Plant operator, thermodynamics

In apphcation to electric utihty power generation, MHD is combined with steam (qv) power generation, as shown in Figure 2. The MHD generator is used as a topping unit to the steam bottoming plant. From a thermodynamic point of view, the system is a combined cycle. The MHD generator operates in a Brayton cycle, similar to a gas turbine the steam plant operates in a conventional Rankine cycle (11). 

Chemical scaling is another form of fouling that occurs in NF and RO plants. The thermodynamic solubility of salts such as calcium carbonate and calcium and barium sulfate imposes an upper boundary on the system recovery. Thus, it is essential to operate systems at recoveries lower than this critical value to avoid chemical scaling, unless the water chemistry is adjusted to prevent precipitation. It is possible to increase system recovery by either adjusting the pH or adding an antisealant, or both. 

Usually, a gas turbine plant operates on open circuit , with internal combustion (Fig. 1.3). Air and fuel pass across the single control surface into the compressor and combustion chamber, respectively, and the combustion products leave the control surface after expansion through the turbine. The open circuit plant cannot be said to operate on a thermodynamic cycle however, its performance is often assessed by treating it as equivalent to a closed cyclic power plant, but care must be taken in such an approach. 

Note that all three models give almost the same exit conversion and yield for methane and carbon dioxide and that the second unit (2) is also operating relatively closely to its thermodynamic equilibrium, though further away from it when compared to Plant (1). The close agreement between the industrial performance data and the simulated data for the reformers (1) and (2) that was obtained by three different diffusion-reaction models validates the models that we have used, at least for plants operating near their thermodynamic equilibria. 

The column description, product specifications, total plant operation time, number and size of available storage vessels, etc. are given in Table 6.8. For proprietary reasons the names of the components in the feed mixture are disguised and thermodynamic data ore omitted. Relative product values and feed costs are given in Table 6.10 (operating costs have also been scaled). 

Unsteady-state or dynamic simulation accounts for process transients, from an initial state to a final state. Dynamic models for complex chemical processes typically consist of large systems of ordinary differential equations and algebraic equations. Therefore, dynamic process simulation is computationally intensive. Dynamic simulators typically contain three units (i) thermodynamic and physical properties packages, (ii) unit operation models, (hi) numerical solvers. Dynamic simulation is used for batch process design and development, control strategy development, control system check-out, the optimization of plant operations, process reliability/availability/safety studies, process improvement, process start-up and shutdown. There are countless dynamic process simulators available on the market. One of them has the commercial name Hysis [2.3]. 

Details of steam power plants and internal-combustion engines can be found in E. B. Woodruff, H. B. Lammers, and T. S. Lammers, Steam Plant Operation, 6th ed., McGraw-Hill, New York, 1992 and C. F. Taylor, The Internal Combustion Engine in Theory and Practice Thermodynamics, Fluid Flow, Perjormance, MIT Press, Boston, 1984. 

University offers many programs in this field, from subroutines to major computational systems. Chemical engineers utilize computers to develop more thermodynamically efficient procedures and to consolidate overall plant operations, especially in the areas of energy consumption, reaction rates, and hazardous waste problems. 

For most of the chemical products given in Table 1, the synthesis takes place at elevated pressures from typically 20 bar and above. Most syngas plants operate at 20-40 bar, although the thermodynamics shows that higher conversions can be obtained at lower pressures. However, the cost associated with larger equipment and syngas compression renders often syngas manufacture at low pressures prohibitive for these applications. 

More Difficult Systems. The above discussions pertain to easy systems (1) small, nonpolar or slightly polar molecules for equations of state and (2) nonelectrolyte, nonpolymeric substances considerably below their critical tenperatures for liquid-state activity-coefficient models. Most simulators have some models for electrolytes and for polymers, but these are likely to be even more uncertain than for the easy systems. Again, the key is to find some data, even plant operating data, to verify and to calibrate the models. If the overall recovery from a multistage separation is known, for exanple, one can simulate the column, using the best-known thermodynamic model, and the deviation between the plant datum and the simulator result is a crude (optimistic) estimate of the uncertainty. 

