Synthesis Gas. James G. Speight
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Название: Synthesis Gas
Автор: James G. Speight
Издательство: John Wiley & Sons Limited
Жанр: Физика
isbn: 9781119707899
isbn:
2.5.5.1 Primary Gasification
Primary gasification involves thermal decomposition of the raw feedstock via various chemical processes (Table 2.6) and many schemes involve pressures ranging from atmospheric to 1000 psi. Air or oxygen may be admitted to support combustion to provide the necessary heat. The product is usually a low heat content (low-Btu) gas ranging from a carbon monoxide/hydrogen mixture to mixtures containing varying amounts of carbon monoxide, carbon dioxide, hydrogen, water, methane, hydrogen sulfide, nitrogen, and typical tar-like products of thermal decomposition of carbonaceous feedstocks are complex mixtures and include hydrocarbon oils and phenolic products (Dutcher et al., 1983; Speight, 2011a, 2013, 2014b).
Table 2.6 Types of reactions that occur in a gasifier.
| 2 C + O2 → 2 CO |
| C + O2 → CO2 |
| C + CO2 → 2 CO |
| CO + H2O → CO2 + H2 (shift reaction) |
| C + H2O → CO + H2 (water gas reaction) |
| C + 2 H2 → CH4 |
| 2 H2 + O2 → 2 H2O |
| CO + 2 H2 → CH3OH |
| CO + 3 H2 → CH4 + H2O (methanation reaction) |
| CO2 + 4 H2 → CH4 + 2 H2O |
| C + 2 H2O → 2 H2 + CO2 |
| 2 C + H2 → C2H2 |
| CH4 + 2 H2O → CO2 + 4 H2 |
Devolatilization of the feedstock occurs rapidly as the temperature rises above 300°C (570oF). During this period, the chemical structure is altered, producing solid char, tar products, condensable liquids, and low molecular weight gases. Furthermore, the products of the devolatilization stage in an inert gas atmosphere are very different from those in an atmosphere containing hydrogen at elevated pressure. In an atmosphere of hydrogen at elevated pressure, additional yields of methane or other low molecular weight gaseous hydrocarbon derivatives can result during the initial gasification stage from reactions such as: (i) direct hydrogenation of feedstock or semi-char because of any reactive intermediates formed and (ii) the hydrogenation of other gaseous hydrocarbon derivatives, oils, tars, and carbon oxides. Again, the kinetic picture for such reactions is complex due to the varying composition of the volatile products which, in turn, are related to the chemical character of the feedstock and the process parameters, including the reactor type.
A solid char product may also be produced, and may represent the bulk of the weight of the original feedstock, which determines (to a large extent) the yield of char and the composition of the gaseous product.
2.5.5.2 Secondary Gasification
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 СКАЧАТЬ