Laboratory studies of the rapid pyrolysis and desulphurization of a Texas lignite

Rapid heating of Alcoa D lignite particles during ‘free-fall’ through a counterflowing pyrolysis gas is an effective method of producing a low sulphur char. For 200 μm particles with residence times of seconds in steam, the organic sulphur of the lignite is reduced from ? 1.3 wt % to ? 0.8 wt % over a temperature range ≈ 700–800 °C. Similar levels of desulphurization were achieved with particles as large as 550 μm, even with shorter residence times. Devolatilization is rapid and substantial with the production of significant quantities of olefins. Steam gasification becomes important above 700 °C for the 200 μm particles. By 820 °C, the conversion of coal to gas is twice as large with steam as for nitrogen, and by 870 °C, it is about four times larger. Chars are reactive and of high surface area. Limited testing suggests that the reduced sulphur chars can be burned directly with emissions of SO₂ below 0.5 g/10⁶J (1.2 lb/10⁶ Btu).     

Possibilities and state of development of nuclear coal gasification processes

By the development work of the last years and the successful operation of a experimental reactor it is clear today that the high temperature reactor is capable to produce heat at a temperature level of 950° C. This heat can be used in different industrial processes, especially for coal gasification. The processes of hydrogasification and steam gasification have been tested in large pilot plants in the past and are thought to be feasible today in connection with use of nuclear energy. In this paper the main aspects of these processes, of the nuclear reactor and of the heat exchanger system are presented and discussed. Questions like the choice and qualification of high temperature materials, the tritium contamination of the product gas and the aspects of licensing are key points of the technical realisation of nuclear process heat applications. This paper tries to summarize some of these results of the development programm of the PNP-Project (Prototyp Nukleare Prozeβwärme) in Germany, which is a common Projekt of German Companies financed by the government.     

Dynamic experimental simulation of hydrogen oriented underground gasification of lignite

The main goal of the study presented in the paper was to experimentally demonstrate the feasibility of lignite gasification to hydrogen-rich gas under the underground conditions simulated in the ex situ reactor. The in situ gasification conditions were simulated both in respect to the coal seam and the surrounding stratum. In the 54-h experiment the process of lignite gasification with oxygen and steam as gasifying medium was tested. The experiment was initially divided into three stages: the ignition stage, the oxygen stage and the steam stage.The gas produced in the steam gasification stage was characterized by the calorific value of 7.8 MJ/m³ and average hydrogen content of 46.3 vol.%. Unfortunately a rapid decrease in the temperature levels and in the amount of produced gas proved that the tested lignite of 53 vol.% moisture content was not suitable for steam gasification. A great amount of thermal energy was consumed for water evaporation which led to a considerable heat loss. An addition of stoichiometric amount of water in the system by adding steam caused the seam to extinguish. Thus only oxygen could be used as the gasifying medium in the gasification of the tested lignite. The average calorific value of gas produced in the stable operation during oxygen gasification stage equaled 5.2 MJ/m³ with the average gas production rate of 16.0 m³/h and the average hydrogen content in the produced gas of 26.4 vol.%.     

串行流化床煤气化试验

针对串行流化床煤气化技术特点,以水蒸气为气化剂,在串行流化床试验装置上进行煤气化特性的试验研究,考察了气化反应器温度、蒸汽煤比对煤气组成、热值、冷煤气效率和碳转化率的影响。结果表明,燃烧反应器内燃烧烟气不会串混至气化反应器,该煤气化技术能够稳定连续地从气化反应器获得不含N₂的高品质合成气。随着气化反应器温度的升高、蒸汽煤比的增加,煤气热值和冷煤气效率均会提高,但对碳转化率影响有所不同。在试验阶段获得的最高煤气热值为6.9 MJ•m^-3,冷煤气效率为68％,碳转化率为92％。     

Experimental simulation of hard coal underground gasification for hydrogen production

