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Chapter 9: Problem 58

An ultimate analysis of a coal is a series of operations that yields the percentages by mass of carbon, hydrogen, nitrogen, oxygen, and sulfur in the coal. The heating value of a coal is best determined in a calorimeter, but it may be estimated with reasonable accuracy from the ultimate analysis using the Dulong formula: $$H H V(\mathrm{k} J / \mathrm{kg})=33,801(\mathrm{C})+144,158[(\mathrm{H})-0.125(\mathrm{O})]+9413(\mathrm{S})$$ where (C), (H), (O), and (S) are the mass fractions of the corresponding elements. The 0.125(O) term accounts for the hydrogen bound in the water contained in the coal. (a) Derive an expression for the higher heating value ( \(H H V\) ) of a coal in terms of \(\mathrm{C}, \mathrm{H}, \mathrm{O},\) and \(\mathrm{S},\) and compare your result with the Dulong formula. Suggest a reason for the difference. (b) A coal with an ultimate analysis of \(75.8 \mathrm{wt} \% \mathrm{C}, 5.1 \% \mathrm{H}, 8.2 \% \mathrm{O}, 1.5 \% \mathrm{N}, 1.6 \% \mathrm{S},\) and \(7.8 \%\) ash (noncombustible) is burned in a power-plant boiler fumace. All of the sulfur in the coal forms \(\mathrm{SO}_{2}\) The gas leaving the furnace is fed through a tall stack and discharged to the atmosphere. The ratio \(\phi\) (\(\mathrm{kg} \mathrm{SO}_{2}\) in the stack gas/kJ heating value of the fuel) must be below a specified value for the power plant to be in compliance with Environmental Protection Agency regulations regarding sulfur emissions. Estimate \(\phi\), using the Dulong formula for the heating value of the coal. (c) An earlier version of the EPA regulation specified that the mole fraction of \(\mathrm{SO}_{2}\) in the stack gas must be less than a specified amount to avoid a costly fine and the required installation of an expensive stack gas scrubbing unit. When this regulation was in force, a few unethical plant operators blew clear air into the base of the stack while the furnace was operating. Briefly explain why they did so and why they stopped this practice when the new regulation was introduced.

Short Answer

Expert verified
The Dulong formula does not need further derivation. The mass ratio of \(SO_2\) emitted per kJ of energy produced can be calculated from the mass fractions of the elements and the Dulong formula. The plant operators stopped blowing fresh air into the stack after the regulations changed because it no longer helped lower the mass ratio of \( SO_2\) that is emitted.

Step by step solution

01

Converting mass percentages into mass fractions

Before proceeding with the task, first, the mass percentages need to be converted into mass fraction. Mass fraction is the ratio of the mass of a component to the total mass of the mixture. Hence, for each element in the coal, its mass fraction would be its mass percentage divided by 100.
02

Deriving the higher heating value (HHV)

With the corresponding mass fractions of the elements, we can derive the Higher Heating Value (HHV) from the Dulong formula. The Dulong formula already states the heating value as: \[HHV (kJ/kg) = 33,801(C) + 144,158[(H)-0.125(O)] + 9413(S)\]. Since this is already in terms of C, H, O, and S, no further derivation is required.
03

Calculating the heating value using the Dulong formula

To calculate \(\phi\), first, determine the heating value of the coal using the Dulong formula, substituting the mass fractions of the elements obtained in step 1.
04

Computing the amount of \(SO_2\)

Since all Sulphur turns into \(SO_2\), for every kg of S, we can obtain 1 mole of \(SO_2\). By using the molar mass of \(SO_2\) (approximately 64 g/mol), we can calculate how many kg of \(SO_2\) a kg of coal produces.
05

Estimating \(\phi\)

The ratio \(\phi\) is the ratio of \(\frac{kg SO_2}{kJ of heating value of fuel}\). Divide the amount of \(SO_2\) produced (found in step 4) by the heating value of the fuel (found in step 3), to estimate \(\phi\).
06

Understanding environmental regulations' impact on plant operators' practice

For the last part of the exercise, we need to understand why some plant operators blow clear air into the stack while the furnace is operating. This helped dilute the \(SO_2\) in the stack gas, thereby decreasing set the mole fraction of \(SO_2\). When regulations changed and focused on the mass ratio instead of the molar ratio of \(SO_2\), this practice became ineffective, because just diluting the \(SO_2\) gas with air does not change the mass of \(SO_2\) emitted.

