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ENGINEERING DESIGN SEMINAR

Energy
Balances

INTRODUCTION

At UOP, the preparation of a Schedule A design package involves both process and project engineering. While the project engineer is directly responsible for the specifications that make up the design package, all design work on a particular project begins with the process engineer. After determining the overall material balance or mol balance for a unit, the process engineer will then calculate an energy balance. The energy balance, as well as defining the duties for heaters and heat exchangers, allows the calculation of tray loadings around the fractionation columns so that tray sizing may be done. The energy balance also permits the evaluation of alternatives to a particular design problem and the optimization of the process with respect to capital cost and utility consumption.

During this session, UOP methods for calculating various items associated with the preparation of energy balances will be presented. The following topics will be covered:

Review First Law of Thermodynamics Definition of Enthalpy and Base States Calculation of Pure Component Enthalpy
-

Calculation of Latent Heat

- ldeal Vapor Enthalpy - Calculation of Enthalpy Correction for Pressure


Enthalpy Mixing Rules Calculation of ldeal Vapor Enthalpy of Mixtures Calculation of Heat of Reaction

FIRST L A W OF THERMODYNAMICS

The first law of thermodynamics, which deals with the conservation of energy, can be expressed in equation form as follows:

The various forms of energy in the above equation are defined as follows:

(a) Internal energy (b) Flow energy to force mass m in (or out) of the system at pressure p with unit volume V (c) Kinetic energy of the streams (d) Potential energy referred to some datum (e) Surface energy (may be very large term for sprays, emulsions, etc.)

(0

Net heat added to the system

(g) Work in all its forms done by the system (h) Net change in energy content within the system (changes of inventory, temperature, composition, elevation, etc.)

The terms in the above energy equation are defined as follows:

Z = height above some datum,f i


u = velocity,fils p = pressure, 1bf/ft2 V = specific volume, ft3/lbm
U = internal energy,ft . lbfllb,

CQ= heat added to system, ft .Ibflh C W = work done by the system,ft .lbf / h
g = accelerationof gravity, ft/s2 g, = gravitationalconstant,ft ./bm/1bf .s 2

m = massflowrate,Ib/h
ES = surface energy, ft . Ibf / h
A E = net change in energy content of system, ft . Ibf / h

In general, the term g/gc is equal to unity since g = g , = 32.2.

Multiplying out all of the terms in the first law equation gives the units of f?. Ibdh which, when divided by the factor 778 is equivalent to the more customary energy units of Btulh.

For flow processes at constant pressure where changes of internal energy are large, while kinetic, potential and surface energy changes are small, for steady state, the above equation for the first law of thermodynamics reduces to the following:

1Q = m2Up + m2p2V2 + 1W - mlUl - mlplVl


Since U + pV occurs repeatedly, it has been defined as ENTHALPY and is given the symbol H, so that:

Internal energy U is related to the translational, rotational, and vibrational energy of the molecules of a substance. Since it is not possible to measure the absolute value of internal energy and, hence enthalpy,
it is necessary to define an arbitrary base state where enthalpy is zero. UOP defines the base state

for all hydrocarbons, water, carbon dioxide, and hydrogen sulfide as liquid at 60'F and

the base state for hydrogen, oxygen, nitrogen and carbon monoxide a s vapor at 60'F
and zero psia.

The choice of a base state temperature is not important, since all use of enthalpy in the design of equipment (e.g. heaters and heat exchangers) is dependent on the difference in enthalpy between inlet and outlet streams. Nowhere is the absolute value of enthalpy used to specify a piece of equipment.

Although enthalpy is a function of both temperature and pressure, two special cases are met where the pressure effect may be neglected: (1) The enthalpy of an ideal gas is independent of pressure, and the pressure effect can be ignored when the ideal gas law is used; (2) the enthalpies of liquids and solids are not greatly affected by pressure, and under ordinary conditions, unless pressures of several atmospheres are involved, the effect of pressure on the enthalpy of a liquid or solid may be neglected. At constant pressure, or under conditions where the effect of pressure on enthalpy may be neglected, the enthalpy difference over a temperature range is given by the following equation:

Where:
C' = means specific betweenT2 andT1,Btu/lb." F
P

m = mass flowrate,lb/h T = temperature," F

= enthalpy,Btu/h

PURE COMPONENT ENTHALPIES

To calculate the enthalpy of a pure component, we make use of the following:

The latent heat of vaporization. The effect of pressure on vapor enthalpy. The specific heat of the ideal vapor.

There are several methods available for calculating the latent heat of vaporization of a pure component, one of which is the famous Clapeyron equation:

Where:
VP = vapor pressure, psia

T = absolute temperature," R
R = gas constant, 7.987 Btu/lbmol." R

3.