In 1992, about 6.5 billion lb acetic acid was produced worldwide, of which about 3.6 billion lb was produced in the United States [1]. The current commercial processes for its production include oxidation of ethanol (acetaldehyde), oxidation of butane-butene mixture or naphtha, and carbonylation of methanol or methyl acetate. These are catalytic processes. The last, liquid-phase carbonylation of methanol using a rhodium and iodide catalyst, has become the dominant process since its introduction in the late 1960s, and accounted for about half the production of acetic acid in the United States [2]. That represents a conversion of 1.5 x 106 ton per year of methanol into 2.8 x 106 ton per year of acetic acid. In the United States, 80% of actual plant operation capacity is based on this technology [3]. The reaction is thermodynamically favorable [4], and the theoretical conversion is practicalty 100% at 389 K ... 

Modern refineries deal with a multitude of complex systems that may require different thermodynamic models for each refinery plant and its associated process model. For example, we cannot model the sour gas units that deal with acid gases and water with the same thermodynamic model that we use for the crude fractionation system. In fact, reasonable thermodynamic models form the heart of any process model. Chen et al. [7] have documented the variety of thermodynamic models available for frequently encoxmtered chemical and physical systems. Agarwal et. al [18] present a detailed account about the pitfalls of choosing a poor thermodynamic system for process models and the undesired consequences of using these poor models to modify plant operations. Process model developers and users must be aware of the underlying thermodynamics and its limitations. 

The previous section has described how engineering simulations are valuable in improving plant operations. To produce accurate results, several composition-based properties are required to model the melt—its density, specific heat capacity, and dissolution thermodynamics— but the most important properties are the viscosity and thermal conductivity. 

Dehydrogenation of /i-Butane. Dehydrogenation of / -butane [106-97-8] via the Houdry process is carried out under partial vacuum, 35—75 kPa (5—11 psi), at about 535—650°C with a fixed-bed catalyst. The catalyst consists of aluminum oxide and chromium oxide as the principal components. The reaction is endothermic and the cycle life of the catalyst is about 10 minutes because of coke buildup. Several parallel reactors are needed in the plant to allow for continuous operation with catalyst regeneration. Thermodynamics limits the conversion to about 30—40% and the ultimate yield is 60—65 wt % (233). 

Isomerization. Isomerization of any of the butylene isomers to increase supply of another isomer is not practiced commercially. However, their isomerization has been studied extensively because formation and isomerization accompany many refinery processes maximization of 2-butene content maximizes octane number when isobutane is alkylated with butene streams using HF as catalyst and isomerization of high concentrations of 1-butene to 2-butene in mixtures with isobutylene could simplify subsequent separations (22). One plant (Phillips) is now being operated for this latter purpose (23,24). The general topic of isomerization has been covered in detail (25—27). Isomer distribution at thermodynamic equiUbrium in the range 300—1000 Kis summarized in Table 4 (25). 

The surprise was finally clarified by remembering that this was an air operated plant built in a thermodynamic cycle, (the Brayton or gas turbine cycle) with a 18,000 HP air compressor. This generated 5 MW of salable... 

The second law of thermodynamics may be used to show that a cyclic heat power plant (or cyclic heat engine) achieves maximum efficiency by operating on a reversible cycle called the Carnot cycle for a given (maximum) temperature of supply (T ax) and given (minimum) temperature of heat rejection (T jn). Such a Carnot power plant receives all its heat (Qq) at the maximum temperature (i.e. Tq = and rejects all its heat (Q ) at the minimum temperature (i.e. 7 = 7, in) the other processes are reversible and adiabatic and therefore isentropic (see the temperature-entropy diagram of Fig. 1.8). Its thermal efficiency is... 

A much more selective reaction is possible by using vapor-phase fluonnahon over a chromia" catalyst at 300 to 400 °C, but conversions are thermodynamically limited to 10-20% under acceptable operating conditions [fO 11 Despite this disadvantage, this process has been selected by ICI and Hoechst for their first plants... 

This remarkable result shows that the efficiency of a Carnot engine is simply related to the ratio of the two absolute temperatures used in the cycle. In normal applications in a power plant, the cold temperature is around room temperature T = 300 K while the hot temperature in a power plant is around T = fiOO K, and thus has an efficiency of 0.5, or 50 percent. This is approximately the maximum efficiency of a typical power plant. The heated steam in a power plant is used to drive a turbine and some such arrangement is used in most heat engines. A Carnot engine operating between 600 K and 300 K must be inefficient, only approximately 50 percent of the heat being converted to work, or the second law of thermodynamics would be violated. The actual efficiency of heat engines must be lower than the Carnot efficiency because they use different thermodynamic cycles and the processes are not reversible. 

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