB) gasifier is investigated. The effects of operation condition on gas composition, carbon conversion and gasification efficiency were studied. A simple CFB coal gasification district mathematical model has been set up. The effects of coal type and CFB operating conditions on CFB coal gasification are discussed based on the CFB gasification test and model simulation. The main operation parameters in CFB gasification system are coal type, gas superficial velocity, circulating rate of solids and reaction temperature. It is found that CO concentration and carbon conversion increase with increasing solids circulating rate and decreasing gas velocity due to the increase in gas residence time and solids holdup in the CFB. The carbon conversion increases with increasing temperature and O₂ concentration in the inlet gas. The experimental results prove that the CFB gasifier works well for high volatile, high reactivity coal.     

The Gibbs Free Energy Gradient Method for RDF gasification modelling

Starting from an equilibrium model for gasification, this research group has devised a new mathematical model, the so called Gibbs Free Energy Gradient Method Model (GMM). This model permits to bypass the semi-qualitative view, typical of equilibrium models, which assume very restrictive hypotheses such as equilibrium state for all the reactions involved in gasification process, complete conversion of carbon matter, gasification products in gas phase only. GMM model overcomes these limitations providing a quantitative point of view, even though the hypothesis of no tar production affects both models.GMM model has been applied to RDF gasification, supplying reliable results in the gasification process analysis. Model computations in terms of gas yield, gas composition, low heating value and H₂ yield, have been compared with literature results, showing that computed data are in good agreement with experimental ones.     

Effect of CO<Subscript>2</Subscript> addition on lignite gasification in a CFB reactor: A pilot-scale study

The addition of carbon dioxide to the gasification media during lignite gasification is introduced. The paper presents thermodynamic grounds of CO₂ enhanced gasification using a simplified equilibrium model. Experimental tests conducted using a pilot-scale circulating fluidized bed gasifier are discussed. Detailed analysis of the CO₂/C ratio on process conditions, namely on the process gas composition, lower heating value and H₂/CO ratio, is provided. Process gas composition implies that the gas is suitable for heat and power generation. Alternatively, CO₂ enhanced gasification could be considered as a carbon capture and utilization technology when external, renewable heat supply to the process is used. The results thus obtained are the initial step toward development of the CO₂ enhanced gasification process.     

Nitrous oxide decomposition and reduction over copper catalysts supported on various types of carbonaceous materials

Copper supported on three different allotropic forms of carbon materials have been prepared and evaluated as catalysts for the N₂O decomposition and reduction reactions. It was found that all the catalysts underwent severe deactivation during the N₂O decomposition reaction due to the gasification of carbon substrates. This behavior was particularly evident when activated carbon was used as the support medium. The chemical identity of the active entity involved in the carbon gasification process is believed to consist of a mixture of Cu⁺ and Cu²⁺ species and, according to the well established mechanism, the reaction proceeds in such a manner so that the surface of the catalyst undergoes a redox cycle at the gas/solid carbon interface. The introduction of CO into the system was shown to result not only in an enhancement in the activity of the desired N₂O decomposition reaction, but also served to inhibit the deleterious carbon gasification process. In addition, this procedure stabilized the copper particles in the metallic state, which is the active species responsible for the dissociation of N₂O. Copper dispersed on a diamond substrate appeared to attain the highest activity for the N₂O reduction reaction, a feature that is associated with the ability of the metal to undergo a wetting and spreading action on the support surface, possibly resulting in an epitaxial relationship between the two components.     

Numerical modeling of a jetting fluidized bed gasifier and the comparison with the experimental data

A model for a jetting fluidized bed gasifier is developed, treating the grid, bubble and freeboard zones in series. Reactions including char combustion, steam gasification, CO₂ gasification and water–gas shift reaction are taken into account. The effects on model predictions of assumptions regarding the primary products of char combustion and char reactivity factor are analyzed by comparing the predictions with experimental data from a bench-scale jetting fluidized bed gasifier using different kinds of chars. Contributions of various reactions and different zones and phases to carbon conversion are analyzed.     

Comprehensive study of the influence of total pressure on products yields in fluidized bed gasification of wood sawdust

Wood sawdust gasification experiments were performed in a steam fluidized bed at 800 °C between 2 and 10 bar. An evolution of gas yields with time was measured during the tests, and especially an increase of hydrogen and carbon dioxide yields. This test duration effect was ascribed to char build-up in the bed. As tests proceed, the contribution of char steam gasification to gas yield increases, and the catalytic effect of char on hydrocarbons and tar conversion and on water-gas shift reaction is enhanced.As total pressure increases from 2 to 10 bar, hydrogen, carbon dioxide and methane yields increase by 16%, 53% and 38% respectively, whereas carbon monoxide yield decreases by 33%. The changes in gaseous yields with pressure can be partly explained by the influence of pressure on gas phase reactions (acceleration of water-gas shift kinetics and change in hydrocarbon reactions). The increase of methane yield with pressure is rather suggested to be linked to a change in secondary pyrolysis reactions scheme under high pressure.     