= latent heat, Btu/lbmol

Since this form of the equation has been integrated assuming that the latent heat is constant over a temperature range, it has limited applicability.

In 1938, Kistyakowski proposed the following equation for the calculation of the latent heat of hydrocarbons and other non-polar compounds:

Where:

iLb = latent heat at the normal boiling point, Btu/lbmol


Tb = normal boiling point," R

For calculation of latent heat at temperatures other than the normal boiling point, the following equation by Watson can be used:

Where:
= latent heat at temperatureT (" R),Btu/lbmol or Btullb

Tc = critical temperature, " R T b = rormal boiling point, " R

Although this is a very good relationship, it seems to predict heats of vaporization within only about 5 pct generally. This is not considered satisfactory for UOP design calculations, hence the approach of comparing the latent heat of two materials at equivalent conditions, where one of the materials is known and understood thoroughly.

It can be shown rigorously that the ratio of the latent heat of a substance to the latent heat of a reference substance is very nearly a constant at the same reduced temperature, or

Where: q = latentheatratio

A = latent heat of pure component, Btu/lb 2, = la tent hea t of water at the reduced temperature pure component, Btullb

By knowing the latent heat of a pure component at its normal boiling point through experimentation or estimation using one of the above equations, the latent heat ratio can be determined. This then allows the calculation of the latent heat at any other temperature with reasonably good accuracy. Because its properties are well known, water was chosen as the reference substance and the variation of the latent heat with reduced temperature was very carefully fitted over the whole temperature range from freezing to critical, using the normal boiling point as the basis. The latent heat for water can be calculated from the following equation:

Where:

A , = latentheatatT,,Btu/lb
T r = reduced temperature of pure component n = exponent which is a function of T,

The exponent "nu in the above equation can be determined by interpolation from Table No.1 or from the following equation:

The attached Enthalpy Correction for Gases and Vapors chart by Hougen and Watson is based on the equation of state (PV = ZRT) and the theorem of corresponding states. It allows the calculation of the correction to be applied to the ideal vapor enthalpy to account for the effects of pressure or non-ideality of a pure component. Note that the units are gmcaVgmmoVK which is exactly equivalent to Bt~/lbmol/~R.

The specific heat of an ideal vapor is commonly available in the literature in the form of curves, tabulations, or equations in the form:

Where:
Cp = specific heat, Btullb. F

T = temperature, O F o r 0R o r 0C

A, 5,C, = constants specific to each substance

In order to determine the change in ideal vapor enthalpy for a compound between two temperatures, it is necessary to integrate the above equation, which results in the following:

T~-T,)+B(T$ -T~)/~+c(T:-~:)/3]
Where:
AH = change in vapor enthalpy betweenT2 and T I ,Btulh

m = mass flowrate, Iblh T = temperature, " Fo r 0R o r 0C

Consider the typical enthalpy versus temperature curve for a pure component given in Figure 1. For convenience, we will use the following subscript notation:

sl = saturated liquid (liquid at its bubble point)

sv = saturated vapor (vapor at its dew point)

Figure 1

Enthalpy vs TemperatureDiagram

60

T2 Temperature, O F

We have now seen how to calculate the latent heat of vaporization, the specific heat of the ideal vapor, and the effect of pressure on enthalpy. In order to calculate the saturated liquid enthalpy Hsl at T2, we make use of all of these concepts, which may be summarized in the following procedure:
1.

Hsl at 60" F is equal to zero (by definition).

2.

Calculate the latent heat at 60F and add it to H,lV60 to get the saturated vapor enthalpy HSv,60.

H s v , 6 ~= Hsl,60 + jb60

3.

Calculate the enthalpy correction at 60F due to lack of ideal behavior from the Enthalpy Correction for Gases and Vapors chart. Then:

4.

Calculate the change in ideal gas enthalpy between T2 and 60F from known Cp.

5.

Calculate the enthalpy correction at T2 due to lack of ideal behavior from the Enthalpy Correction for Gases and Vapors chart. Then:

6.

Calculate the latent heat at T2 and subtract it from the saturated vapor enthalpy at T2 to get the saturated liquid enthalpy at T2.

The various terms above are defined as follows:

HsI = saturated liquid enthalpy, Btullb Hsv = saturated vapor enthalpy, Btullb

? . = latent heat, Btullb


H* = enthalpy of ideal gas, Btullb (H* - H ) = enthalpy correction due to non - ideal behavior, Btu/lb

ENTHALPY MIXING RULES

Obviously, it is not too often that we are able to work with a system that has a only one pure component or even a manageable number of pure components. If we are working with a mixture of a few pure components, it will be necessary :o blend the enthalpies of these components to get the enthalpy of the mixture. When computing vapor mixture enthalpy, mixing of component contributions is
done at zero pressure while accumulating pseudo critical temperature and pressure values for the mixture. The entire mixture is then corrected for pressure using pseudo

critical values as if the mixture were a pure substance.