The main objective of this study was the assessment of the feasibility of applying the underground hard coal gasification in the production of a hydrogen-rich gas. In the course of the experiment the so-called two-stage gasification process in which oxygen and steam were supplied to the reaction zone separately in alternate stages was investigated. For this purpose a special surface reactor has been constructed, in which the underground conditions were to be imitated both in respect to the coal seam and the surrounding rock layers. The surface simulation of the underground gasification was carried out on extra large coal samples, which allowed the recreation of near real underground conditions. In the reactor an experiment lasting almost 7 days has been performed, with the average hourly gas yields of 7.8 m³/h and 9.2 m³/h for the oxygen and the steam gasification stages, respectively. The average hydrogen concentration during the oxygen stage (heating up) was 15.28% with the maximum of 54.4%. The average hydrogen concentration during the steam stage was 53.77% with the maximum of 62.90%. Thus the feasibility of hydrogen-rich gas production in the process of underground gasification of hard coal has been demonstrated. During the course of the surface experiment an original and unprecedented database of temperature profiles has been acquired which now constitutes an invaluable source of thermodynamic information for the prospective underground gasification activities.     

Technology and economics of coal gasification

The best known commercial coal gasification processes which use oxygen (air) and steam as gasifying media are the gas producer process (normal pressure, fixed bed), Lurgi process (high pressure, fixed bed), Winkler process (normal pressure, fluidized bed) and Koppers-Tetzek process (normal pressure, entrained). Fixed bed and fluidized bed processes are suitable for gasification of noncaking and weakly caking coals with high ash fusion temperatures (> 1200°C). The entrained system is suitable for gasification of any coal. Low-caloric gas (～ 150 Btu/scf) can be produced by the gas producer, Lurgi and Kinkier processes; medium- (～ 300 Btu/scf) and high-caloric (～ 950 Btu/scf) gas by any process. Lurgi and Koppers-Totzek processes are preferred processes for production of synthesis gas at the present time. The costs (/Btu) of production of low-caloric gas are the lowest followed by the medium- and high-caloric gas costs (see Figure 6). The costs of gas production from coal are mainly dependent on the efficiency of the gasification process, scale of operation and the cost of fuel.     

Composition and reactivity of coal from the Khoot deposit in Mongolia

The composition and reactivity characteristics of Khoot coal from Mongolia in the processes of pyrolysis, gasification, thermal dissolution, and the production of porous materials were determined. It was established that the coal is characterized by high activity in the reactions of destruction. In the process of semicoking, the yield of liquid tar was as high as 10%. Highly porous activated carbons with specific surface areas to 900 m²/g and high sorption capacities were obtained by the steam activation of carbonizates. To 60.8% liquid products at low gas formation can be obtained from the Khoot coal in the process of thermal dissolution in a hydrogen-donor solvent at 450°C without the use of hydrogen.     

Coal gasification in steam at very high temperatures

Gasification of pulverized coal in steam has been investigated at heating rates of 10⁶ K/s and peak gas temperatures of 3300 K. These severe conditions were achieved in a batch process reactor by igniting a stoichiometric hydrogen-oxygen mixture in which the coal had been blown into turbulent suspension. Subsequent gas-phase combustion was followed by heat conduction from the nascent steam to the coal. Variable solids/gas mass ratios were investigated. Stabilized carbon gasification yields as high as 80% were achieved.     

Low temperature catalytic steam gasification of HyperCoal to produce H2 and synthesis gas

HyperCoal is an ultra clean coal with ash content <0.05 wt%. Catalytic steam gasification of HyperCoal was carried out with K₂CO₃ at 775–650 °C for production of H₂ rich gas and synthesis gas. The catalytic gasification of HyperCoal showed nearly four times higher gasification rate than raw coal. The major gases evolved were H₂: 63 vol%, CO: 6 vol% and CO₂: 30 vol%. Catalyst was recycled for four times without any significant rate loss. The partial pressure of steam was varied from 0.5 atm to 0.05 atm in order to investigate the effect of steam pressure on H₂/CO ratio. The H₂/CO ratio decreased from 9.5 at 0.5 atm to 1.9 at 0.05 atm. No significant decrease in gasification rate was observed due to change in partial pressure of steam. Gasification rate decreased with decreasing temperature and become very slow at 650 °C. The preliminary results showed that HyperCoal, an ash less coal, could be a potential hydrocarbon resource for H₂ and synthesis gas production at low temperature by catalytic steam gasification process.     

