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Secondary gasification usually involves the gasification of char from the primary gasifier, which is typically achieved by reaction of the hot char with water vapor to produce carbon monoxide and hydrogen:

The reaction requires heat input (endothermic) for the reaction to proceed in its forward direction. Usually, an excess amount of steam is also needed to promote the reaction. However, excess steam used in this reaction has an adverse effect on the thermal efficiency of the process. Therefore, this reaction is typically combined with other gasification reactions in practical applications. The hydrogen-carbon monoxide ratio of the product synthesis gas depends on the synthesis chemistry as well as process engineering.

The mechanism of this reaction section is based on the reaction between carbon and gaseous reactants, not for reactions between feedstock and gaseous reactants. Hence the equations may over-simply the actual chemistry of the steam gasification reaction. Even though carbon is the dominant atomic species present in feedstock, feedstock is more reactive than pure carbon. The presence of various reactive organic functional groups and the availability of catalytic activity via naturally occurring mineral ingredients can enhance the relative reactivity of the feedstock – for example anthracite, which has the highest carbon content among all ranks of coal (Speight, 2013), is most difficult to gasify or liquefy.

After the rate of devolatilization has passed a maximum another reaction becomes important – in this reaction the semi-char is converted to char (sometimes erroneously referred to as stable char) primarily through the evolution of hydrogen. Thus, the gasification process occurs as the char reacts with gases such as carbon dioxide and steam to produce carbon monoxide and hydrogen. The resulting gas (producer gas or synthesis gas) may be more efficiently converted to electricity than is typically possible by direct combustion. Also, corrosive elements in the ash may be refined out by the gasification process, allowing high temperature combustion of the gas from otherwise problematic feedstocks (Speight, 2011a, 2013, 2014b).

Oxidation and gasification reactions consume the char and the oxidation and the gasification kinetic rates follow Arrhenius type dependence on temperature. On the other hand, the kinetic parameters are feedstock specific and there is no true global relationship to describe the kinetics of char gasification – the characteristics of the char are also feedstock specific. The complexity of the reactions makes the reaction initiation and the subsequent rates subject to many factors, any one of which can influence the kinetic aspects of the reaction.

Although the initial gasification stage (devolatilization) is completed in seconds or even less at elevated temperature, the subsequent gasification of the char produced at the initial gasification stage is much slower, requiring minutes or hours to obtain significant conversion under practical conditions and reactor designs for commercial gasifiers are largely dependent on the reactivity of the char and also on the gasification medium (Johnson, 1979; Sha, 2005). Thus, the distribution and chemical composition of the products are also influenced by the prevailing conditions (i.e., temperature, heating rate, pressure, residence time, etc.) and, last but not least, the nature of the feedstock. Also, the presence of oxygen, hydrogen, water vapor, carbon oxides, and other compounds in the reaction atmosphere during pyrolysis may either support or inhibit numerous reactions with feedstock and with the products evolved.

The reactivity of char produced in the pyrolysis step depends on the nature of the feedstock and increases with oxygen content of the feedstock but decreases with carbon content. In general, char produced from a low-carbon feedstock is more reactive than char produced from a high-carbon feedstock. The reactivity of char from a low-carbon feedstock may be influenced by catalytic effect of mineral matter in char. In addition, as the carbon content of the feedstock increases, the reactive functional groups present in the feedstock decrease and the char becomes more aromatic and cross-linked in nature (Speight, 2013). Therefore, char obtained from high-carbon feedstock contains a lesser number of functional groups and higher proportion of aromatic and cross-linked structures, which reduce reactivity. The reactivity of char also depends upon thermal treatment it receives during formation from the parent feedstock – the gasification rate of char decreases as the char preparation temperature increases due to the decrease in active surface areas of char. Therefore, a change of char preparation temperature may change the chemical nature of char, which in turn may change the gasification rate.

Typically, char has a higher surface area compared to the surface area of the parent feedstock, even when the feedstock has been pelletized, and the surface area changes as the char undergoes gasification – the surface area increases with carbon conversion, reaches maximum and then decreases. These changes in turn affect gasification rates – in general, reactivity increases with the increase in surface area. The initial increase in surface area appears to be caused by cleanup and widening of pores in the char. The decrease in surface area at high carbon conversion may be due to coalescence of pores, which ultimately leads to collapse of the pore structure within the char.

Heat transfer and mass transfer processes in fixed- or moving-bed gasifiers are affected by complex solids flow and chemical reactions. Coarsely crushed feedstock settles while undergoing heating, drying, devolatilization, gasification and combustion. Also, the feedstock particles change in diameter, shape, and porosity – non-ideal behavior may result from certain types of chemical structures in the feedstock, gas bubbles, and channel and a variable void fraction may also change heat and mass transfer characteristics.

An important factor is the importance of the pyrolysis temperature as a major factor in the thermal history, and consequently in the thermodynamics of the feedstock char. However, the thermal history of a char should also depend on the rate of temperature rise to the pyrolysis temperature and on the length of time the char is kept at the pyrolysis temperature (soak time), which might be expected to reduce the residual entropy of the char by employing a longer soak time.

Alkali metal salts are known to catalyze the steam gasification reaction of carbonaceous materials, including coal. The process is based on the concept that alkali metal salts (such as potassium carbonate, sodium carbonate, potassium sulfide, sodium sulfide, and the like) will catalyze the steam gasification of feedstocks. The order of catalytic activity of alkali metals on the gasification reaction is:

Catalyst amounts on the order of 10 to 20% w/w potassium carbonate will lower bituminous coal gasifier temperatures from 925°C (1695^oF) to 700°C (1090^oF) and that the catalyst can be introduced to the gasifier impregnated on coal or char. In addition, tests with potassium carbonate showed that this material also acts as a catalyst for the methanation reaction. In addition, the use of catalysts can reduce the amount of tar formed in the process. In the case of catalytic steam gasification of coal, carbon deposition reaction may affect catalyst life by fouling the catalyst active sites. This carbon deposition reaction is more likely to take place whenever the steam concentration is low.

Ruthenium-containing catalysts are used primarily in the production of ammonia. It has been shown that ruthenium catalysts provide five to 10 times higher reactivity rates than other catalysts. However, ruthenium quickly becomes inactive due to its necessary supporting material, such as activated carbon, which is used to achieve effective reactivity. However, during the process, the carbon is consumed, thereby reducing the effect of the ruthenium catalyst.

Catalysts can also be used to favor or suppress the formation of certain components in the gaseous product by changing the chemistry of the reaction, the rate of reaction, and the thermodynamic balance of the reaction. For example, in the production of synthesis gas (mixtures of hydrogen and carbon monoxide), methane is also produced in small amounts. Catalytic gasification can be used to either promote methane formation or suppress it.