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Dulong Formula
The Dulong Formula is a classic way to estimate the higher heating value (HHV) of coal from its elemental composition. Dulong's formula provides a mathematical expression to calculate the energy produced when coal is burned, which is crucial for optimizing industrial energy usage. In the formula- \(HHV (kJ/kg) = 33,801(C) + 144,158[(H)-0.125(O)] + 9413(S)\),- \(C\) is the mass fraction of carbon,\(H\) is the mass fraction of hydrogen,\(O\) is the mass fraction of oxygen,\(S\) is the mass fraction of sulfur.The term \(0.125(O)\) adjusts for the oxygen forming water with hydrogen in the coal. It's crucial to realize this formula isn't an exact calorimetric measure, but rather an estimate based on coal's ultimate analysis. It's especially useful in situations where direct measurement isn't feasible.
Higher Heating Value
The Higher Heating Value (HHV) quantifies the total energy released in combustion, considering the latent heat of vaporization of water. HHV differs from Lower Heating Value (LHV), which excludes the energy from condensing water vapor. In the context of coal, understanding HHV is vital for assessing fuel efficiency. HHV provides insights into how much usable energy is obtained from burning a specific fuel mass. In Dulong's formula: - HHV incorporates corrections for water vapor, - Meaning the latent heat from water turning to vapor is included in energy output. This comprehensive understanding aids engineers and scientists in evaluating and comparing fuel efficiency, which is integral for power plants and thermal energy systems.
Environmental Regulations
Environmental regulations, set by authorities like the Environmental Protection Agency (EPA), aim to minimize pollution and its impacts on the environment. For coal-burning power plants, specific standards limit sulfur dioxide (SO鈧�) emissions. Historically, regulations have evolved: - Earlier, mole fraction limits for SO鈧� in stack gases were enforced. - Now, the focus is on the mass of SO鈧� per unit of energy produced. By changing the focus to the mass ratio rather than the mole ratio, the regulation pushed for actual reductions in sulfur emissions, rather than simply diluting them with additional air. This is crucial for ensuring that environmental standards increase air quality and protect ecosystems from acid rain and other harmful consequences of sulfur pollution.
Sulfur Emissions
Sulfur emissions from burning coal can result in the production of sulfur dioxide (SO鈧�), a significant environmental pollutant. When coal containing sulfur is burned, it reacts with oxygen to form SO鈧� gas, which can contribute to acid rain.Key points about sulfur emissions include:- For each mass of sulfur combusted, a specific mass of SO鈧� is produced.- Understanding the sulfur content in coal helps estimate potential SO鈧� emissions.- Managing sulfur emissions is essential for meeting environmental standards.By calculating the ratio \(\phi = \frac{kg \, of \, SO_2}{ kJ \, of \, heating \, value}\), power plants can assess compliance with emission limits, contributing to reduced environmental impact.
Ultimate Analysis
Ultimate analysis in coal analysis refers to the detailed breakdown of a fuel's elemental composition. It identifies the percentages of carbon, hydrogen, sulfur, nitrogen, and oxygen present in the coal. Understanding ultimate analysis helps in: - Estimating energy content, like through the Dulong Formula, - Predicting emissions from combustion, - Deciding which coals are most suitable for specific applications. Ultimate analysis is foundational for industries in selecting the right type of coal for energy production. It provides essential data to optimize combustion processes and adherence to environmental regulations.