An investigation of the design variables for producing activated carbons from victorian brown coals by reaction with steam

Activation of Latrobe Valley brown coal by reaction with steam was investigated in a continuous indirectly heated shaft activator. The variables studied were the degree of coal gasification achieved, the ratio of steam feed rate to coal feed rate and temperature of activation. The most important of these variables is the degree of gasification of the coal. The ratio of steam feed rate to solids feed rate is unimportant when the value of this variable is greater than 0.036 g/g, and temperature is unimportant in the range 720–930°C. Process limitations which can be caused by channelling of both gas and solids and by heat transfer limitations have been discussed briefly.     

Synthesis gas and char production from Mongolian coals in the continuous devolatilization process

Devolatilization of Mongolian coal (Baganuur coal (BC), Shievee Ovoo coal (SOC), and Shievee Ovoo dried coal (SOC-D)) was investigated by using bench-sized fixed-bed and rotary kiln-type reactors. Devolatilization was assessed by comparing the coal’s type and dry basis, temperature, gaseous flux, tar formation/generation, devolatilization rate, char yield, heating value, and the components of the raw coal and char. In the fixed bed reactor, higher temperatures increased the rate of devolatilization but decreased char production. BC showed higher rates of devolatilization and char yields than SOC or SOC-D. Each coal showed inversely proportional devolatilization and char yields, though the relation was not maintained between the different coal samples because of their different contents of inherent moisture, ash, fixed carbon, and volatile matter. Higher temperatures led to the formation of less tar, though with more diverse components that had higher boiling points. The coal gas produced from all three samples contained more hydrogen and less carbon dioxide at higher temperatures. Cracking by multiple functional groups, steam gasification of char or volatiles, and reforming of light hydrocarbon gas increased with increasing temperature, resulting in more hydrogen. The water gas shift (WGS) reaction decreased with increasing temperature, reducing the concentration of carbon dioxide. BC and SOC, with retained inherent moisture, produced substantially higher amounts of hydrogen at high temperature, indicating that hydrogen production occurred under high-temperature steam. The continuous supply of steam from coal in the rotary kiln reactor allowed further exploration of coal gas production. Coal gas mainly comprising syngas was generated at 700–800 °C under a steam atmosphere, with production greatest at 800 °C. These results suggest that clean char and high value-added syngas can be produced simultaneously through the devolatilization of coal at lower temperature at atmospheric pressure than the entrained-bed type gasification temperature of 1,300–1,600 °C.     

Ash-agglomerating gasification of coal in a spouted bed reactor

Australian bituminous coal (Hoskisson) was gasified with oxygen and steam in a 0.4m diameter spouted bed reactor at atmospheric pressure and temperatures of 1050–1170 °C to produce medium calorific value gas. High-ash agglomerates fell through the throat of the spouted bed under restricted gasification conditions, with no simultaneous loss of coal. The effects of temperature, steam-oxygen ratio, coal feed rate and coal size on carbon conversion, production of ash agglomerates, gas composition and decompsition of steam were established.     