Where:

w; = mass flowrate of component i, Ib/h HSl,; = saturated liquid enthalpy of component i , Btullb
H; = ideal vapor enthalpy of component i , Btullb

For liquid mixture enthalpy, the contribution of each component is computed (saturated liquid) for its vapor pressure at the stated temperature. If a component is at a temperature above its critical, the enthalpy contribution to the liquid mixture is assumed to lie along a curve (enthalpy diagram) through the critical point and parallel with the ideal vapor enthalpy curve. The difference between the ideal vapor enthalpy and the liquid enthalpy above the critical temperature can be calculated from the following equation: AHcp = 5 . 2 2 9 2 ( ~ ~ / m wt) ol

Where:
A HCp= enthalpy difference, Btullb

Tc = critical temperature," R rnol wt = molecular weight, Ib/lbmol

SAMPLE

PROBLEM

Calculate the latent heat ratio (q) for normal pentane, using water as the reference substance, at the normal boiling point for normal pentane.

Tc =385.gF
1 , = 153.6Btu/lb(latent heat at normal boiling point)

T b = 96.93" F (normal boiling point)

SOLUTION

The exponent "nuin the equation for the latent heat of water can either be calculated from the equation for n or interpolaied from the data given in Table No. 1.

Then:

and:

IDEAL VAPOR ENTHALPY OF MIXTURES

If we are designing a system wherein the materials are a blend of many components such as naphtha,

kerosine, or diesel oil, the previously described method for calculation of pure component enthalpies is not very practical, even if one has access to a computer. In order to calculate the ideal vapor enthalpy or, for that matter, saturated vapor enthalpy or saturated liquid enthalpy, we make use of the fact that ideal vapor enthalpies, when plotted against the ideal vapor enthalpy of one reference substance at equal
reduced temperature produce nearly perfect straight lines from about 0.3 to 1.5 Tr. We thus need

only two values of ideal vapor enthalpy to establish values over the entire range of interest. This is done as follows:

1.

Given the API gravity and ASTM distillation for a material, calculate the UOP K, molecular weight, molal average boiling point (NBP), critical temperature, critical pressure and estimate the vapor pressure at 60" F.

2.

Using the API gravity and UOP K, obtain the linear specific heat of the liquid at 60" F and the normal boiling point (NBP) from chart RE F-1. The saturated liquid enthalpy at the normal boiling point can then be calculated as follows:

Where:
NBP = normal boiling point, " F

C, = liquid specific heat, Btu/lb." F

3.

Using molecular weight and normal boiling point, obtain the latent heat of vaporization at the normal boiling point from chart RE F-3. Then, add the latent heat to the saturated liquid enthalpy to get the saturated vapor enthalpy at the normal boiling point.

4.

Calculate the enthalpy correction at the normal boiling point due to lack of ideal behavior from the Enthalpy Correction for Gases and Vapors chart. Then,

This is then one of the two points required to define the ideal vapor enthalpy curve for the mixture.

5.

Using the reduced temperature for the substance at its normal boiling point, calculate "n" for water, and the latent heat of water ( A w ) ?t this temperature.

6.

Calculate the latent heat ratio, q, for the substance from the following:

7.

Calculate the reduced temperature of the substance at the datum temperature, 60F from the following:

8.

Again, calculate "nu for water using the reduced temperature calculated in step 7. Then, compute the latent heat of vaporization of water ('w.60) for this reduced temperature.

9.

Compute the latent heat of vaporization of the substance at 60F from the following:

10.

Since the datum liquid has zero enthalpy at 60F, the enthalpy of the saturated vapor at 60F is equal to the latent heat of vaporization at 60F.

11.

At 6OSF, calculate the reduced vapor pressure. Use this to calculate the enthalpy correction at 60F due to lack of ideal behavior from the Enthalpy Correction for Gases and Vapors chart. Then,

This is then the second point required to fix the ideal vapor enthalpy at any temperature.

12.

At each of the reduced temperatures for the substance, calculate the corresponding temperature for normal hexane from the following:

13.

For each of the temperatures calculated for normal hexane in step 12, calculate the ideal vapor enthalpy of normal hexane from the equation given in Table 2.

14.