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Most popular questions from this chapter

The standard heat of the combustion reaction of liquid \(n\) -hexane to form \(\mathrm{CO}_{2}(\mathrm{g})\) and \(\mathrm{H}_{2} \mathrm{O}(\mathrm{l}),\) with all reactants and products at \(77^{\circ} \mathrm{F}\) and 1 atm, is \(\Delta H_{\mathrm{r}}^{\prime}=-1.791 \times 10^{6} \mathrm{Btu} .\) The heat of vaporization of hexane at \(77^{\circ} \mathrm{F}\) is \(13,550 \mathrm{Btu} / \mathrm{b}\) -mole and that of water is \(18.934 \mathrm{Btu} / \mathrm{h}\) -mole. (a) Is the reaction exothermic or endothermic at \(77^{\circ} \mathrm{F}\) ? Would you have to heat or cool the reactor to keep the temperature constant? What would the temperature do if the reactor ran adiabatically? What can you infer about the energy required to break the molecular bonds of the reactants and that released when the product bonds form? (b) Use the given data to calculate \(\Delta H_{\mathrm{r}}^{\mathrm{r}}\) (Btu) for the combustion of \(n\) -hexane vapor to form \(\mathrm{CO}_{2}(\mathrm{g})\) and \(\overline{\mathrm{H}}_{2} \mathrm{O}(\mathrm{g})\) (c) If \(\dot{Q}=\Delta \dot{H},\) at what rate in \(\mathrm{B}_{\text {tu } / \mathrm{s}}\) is heat absorbed or released (state which) if \(120 \mathrm{lb}_{\mathrm{n}} / \mathrm{s}\) of \(\mathrm{O}_{2}\) is consumed in the combustion of hexane vapor, water vapor is the product, and the reactants and products are all at \(77^{\circ} \mathrm{F} ?\) (d) If the reaction were carried out in a real reactor, the actual value of \(\dot{Q}\) would be greater (less negative) than the value calculated in Part (c). Explain why.

In the production of many microelectronic devices, continuous chemical vapor deposition (CVD) processes are used to deposit thin and exceptionally uniform silicon dioxide films on silicon wafers. One CVD process involves the reaction between silane and oxygen at a very low pressure. $$\mathrm{SiH}_{4}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \rightarrow \mathrm{SiO}_{2}(\mathrm{s})+2 \mathrm{H}_{2}(\mathrm{g})$$ The feed gas, which contains oxygen and silane in a ratio \(8.00 \mathrm{mol} \mathrm{O}_{2} / \mathrm{mol} \mathrm{SiH}_{4},\) enters the reactor at 298 \(\mathrm{K}\) and 3.00 torr absolute. The reaction products emerge at \(1375 \mathrm{K}\) and 3.00 torr absolute. Essentially all of the silane in the feed is consumed. (a) Taking a basis of \(1 \mathrm{m}^{3}\) of feed gas, calculate the moles of each component of the feed and product mixtures and the extent of reaction, \(\xi\) (b) Calculate the standard heat of the silane oxidation reaction (kJ). Then, taking the feed and product species at \(298 \mathrm{K}\left(25^{\circ} \mathrm{C}\right)\) as references, prepare an inlet-outlet enthalpy table and calculate and fill in the component amounts (mol) and specific enthalpies (kJ/mol). (See Example 9.5-1.) Data $$\left(\Delta \hat{H}_{\mathrm{f}}\right)_{\mathrm{SiH}_{4}(\mathrm{g})}=-61.9 \mathrm{kJ} / \mathrm{mol}, \quad\left(\Delta \hat{H}_{\mathrm{f}}^{\mathrm{o}}\right)_{\mathrm{SiO}_{2}(\mathrm{s})}=-851 \mathrm{kJ} / \mathrm{mol}$$ $$\left(C_{p}\right)_{\mathrm{SiH}_{4}(g)}[\mathrm{k} \mathrm{J} /(\mathrm{mol} \cdot \mathrm{K})]=0.01118+12.2 \times 10^{-5} T-5.548 \times 10^{-8} T^{2}+6.84 \times 10^{-12} T^{3}$$ $$\left(C_{p}\right)_{\mathrm{SiO}_{2}(\mathrm{s})}[\mathrm{kJ} /(\mathrm{mol} \cdot \mathrm{K})]=0.04548+3.646 \times 10^{-5} T-1.009 \times 10^{3} / T^{2}$$ The temperatures in the formulas for \(C_{p}\) are in kelvins. (c) Calculate the heat ( \(k\) J) that must be transferred to or from the reactor (state which it is). Then determine the required heat transfer rate ( \(\mathrm{kW}\) ) required for a reactor feed of \(27.5 \mathrm{m}^{3} / \mathrm{h}\).