Correlation of gasification rates of various coals measured by a rapid heating method in a steam atmosphere at relatively low temperatures

Twenty-five kinds of coals (carbon content on dry ash-free basis, C[%], ranges from 65.0 to 92.8%) were pyrolysed and gasified simultaneously by use of a rapid heating method (heating rate ≈ 1600 K min⁻¹) in steam at temperatures between 750 and 850 °C to clarify the factors which control the gasification rates of various coals. The relationships were examined in detail between the reactivity of each coal, represented by the initial gasification rate − r_cm0, and various properties such as pore surface area of char, ultimate and proximate analyses of coal, reflectance of coal, contents of metals in char, and the amount of oxygen trapped by char. For gasification at 800 °C, the relation between − r_cm0 and the carbon content C[%] changed abruptly at C ≈ 75–80%. For higher rank coals (C > 75–80%), − r_cm0 was rather small and was well correlated by C[%]. On the other hand, the plot of − r_cm0versus C % scattered largely for the lower rank coals (C < 75–80%). For these coals, the rate of CO₂ formation was much greater than that of CO formation, and was almost proportional to − r_cm0. The CO₂ formation reaction is known to be catalysed by alkali or alkaline earth metals such as Na, K and Ca. Then the reactivities of lower rank coals were supposed to be controlled mainly by the catalytic effect of the minerals in the coal.     

煤气化工艺的发展趋势之一：—两段气化法

如果仔细观察近年来国外开发的和正在开发的各种煤气化工艺,不难发现采用两段气化工艺的愈来愈多,这种气化方法既保持了气流床气化的碳效率高、生产能力大的特点,又吸取了逆流气化的优点,将高温煤气显热用于煤气化反应,使煤气出口温度下降,煤气夹带的熔融液渣固化,因此使气流床气化工艺更趋完善。     

Production of Hydrogen and Syngas via Steam Gasification of Glycerol in a Fixed-Bed Reactor

Glycerol is one of the by-products of transesterification of fatty acids to produce bio-diesel. Increased production of bio-diesel would lead to increased production of glycerol in Canadian market. Therefore, the production of hydrogen, syn gas and medium heating value gas is highly desirable to improve the economics of bio-diesel production process. In this study, steam gasification of pure and crude glycerol was carried out in a fixed-bed reactor at the liquid hourly space velocity (LHSV) and temperature of 0.77 h^?1 and 800 °C, respectively. In this process, the effects of different packing materials such as quartz particle and silicon carbide were studied. Catalytic steam gasification was performed in the presence of commercial Ni/Al₂O₃ catalyst in the range of steam to glycerol weight ratio of 0:100–50:50 to produce hydrogen or syngas when LHSV was maintained constant at 5.4 h^?1. Pure glycerol was completely converted to gas containing 92 mol% syngas (molar ratio of H₂/CO ≈ 1.94) and the calorific value of 13 MJ/m³ at 50:50 weight ratio of steam to glycerol. Hydrogen yield was increased by 15 mol% via the steam gasification process when compared to pyrolysis process. The presence of catalyst increased further the production of hydrogen and total gas in case of both pure and crude glycerol indicating their strong potential of making hydrogen or syngas. Maximum hydrogen, total gas and syn gas production of 68.4 mol%, 2.6 L/g of glycerol and 89.5 mol% were obtained from glycerol using Ni/Al₂O₃ catalyst at temperature and steam to glycerol ratio of 800 °C and 25:75, respectively.     

Gasification of lignite and hard coal with air and oxygen enriched air in a pilot scale ex situ reactor for underground gasification

The main goal of the study presented in the paper was an experimental comparison of the underground lignite and hard coal seams air gasification simulated in the ex situ reactor. In the study lignite and hard coal were gasified with oxygen, air and oxygen enriched air as gasification agents in the 50- and 30-h experiments, respectively, with an intrinsic coal and strata moisture content as a steam source. Application of air as a sole gasification agent was problematic for a resulting rapid decrease in temperatures, deterioration of gas quality and, finally, cessation of gasification reactions. Use of oxygen/air mixture of an optimum ratio led to valuable gas production. In lignite seam gasification with oxygen/air (of 4:2 volume ratio) the average H₂ and CO contents in product gas were 23.1 vol.% and 6.3 vol.%, respectively, and the calorific value was 4.18 MJ/m³, whereas in hard coal gasification with the oxygen/air ratio (of 2:3 volume ratio) the average H₂ and CO contents in produced gas were 18.7 vol.% and 17.3 vol.%, respectively, and product gas calorific value equaled 5.74 MJ/m³.     