The ideal vapor enthalpy of substance "X" is linearly related to the ideal vapor enthalpy of normal hexane at equal reduced temperature (see Figure 2). Compute the slope "B" and intercept "A" of a straight line through the two points from the following:

Figure 2

Ideal Vapor Enthalpy o f Mirfures

H * ~ 6 ~

H*~BP

"X"Ideal Vapor Enthalpy, HXC


EDSR0011M

As you can see, this procedure can be extremely tedious and time consuming unless one is able to perform the calculations on a computer. Therefore, UOP has simplified the calculation of the enthalpy for these types of mixtures through the use of PD chart 870 (liquids) and PD chart 189 (vapors). These charts require only the UOP K and cubic average boiling point (CABP) for a mixture.

HEAT OF REACTION

Consider the enthalpy-temperature curve for a reactor as given in Figure 3. The feed to the reactor is heated from 60'F to the reactor inlet temperature (TI) along path 1.

Figure 3

Heat o f Reaction

Temperature, O F

For a truly adiabatic reactor without any heat loss, the reaction would proceed along path 2 to the outlei temperature (T2) and the enthalpy of the products would equal the enthalpy of the reactants. The products are then cooled back down to 60'F along path 3, but we note that their enthalpy is no longer zero, which is in violation of the UOP definition for the base state enthalpy of most materials. In order to overcome this apparent discrepancy, UOP considers that the enthalpy of the products will be different (either larger or greater) than the enthalpy of the reactants by the value of the heat of reaction. The enthalpy will actually follow path 4 through the reactor and path 5 when the products are cooled down to 60'F so that the enthalpy of the products is equal to zero.

In order to calculate the heat of reaction, given the amounts and the chemical species of the reacting components and their products, we can either sum up the heats of combustion or the heats of formation. UOP uses the gross values of the heat of combustion (the larger value). This is based on cooling the products to make liquid water and gaseous carbon dioxide. We also use the higher value of the heat of combustion for hydrogen, also condensing to liquid water. Heats of combustion, as given in the PD charts or in the literature, are always negative, whereas the heat of formation can be either positive or negative. Heats of combustion or heats of formation must be consistent with the UOP defined base state for the pure component.

Heat of reaction can have the units of Btullb, kcallkg, Btullbmol, or kcallkgmol. However, care must be taken in expressing the heat of reaction in terms of the mass or mols of one of the reactants or products. Consider the following hypothetical chemical reaction:

If the heat of reaction is to be calculated in terms of Btullbmol of product D, then it can be calculated from either of the following:
AH, = (heat of combustion)rea, - (heat of combustion)prods

or:

AH, = (heat of f o r m a t j ~ n) (heat ~~~ of formation)react

where the heat of combustion or the heat of formation is expressed in Btullbmol.

If the heat of reaction is calculated from the first equation above by adding up the molal heats of combustion of the reactants and subtracting the molal heats of combustion of the products, the sign of A Hr will tell if the reaction is exothermic or endothermic. If the sum for the products (that is, a greater negative value) exceeds that for the reactants, the products contain more heating value than the reactants and the reaction is endothermic, or you have to put heat in to make it go. In this case, our sign convention requires that A Hr comes out positive.

A H,is positive + endothermic

AH, is negative + exothermic

The reason for giving the heat of reaction a negative value in the basic equation is that if heat were removed from the process to keep it isothermal, you think of subtracting heat from the reactor. If the heat of reaction is negative, this amount of heat has to be added to the reactor feed on our heat and weight balance forms in order to get the heat content of the reactor effluent, providing that it is an adiabatic reactor. A safe way to remember this is always to subtract the heat of reaction from ,the reactor feed enthalpy to get the reactor effluent enthalpy.

EXAMPLE

PROBLEM

Calculate the heat of reaction in terms of Btullbmol of benzene for the following reaction:
Benzene + Orthoxylene+ (2)Toluene

SOLUTION

The gross heat of combustion for each component in the above reaction can be found in chart RE-C-1C. AH,

,* = - 17992Btullb benzene
= - 18253Btu/lb toluene

In order to express the heat of reaction in terms of Btu/lbmol of benzene, the above heats of combustion must be converted to this unit.

Then: AH, = (- 1405319 - 1958227)- (-3363444) = -102Btu/lbmol Bz(exothermic)


. .

..

Table No. 1

The following is a tabulation of the value for the exponent "n" in the equation for the latent heat of water as a function of the reduced temperature (T,):

Table No. 2

IDEAL VAPOR ENTHALPY OF NORMAL HEXANE

Where:

H* = idealvapor enthalpy, Btullb T = temperature," F


A = 136.0560 1

8 = 0.34723124

C = 0.33364344x 1 o - ~
D = -0.74387463x

E = 0.72659273x lo-"

Energy Balances

Review First Law of Thermodynamics Definition of Enthalpy and Base States

Calculation of Pure Compon~nt Enthalpy Enthalpy Mixing Rules Ideal Vapor Enthalpy of Mixtures Calculation of Heat of Reaction

Why Use Energy Balances?