Variation of the pore structure of coal chars during gasification

The variation of the pore structure of several coal chars during gasification in air and carbon dioxide was studied by argon adsorption at 87 K and CO₂ adsorption at 273 K. It is found that the surface area and volume of the small pores (<10 Å) do not change with carbon conversion when the coal char is gasified in air, while those of the larger pores (10-20 Å, 20-50 Å, 50-2500 Å) increase with increase of carbon conversion. However in CO₂ gasification, all the pores in different size ranges increase in surface area and volume with increase of carbon conversion. Simultaneously, the reaction rate normalized by the surface area of the pores >10 Å for air gasification is constant over a wide range of conversion (>20%), while for CO₂ gasification similar results are obtained using the total surface area. However, in the early stages of gasification (<20%) the normalized reaction rate is much higher than that in the later stage of gasification, due to existence of more inaccessible pores in the beginning of gasification. The inaccessibility of the micropores to adsorption at low and ambient temperatures is confirmed by the measurement of the helium density of the coal chars. The random pore model can fit the experimental data well and the fitted structural parameters match those obtained by physical gas adsorption for coal chars without closed pores.     

Recovery of carbon fibres and production of high quality fuel gas from the chemical recycling of carbon fibre reinforced plastic wastes

A solvolysis process to depolymerize the resin fraction of carbon fibre reinforced plastic waste to recover carbon fibre, followed by hydrothermal gasification of the liquid residual product to produce fuel gas was investigated using batch reactors. The depolymerisation reactions were carried out in ethylene glycol and ethylene glycol/water mixtures at near-critical conditions of the two solvents. With ethylene glycol alone the highest resin removal of 92.1% was achieved at 400 °C. The addition of water to ethylene glycol led to higher resin removals compared to ethylene glycol alone. With an ethylene glycol/water ratio of 5, at 400 °C, resin removal was 97.6%, whereas it was 95.2% when this ratio was 3, at the same temperature. The mechanical properties of the recovered carbon fibre were tested and showed minimal difference in strength compared to the virgin carbon fibre. The product liquid, containing organic resin degradation products was then subjected to catalytic supercritical water gasification at 500 °C and 24 MPa in the presence of NaOH and Ru/Al₂O₃ as catalysts, respectively. Up to 60 mol.% of H₂ gas was produced with NaOH as catalyst, and 53.7 mol.% CH₄ gas was produced in the presence of Ru/Al₂O₃.     

Modeling of catalytic gasification kinetics of coal char and carbon

Calcium- and potassium-catalyzed gasification reactions of coal char and carbon by CO₂ are conducted, and the common theoretical kinetic models for gas-carbon (or char) reaction are reviewed. The obtained experimental reactivities as a function of conversion are compared with those calculated based on the random pore model (RPM), and great deviations are found at low or high conversion levels as predicted by theory. Namely, calcium-catalyzed gasification shows enhanced reactivity at low conversion levels of <0.4, whereas potassium-catalyzed gasification indicated a peculiarity that the reactivity increases with conversion. CO₂ chemisorption analysis received satisfactory successes in both interpreting catalytic effects and correlating the gasification reactivity with irreversible CO₂ chemical uptakes (CCU_ir) of char and carbon at 300 °C. In details, calcium and potassium additions led to significant increases in CCU_ir and correspondent high reactivities of the char and carbon. Furthermore, CCU_ir of char and carbon decreased with conversion for calcium-catalyzed reaction but increased for potassium-catalyzed one, corresponded to the tendency of their reactivity. The RPM is extended and applied to these catalytic gasification systems. It is found that the extended RPM predicts the experimental reactivity satisfactorily. The most important finding of this paper is that the empirical constants in the extended RPM correlate well with catalyst loadings on coal.     

高效能两段组合式煤气化过程热态试验

针对现有气流床气化技术在显热回收方面的不足,华东理工大学洁净煤技术研究所创新性开发煤基两段组合式气化工艺。在所建立的两段组合式煤气化炉热态试验装置上,考察了二段处理煤量和一段出口煤气组成对出口煤气热值、有效气浓度、二段碳转化率、水蒸气和二氧化碳转化率的影响。试验结果表明此气化工艺能有效利用一段炉煤气中的显热,提高气化炉出口煤气热值;二段适宜加入褐煤量为1400g,是一段处理量的10%;二段加煤量过多会降低二段煤层反应温度和促使焦油的生成;随着一段气化炉出口煤气所含水蒸气、CO2等气化剂浓度的增加,其对显热回收的作用就更明显;该工艺能减少CO2排放,具有良好的环境效益。     