Effect of operating conditions on gas components in the partial coal gasification with air/steam

With increasing environmental considerations and stricter regulations, coal gasification, especially partial coal gasification, is considered to be a more attractive technology than conventional combustion. Partial coal gasification was conducted in detail under various experimental conditions in a lab-scale fluidized bed to study the factors that affected gas components and heating value, including fluidized air flow rate, coal feed rate, and steam feed rate, gasification temperature, static bed height, coal type and catalyst type. The experiment results indicate that gasification temperature is the key factor that affects components and the heating value of gas is in direct proportion to gasification temperature. There exists a suitable range of fluidized air flow rate, coal feed rate, steam feed rate and static bed height, which show more complex effect on gas components. High rank bitumite coal is much more suitable for gasification than low rank bitumite coal. The concentrations of H₂, CO and CH₄ of bitumite coal are more than those of anthracite coal. Compounds of alkali/alkaline-earth metals, such as Ca, Na, K etc., enhance the gasification rate considerably. The catalytical effects of Na₂CO₃ and K₂CO₃ are more efficient than that of CaCO₃. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Steam gasification of coal with salt mixture of potassium and nickel in a fluidized bed reactor

Australian coal loaded with a mixed catalyst of K₂SO₄+Ni(NO₃)₂ has been gasified with steam in a fluidized bed reactor of 0.1 m inside diameter at atmospheric pressure. The effects of gas velocity (2-5 U_g/U_mf), reaction temperature (750-900 °C), air/coal ratio (1.6-3.2), and steam/coal ratio (0.63-1.26) on gas compositions, gas yield and gas calorific value of the product gas and carbon conversion have been determined. The product gas quality and carbon conversion can be greatly improved by applying the catalyst; they can also be enhanced by increasing gas velocity and temperature. Up to 31% of the catalytic increment in gas calorific value could be obtained at higher temperatures. In the experimental runs with variation of steam/coal ratio, the catalytic increments were 16-38% in gas calorific value, 14-57% in carbon conversion, 5-46% in gas yield, and 7-44% in cold gas efficiency. With increasing fluidization gas velocity and reaction temperature, the unburned carbon fraction of cyclone fine for catalytic gasification decreased 4-18% and 13-16%, respectively, compared to that for non-catalytic gasification. Presented at the Int’l Symp. on Chem. Eng. (Cheju, Feb. 8–10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University.     

Effect of pre-oxidation on reactivity of chars in steam

The effects of pre-oxidation of char from Taiheiyo coal, a non-caking bituminous coal, in the 400–550 °C temperature range on its gasification reactivity with N₂-H₂O at 0.1 MPa (steam partial pressure of 13.2 kPa) have been investigated. The pre-oxidation of char markedly enhances gasification rates at temperatures between 800 and 900 °C. Reactivity is found to parallel the burn-off level during preoxidation at low temperatures (400–430 °C), whereas at relatively high temperatures (480–550 °C), the burn-off level only affects the reactivity slightly. The amount of CO and CO₂ evolved from the preoxidized char by heat treatment is proportional to the burn-off level at low temperatures (400–430 °C), being closely related to the enhancement of the gasification reactivity in steam.     

Effect of operating conditions on tar and gas composition in high temperature air/steam gasification (HTAG) of plastic containing waste

In this work, the high temperature air/steam gasification (HTAG) technique has been tested for a fuel in pellet form made from waste material of woody and plastic origin. The feedstock was gasified in an updraft fixed bed reactor by mixtures of air and steam (102 Nm³/h, 4% to 82% steam) preheated to 1400 °C, a temperature well above the fluid temperature of the feedstock. The produced gas was analyzed with respect to composition, including a detailed characterization of the tar. Lower heating values up to 9.5 MJ/Nm³ and gas yields as high as 3.4 Nm³/kg were reported, indicating the process to be highly efficient for waste-to-energy applications. The composition of the tars, suggested extensive cracking as a result of the high temperatures of the outgoing gas.