All process calculations must:


-

Mass Balance Mol Balance Heat Balance

A tool for calculations Evaluate design alternatives

First Law of Thermodynamics

The total quantity of energy is constant. When energy disappears in one form, it appears simultaneously in other forms.
A (energy of system) + A (energy of surroundings) = 0

A (energy of surroundings) = AQ

+AW

A (energy of system) = A E

+ APE + A KE

Where:
AQ = heat added to system
A W = work done by the system

A E = change in internal energy APE = change in potenial energy

AKE = change in kinetic energy

The various forms of energy in the above equation are defined as follows:

Internal energy Flow energy to force mass m in (or out) of the system at pressure p with unit volume V Kinetic energy of the streams Potential energy referred to some datum Surface energy (may be very large term for sprays, emulsions, etc.). Net heat added to the system Work in all its forms done by the system Net change in energy content within the system (changes of inventory, temperature, composition, elevation, etc.)

The terms in the above equation are defined as follows:

Z = height above some datum,ft


u = velocity, fils p = pressure, lbf /ft2

V = specific volume, fi3/lbm

U = internal energy, ft .lbf/Ib,

C Q = heat added to system, f i . Ibf / h C W = work done by the system,f i . Ibf/h


g =acceleration of gravity, ft/sz g, = gravitational constant, fi . lbm/lbf - sZ m = mass flowrate,Ib/h ES = surface energy, ft .lbf / h
A E = net change in energy content of system, fi . Ibf/h

For flow processes at constant pressure where changes of internal energy are large, while kinetic, potential and surface energy changes are small, for steady state, the above equation for the first law of thermodynamics reduces to the following:

A 0 = m2U2 + m2p2V2 + A W - mlUl - mlplVl

Since U + pV occurs repeatedly, it has been defined as

ENTHALPY and is given the symbol H,so that:

H=U+pV

Enthalpy Base States

Liquidsat 60" F ( H = 0 )

Hydrogen (Hz), oxygen (02), nitrogen (N2), and carbon monoxide (CO) as vapors at 6 0 " and ~ 0 psia.

Pure Component Enthalpy

Calculation of Latent Heat


* *

Ideal Vapor Enthalpy Enthalpy Correction for Pressure

Enthalpy us Temperature Diagram

Temperature, "F
EDSRCC-1101

Latent Heat

There are several methods available for calculating the latent heat of vaporization of a pure component, one of which is the famous Clapeyron equation:

Where:

VP = vapor pressure, psia T = absolute temperature, " R R = gasconstant, 1.987 Btullb mol .OR

3, = latent heat, Btu/lbmol

In 1938, Kistyakowski proposed the following equation for the calculation of the latent heat of hydrocarbons and other non-polar compounds:

Where:

,Ib = latent heat at thenormal boiling point, Btu/lbmol


T b = normal boiling point," R

For calculation of latent heat at temperatures other than the normal boiling point, the following equation by
Watson may be used:

Where:

At = latent heat at temperatureT(" R),Btu/lbmol


T, = critical temperature, " R T b = normal boiling point," R

Latent Heat Ratio

It can be rigorously shown that the ratio of the latent heat of a substance to the latent heat of a reference

substance is very nearly a constant at the same reduced temperature, or

Where:

q = latent heat ratio

2, = latent heat of pure component, Btullb


ibw = latent heat of water at the reduced temperatureof the pure component, Btu/lb ..
The latent heat for water may be calculated from the following equation:

Where:

ibw = la tent heat at T, Btu/lb


T , = reduced temperatureof pure component

n = exponent which is a function of T,

Ideal Vapor Enthalpy

The specific heat of an ideal vapor is commonly available in the literature in the form of curves, tabulations, or equations in the form:

Where:
C , = specific heat Btu/lb-OF T = temperature," F o r 0R o r 0C A, B, C = constants specific to each substance

In order to determine the change in ideal vapor enthalpy for a compound between two temperatures, it is necessary to integrate the above equation to get the following:

Where:

AH = change in vapor enthalpy between T p and T I ,Btulh m = mass flowrate, Ib/h

T = temperature," F or0R or " C

Enthalpy Correction for Gases and Vapors

The Enthalpy Correction for Gases and Vapors chart by Hougen and Watson is based on the equation of state (PV = ZRT) and the theorem of corresponding states.