The synthesis of cthyl chloride is accomplished by reacting ethylene with hydrogen chloride in the presence of an aluminum chloride catalyst: $$\mathrm{C}_{2} \mathrm{H}_{4}(\mathrm{g})+\mathrm{HCl}(\mathrm{g}) \stackrel{\text { catallyst }}{\longrightarrow} \mathrm{C}_{2} \mathrm{H}_{5} \mathrm{Cl}(\mathrm{g}) ; \quad \Delta H_{\mathrm{r}}\left(0^{\circ} \mathrm{C}\right)=-64.5 \mathrm{kJ}$$ Process data and a simplified schematic flowchart are given here. Data Reactor: adiabatic, outlet temperature \(=50^{\circ} \mathrm{C}\) Feed A: \(100 \% \mathrm{HCl}(\mathrm{g}), 0^{\circ} \mathrm{C}\) Feed \(\mathrm{B}: 93\) mole \(\% \mathrm{C}_{2} \mathrm{H}_{4}, 7 \% \mathrm{C}_{2} \mathrm{H}_{6}, 0^{\circ} \mathrm{C}\) Reactor: adiabatic, outlet temperature \(=50^{\circ} \mathrm{C}\) Feed A: 100\% HCl(g), 0"C Feed B: 93 mole\% C_H_4, 7\% C_H_0, 0"C Product C: Consists of 1.5\% of the HCl, 1.5\% of the C_2 \(\mathrm{H}_{4}\), and all of the \(\mathrm{C}_{2} \mathrm{H}_{6}\) that enter the reactor Product D: \(1600 \mathrm{kg} \mathrm{C}_{2} \mathrm{H}_{5} \mathrm{Cl}(\mathrm{l}) / \mathrm{h}, 0^{\circ} \mathrm{C}\) Recycle to reactor: \(\mathbf{C}_{2} \mathrm{H}_{5} \mathrm{Cl}(\mathrm{l}), 0^{\circ} \mathrm{C}\) \(\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{Cl}: \Delta \hat{H}_{\mathrm{y}}=24.7 \mathrm{kJ} / \mathrm{mol}\) (assume independent of \(T\) ) \(\left(C_{p}\right)_{C_{2} H_{3} C(v)}\left[\mathrm{kJ} /\left(\mathrm{mol} \cdot^{\circ} \mathrm{C}\right)\right]=0.052+8.7 \times 10^{-5} T\left(^{\circ} \mathrm{C}\right)\) The reaction is exothermic, and if the heat of reaction is not removed in some way, the reactor temperature could increase to an undesirably high level. To avoid this occurrence, the reaction is carried out with the catalyst suspended in liquid cthyl chloride. As the reaction proceeds, most of the heat liberated goes to vaporize the liquid, making it possible to keep the reaction temperature at or below 50^'C. The stream leaving the reactor contains cthyl chloride formed by reaction and that vaporized in the reactor. This stream passes through a heat exchanger where it is cooled to \(0^{\circ} \mathrm{C},\) condensing essentially all of the cthyl chloride and leaving only unreacted \(\mathrm{C}_{2} \mathrm{H}_{4}, \mathrm{HCl}\), and \(\mathrm{C}_{2} \mathrm{H}_{6}\) in the gas phase. A portion of the liquid condensate is recycled to the reactor at a rate equal to the rate at which ethyl chloride is vaporized, and the rest is taken off as product. At the process conditions, heats of mixing and the influence of pressure on enthalpy may be neglected. (a) At what rates (kmol/h) do the two feed streams enter the process? (b) Calculate the composition (component mole fractions) and molar flow rate of product stream \(\mathrm{C}\). (c) Write an energy balance around the reactor and use it to determine the rate at which ethyl chloride must be recycled. (d) A number of simplifying assumptions were made in the process description and the analysis of this process system, so the results obtained using a more realistic simulation would differ considerably from those you should have obtained in Parts (a)-(c). List as many of these assumptions as you can think of.