Performance of an entrained-flow gasification technology of pulverized coal in pilot-scale plant

Performance of an entrained-flow gasification technology of pulverized coal in pilot-scale plant is introduced. The gasifier was operated for a throughput of 30–45 t coal per day at pressures of 1–3 MPa. Dense-phase pneumatic conveying was employed for coal's feeding to the gasifier using nitrogen and carbon dioxide as carrier gas, respectively. Effects of the operating conditions including oxygen/carbon ratio and steam/carbon ratio on gasification results were investigated, and the concentration of (CO + H₂) in gaseous products reached up to about 97% (vol., dry basis) when CO₂ was employed as carrier gas. Moreover, performances of some important instruments in the conveying system of pulverized coal, such as the level indicator and the solid mass flow meter, were also investigated. The typical operating results in this plant such as (CO + H₂) concentration, oxygen consumption, coal consumption, carbon conversion and cold gas efficiency were almost as good as those of some well-known dry-fed entrained-flow coal gasification plants.     

Coal gasification by a mixture of air and carbon dioxide in the filtration combustion mode

This paper presents the results of a numerical and experimental study of gasification of carbonaceous materials in the filtration combustion mode using mixtures of air with CO₂ as an oxidizer. The results obtained are compared with the results on gasification of carbonaceous materials by a steam–air mixture. It is shown that the replacement of steam in the gaseous oxidizer by an equal volume CO₂ leads to a marked reduction in the combustion temperature. The maximum calorific values of the product gas in coal gasification by a mixture of air and CO₂ are close to the values obtained for steam–air gasification.     

Entrained flow gasification of coal: 1. Evaluation of mixing and reaction processes from local measurements

Local mixing and reaction processes were studied within a laboratory-scale, entrained coal gasifier at atmospheric pressure, using a Utah high-volatile, low-sulphur bituminous coal at a design flow rate of 24.5 kg h⁻¹. The coal-oxygen-steam feed mass ratio was 1.00:0.91:0.27. A water-quenched sample probe was used to collect radial gas and char samples at seven different axial positions in the 124 cm long reactor for the measurement of gasification products and residual char composition. The observed carbon conversion was 79 ± 3%. Coal hydrogen and oxygen were converted more rapidly and more completely than carbon. Devolatilization, which occurred very rapidly near the inlet, led to most of this carbon conversion; heterogeneous char reactions with CO₂ and steam apparently accounted for the balance. Oxygen was consumed through reaction with volatiles very quickly in the upper gasifier region. These data were used to evaluate mixing and reaction characteristics within the reactor. Agreement of measurements with predictions from a generalized two-dimensional entrained coal gasification model was good.     

Catalysed carbon gasification with Ba13CO3

The interaction of barium carbonate with carbon black was studied to understand catalysed CO₂ gasification of carbon. Temperature-programmed reaction with isotopic labelling of the carbonate and the carbon showed that carbon dramatically accelerated the rate of BaCO₃ decomposition to form BaO and CO₂, which rapidly gasified carbon to form CO. Pure BaCO₃ was observed to exchange carbon dioxide with the gas-phase, and the exchange rate was increased significantly by carbon at higher temperatures, due to formation of a carbon-carbonate complex. The interaction of BaCO₃ and C to form a complex occurred well below gasification temperatures, and BaCO₃ did not decompose until after gasification began and the gas phase CO₂ concentration was low. During catalysed gasification, formation of gaseous CO from a surface oxide is shown directly to be the slow step in the reaction. The active catalyst appears to cycle between BaCO₃ and BaO (both of which interact with carbon). The rates of carbonate decomposition, catalytic gasification, and exchange with gaseous CO₂ are all slower for BaCO₃ than for K₂CO₃, indicating the large differences in carbonate-carbon interaction between alkali carbonates and alkaline earth carbonates. The two carbonates apparently follow different reaction mechanisms.     

Conversion of Lower Hydrocarbons in the Presence of Carbon Dioxide: The Theoretic Analysis and Catalytic Tests over Active Carbon Supported Vanadium Oxide

The results of thermodynamic analysis of methane oxidative coupling and dehydrogenation of C₂–C₄ hydrocarbons in the presence of carbon dioxide were compared to the corresponding results in an inert gas atmosphere. Moreover, conversion of alkanes in some undesirable side reactions, such as decomposition of alkanes to the synthesis gas or to carbon oxide and water, as well as the gasification of coke by carbon dioxide in the Boudouard reaction, were investigated. Finally, the results of the theoretical calculations were compared with the experimental data obtained over VO_x/C_act catalyst. The results are discussed in relation to the acid–base properties of the catalyst surface and the atomic charge on the hydrogen most susceptible to abstraction (i.e., the weakest C–H bond in hydrocarbons). Thus, the changes of the catalytic performance in the presence and absence of carbon dioxide are explained.