Correction to be applied to the ideal vapor enthalpy to account for the effects of pressure or non-ideality of a pure component.

Note that the units are gmcal/gmmol/"K which is exactly equivalent to Btu/lbmoVOR.

Enthalpy Mixing Rules

Only ideal gas state (P = 0 ) enthalpies are additive.

Blending of saturated liquid enthalpies.

Where:

wj = mass flo wrate of component i , Ib/h

H,,,

= saturated liquid enthalpy of component i , Btullb

H,? = ideal vapor enthalpy of component i ,Btullb

Enthalpy us Temperafure Diagram

60

T2

Temperature, O F

ldeal Vapor Enthalpy of Mixtures

ldeal vapor enthalpies, when plotted against the ideal vapor enthalpy of one reference substance at equal reduced temperature produce nearly perfect straight lines from about 0.3 to 1.5 Tr.

Ideal Vapor Enthalpy ofMixfures

" X Ideal Vapor Enthalpy, Hx*


EDS-ROO-1102

1.

Given the API gravity and ASTM distillation for a material, calculate the UOP K, molecular weight, molal average boiling point (NBP), critical temperature, critical pressure, and estimate the vapor pressure at 60F. Using the API gravity and UOP K, obtain the linear specific heat of the liquid at GOOF and the normal boiling point (NBP) from chart RE F-1. The saturated liquid enthalpy at the normal boiling point can then be calculated as follows:

2.

Where:
NBP = normal boiling point, F

Cp = liquid specific heat, Btul1b.O F

3.

Using molecular weight and normal boiling point, obtain the latent heat of vaporization at the normal boiling point from chart RE F-3. Then, add the latent heat to the saturated liquid enthalpy to get the saturated vapor enthalpy at the normal boiling point.

4.

Calculate the enthalpy correction at the normal boiling point due to lack of ideal behavior from the Enthalpy Correction for Gases and Vapors chart.

Then:

This is then one of the two points required to define the ideal vapor enthalpy curve for the mixture.

5.

Using the reduced temperature for the substance at its normal boiling point, calculate "nu for water, and the latent heat of water at this temperature.

6.

Calculate the latent heat ratio for the substance from the following:

7.

Calculate the reduced temperature of the substance at the datum temperature, 6 0 O ~ from the following:

8.

Again, calculate "n" for water using the reduced temperature calculated in step 7. Then, compute the latent heat of vaporization of water for this reduced temperature.

9.

Compute the latent heat of vaporization of the substance at 60 F from the following:

10.

Since the datum liquid has zero enthalpy at 60F, the enthalpy of tne saturated vapor at 60F is equal to the latent heat of vaporization at 60F.

1 1.

At ~ o ' F ,calculate the reduced vapor pressure. Use this to calculate the enthalpy correction at 60' F due to lack of ideal behavior from the Enthalpy Correction for Gases and Vapors chart. Then,

This is then the second point required to fix the ideal vapor enthalpy at any temperature.

12.

At each of the reduced temperatures for the substance, calculate the corresponding temperature for normal hexane from the following:

13.

For each of the temperatures calculated for normal hexane in step 12, calculate the ideal vapor enthalpy of normal hexane using the equation given in Table 2.

14.

The ideal vapor enthalpy of substance

"X"is linearly related to the ideal vapor enthalpy of normal

hexane at equal reduced temperature (see Figure 2). Compute ,the slope "B" and intercept "A" of a straight line through the two points from the following:

Ideal Vapor Enthalpy o fMktures

"XuIdeal Vapor Enthalpy, Hx*

Enthalpy o f Mixtures

UOP has simplified the calculation of ,the enthalpy for mixtures with the following charts:

PD chart 870 (liquids) PD chart 189 (vapors)

These charts require only the UOP K and cubic average boiling point (CABP) for a mixture.

Heat o f Reaction

Temperature, O F

Heat

o f Reaction

If the heat. of reaction is to be calculated in terms of Btu/lbmol of product D, then it can be calculated from
either of the following:
A Hr = (heat of combustion)react - (heat of combustion)prods

or:

AHr = (heat of f ~ r r n a t i o n ) ~ (heat ~ , of formation)react

AHr = ( 1 ~ 5 ) ( d H f , ~ ) + ( A H f , ~ ) - ( 2 / 5 ) ( ~ H f , ~ ) - ( 3 / 5 ) ( ~ ~ f , ~ )

EDS0896

UOP

1 1-34

where the heat of combustion or the heat of formation is expressed in Btu/lbrnol


A H,is positive +endothermic

AH, is negative -+ exothermic

Calculate the heat of reaction in terms of Btu/lbmol of benzene for the following reaction:
Benzene + Orthotxylene + (2)Toluene