A dilute aqueous solution of sulfuric acid at \(25^{\circ} \mathrm{C}\) is used to absorb ammonia in a continuous reactor, thereby producing ammonium sulfate, a fertilizer: $$2 \mathrm{NH}_{3}(\mathrm{g})+\mathrm{H}_{2} \mathrm{SO}_{4}(\mathrm{aq}) \rightarrow\left(\mathrm{NH}_{4}\right)_{2} \mathrm{SO}_{4}(\mathrm{aq})$$ (a) If the ammonia enters the absorber at \(75^{\circ} \mathrm{C}\), the sulfuric acid enters at \(25^{\circ} \mathrm{C}\), and the product solution emerges at \(25^{\circ} \mathrm{C}\), how much heat must be withdrawn from the unit per mol of \(\left(\mathrm{NH}_{4}\right)_{2} \mathrm{SO}_{4}\) produced? (All needed physical property data may be found in Appendix B.) (b) Estimate the final temperature if the reactor of Part (a) is adiabatic and the product of the solution contains 1.00 mole \(\%\) ammonium sulfate. Take the heat capacity of the solution to be that of pure liquid water [4.184 kJ/(kg.'C)]. (c) In a real (imperfectly insulated) reactor, would the final solution temperature be less than, equal to, or greater than the value calculated in Part (b), or is there no way to tell without more information? Briefly explain your answer.

Ethylene oxide is produced by the catalytic oxidation of ethylene: $$\mathrm{C}_{2} \mathrm{H}_{4}(\mathrm{g})+\frac{1}{2} \mathrm{O}_{2}(\mathrm{g}) \rightarrow \mathrm{C}_{2} \mathrm{H}_{4} \mathrm{O}(\mathrm{g})$$ An undesired competing reaction is the combustion of ethylene to \(\mathrm{CO}_{2}\) The feed to a reactor contains \(2 \mathrm{mol} \mathrm{C}_{2} \mathrm{H}_{4} / \mathrm{mol} \mathrm{O}_{2} .\) The conversion and yield in the reactor are respectively \(25 \%\) and \(0.70 \mathrm{mol} \mathrm{C}_{2} \mathrm{H}_{4} \mathrm{O}\) produced/mol \(\mathrm{C}_{2} \mathrm{H}_{4}\) consumed. A multiple- unit process separates the reactor outlet stream components: \(\mathrm{C}_{2} \mathrm{H}_{4}\) and \(\mathrm{O}_{2}\) are recycled to the reactor, \(\mathrm{C}_{2} \mathrm{H}_{4} \mathrm{O}\) is sold, and \(\mathrm{CO}_{2}\) and \(\mathrm{H}_{2} \mathrm{O}\) are discarded. The reactor inlet and outlet streams are each at \(450^{\circ} \mathrm{C}\), and the fresh feed and all species leaving the separation process are at \(25^{\circ} \mathrm{C}\). The combined fresh feedrecycle stream is preheated to \(450^{\circ} \mathrm{C}\). (a) Taking a basis of 2 mol of ethylene entering the reactor, draw and label a flowchart of the complete process (show the separation process as a single unit) and calculate the molar amounts and compositions of all process streams. (b) Calculate the heat requirement ( \(k J\) ) for the entire process and that for the reactor alone. Data for gaseous ethylene oxide $$\begin{aligned}\Delta \hat{H}_{\mathrm{f}}^{\prime} &=-51.00 \mathrm{kJ} / \mathrm{mol} \\ C_{p}[\mathrm{J} /(\mathrm{mol} \cdot \mathrm{K})] &=-4.69+0.2061 T-9.995 \times 10^{-5} T^{2} \end{aligned}$$ where \(T\) is in kelvins. (c) Calculate the flow rate \((\mathrm{kg} / \mathrm{h})\) and composition of the fresh feed, the overall conversion of ethylene, and the overall process and reactor heat requirements (kW) for a production rate of \(1500 \mathrm{kg} \mathrm{C}_{2} \mathrm{H}_{4} \mathrm{O} /\) day. Briefly explain the reasons for separating and recycling the ethylene-oxygen stream. (d) One of the attributes of this process defined in the problem statement is extremely unrealistic. What is it?
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