The gross heat of combustion for each component in the above reaction can be found in chart RE-C-1C.
AH,, 8 = - 17992Btu/lb benzne

A H,,T = - 18253Btu/lb toluene

A HC,x = - 18446Btu/lb orthoxylene

In order to express the heat of reaction in terms of Btuilbmol of benzene, the above heats of combustion must be converted to this unit.
AH c , = ~ - 17992Btu/lb (78.108)lblmol = - 1405319Btullb mol Bz

AHc,= ~ - 18253Btullb (92.134)(2)=- 3363444 Btullb mol Bz

Then:
A Hr = (- 1405319- 1958227)- (-3363444)

= - 102 Btu/lb mol BZ(exothermic)

ENERGY BALANCE PROBLEMS

1.

Using Kistyakowski's equation, calculate the latent heat at the normal boiling point in Btullb of the following compounds:

Cyclohexa ne Benzene Toluene Iso-pentane N-octane

2.

Using Watson's equation and the latent heats calculated in the previous problem, determine the latent heat at the indicated temperature for each of the following:

Cyclohexane Benzene Toluene Iso-pentane N-octane

250F 350F 60 and 300" F 200F 150F

3.

The ideal vapor heat capacity for toluene is given by the following equation:

C p = , ? . 8 6 9 + 5 . 2 9 3 ~ 1 0 - ~~2 . 0 8 6 ~ 1 0 +~ 3~ .~ 292~10-~~~
/-

, /

Where:
Cp = heat capacity,Btu/lbmol." F

T = temperature, " F

Calculate the change in the ideal vapor enthalpy of toluene between 300F and 400F.

4.

Using the change in ideal vapor enthalpy calculated in the previous problem and the Enthalpy Correction Chart for Gases and Vapors, determine the change in the saturated vapor enthalpy of toluene between 300F and 400F. The vapor pressure of toluene at 300F is 38.5 psia and at
400F is 116.0 psia.

5.

Calculate the latent heat ratio (q) for methanol, with water as the reference substance, at each of the following temperatures:

Temperature,

O F

Latent heat, Btullb

176 248 356

466.2 4 1 7.6 3 1 8.6

Methanol has the following physical properties:

Critical tem erature, O Critical ressure, sia Molecular wei ht

923.7

32.043

6.

Water at 35F is being pumped from the bottom of a well that is 150 feet deep at the rate of 2000 Iblhr into a vented storage tank that is 30 feet above the ground. To prevent freezing in the winter, a small heater puts 60,000 Btulhr of heat into the water during its transfer from the well to the storage tank. Heat is lost from the whole system at a constant rate of 25,000Btulhr. A 2.0 horsepower pump is being used to pump the water. Assume that about 55 pct of the rated horsepower of the pump goes into the work of pumping the water and the remainder of the horsepower is dissipated as heat. Assuming also that the velocity in the suction and discharge lines is small, what is the rise or fall in the temperature of the water as it enters the storage tank? Assume the specific heat for water of 1.0 Btullb
- O F

is constant over the expected temperature range.

7.

Using Kistyakowski's equation and Watson's equation to calculate latent heats and the Enthalpy Correction for Gases and Vapors chart to calculate the effect of pressure on vapor enthalpy, complete the table below for propylene. Use the following ideal vapor heat capacity equation:

Where:

Cp= heat capacity,Bt~/lbrnol.~ R


T = temperature, R

"F
60
150

Vapor pressure, psia


132 414

sl

sv

H*

Where:

HsI = saturated liquid enthalpy, BtuJlb Hsv = saturatedvapor enthalpy,BtuJlb H* = ideal vapor enthalpy,BfuJlb

8.

Calculate the standard heat of reaction in terms of Btu/lb of benzene for the following reaction: 3 Hz

+ Benzene + Cyclohexane

9.

A mixture of propylene and benzene is vaporized in a steam heater and fed to a reactor to produce cumene. The reactor effluent is condensed and sent to storage. The reaction is represented by the following mol balance:

In:

Ibrnollh
100 800 0

Out:

IbrnoVh
60 760 40

Propylene Benzene
,

Cumene(isopropylbenzene)

Assume that heat loss and pressure drop in the reactor are negligible and that the reaction takes place entirely in the vapor phase. Use the following enthalpy data:

H*, Btullb
6 0"F

400F

450F

500F

Propylene Benzene Cumene

165 189 163

31 5 300 293

34 1 32 1 31 6

369 342 34 1

In this reaction it is customary to express the heat of reaction in terms of Btuflb of propylene reacted.

Complete the attached heat and weight balance for this process.

EDS0896

uoP

11-38

10.

Calculate the ideal vapor enthalpy coefficients (A, 6) for a naphtha having the following properties:

HEAT AND WEIGHT BALANCES


Engineering Design Seminar Energy Balance Problems Cumene Unit

Energy Balances

Answers

ANSWERS TO ENERGY BALANCE PROBLEMS

Problem #I

Kistyakowski's equation is:

Where:
= =

At, Tb

latent heat at the normal boiling point, Btu/lb rnol normal boiling point, O R

Tb, O R

A b , Btu/lb m0l

mol wt, b/lb mol


84.1 78.1 92.1 72.1 114.1

Ab, BtlI/lb
154 166 154 151 130

Cyclohexane Benzene Toluene Iso-pentane N-octane

637 636 691 542 718

12993 12971 14206 10882 14816

Problem #2

Watson's equation is:

Where:

A, Tc
Tb

= latent heat at temperature T ("R), Btullb = critical temperature, O R = normal boiling point, O R

Tb,O R
Cyclohexane Benzene Toluene Toluene Iso-pentane N-octane
637 636 69 1 69 1 542 71 8

Tc," I3
998 1013 1069 1069 830

T,O R
71 0 81 0 520 760 660 61 0

A b ,Btullb
141 131 177 143 124 146

1025

Problem #3

The change in ideal vapor enthalpy of an ideal gas between TI and T2 may be determined from the following equation:

Substituting the equation for C

and integrating gives:

Where for toluene:

Now:

Substituting and solving:

Problem #4

Calculate the reduced conditions at the given temperatures:


PC, psis 590 590

T, O R
860 760

Tc,

O R

Tc
0.80 0.71

P, psia 116.0 38.5

pr

1069 1069

0.20 0.065

Determine the enthalpy correction from the chart at the reduced conditions:

Now:

and:
(HZoo- H&) = 3696.6 Btu/lb mol (Problem3 )

( H ;~ ~~ ~

0= 0 577.3 ) Btujlb

mol

(H:,

- H4,

) = 1282.8 Btu//brnol

(H400- H3O0)= 577.3 - 1282.8 + 3696.6 = 2991.1 Btullb mol

Problem #5

Use the equation for the latent heat of water:

& = 970.3[(1- 1;)/0.4235]~

The exponent "nu may be calculated using either the equation given on page 11 of the notes or interpolated from Table 1 in the notes.

Problem #6

Apply the following general equation,

CQ- C W =m2U*

+m2~2V2 +m2Z2 glgc + m2.2212gc

Since the velocity in the suction and discharge lines is small, the kinetic energy terms will be negligible. Then,
AKE = m2u ;/zgc -mlu :/2gc = o

Let the bottom of the well be the reference line so that Z1 = 0 and Z2 = 180 feet. Then,

= 463 Btulh

The heat lost by the system is 25,000 Btulh while the heater puts 60,000 Btulh into the system. The net heat exchange is:

The pump is doing work on the system at the following rate:

xW

= (-2)hp(O. 55)(33000)ft .lbf/min. hp(60)min/h(1/778)Btulft .lbf

The sign is negative because work is being done on the system.

Since H = pV + U, the equation may now be written with the known quantities as follows:

35000 - (-2799) = AH + 0 + 463

Or:

By definition:

Since water is practically noncompressible and since the anticipated temperature range is small, the heat capacity of water may be assumed to be constant and equal to 1.0 Btu/lb.*. Then,

or:

Problem #7

Following are the required properties for propylene from chart RE-C-1b:

T b= -54" F + 460 = 406" R

PC = 667 psia

mol wt = 42.078 Ibllb mol

Calculate the latent heat of vaporization at the normal boiling point from Kistyakowski's equation:

Ab = Tb(7.583 +4.571/0gloT b )

= (406)(7.58 4.571log406)

Calculate the latent heats of vaporization at 60F and 150F using Watson's equation:

At 60F, the vapor pressure of propylene is 132.0 psia. Then,

/is.,60 = 0 (by definition of base state)

Hs.,GO = 0 + 149.5 = 149.5B t ~ l l b


T, = 5201657 = 0.79

P, = 1321667 = 0.20

From the enthalpy correction chart for gases and vapors:


(H* - H ) / T ~ = 1 . 2 5 ~ a l / g m m oK l -= ~ 1.25 B t u / l b m ~ I . ~ R

Hgo = Hsv,60 + (657)OR(1.25)Btu/lbmol. O R(1/42.078)Ib molllb Hgo = 149.5 + 19.5 = 169.0B t ~ l l b

Now:

At 150F,the vapor pressure of propylene is 414 psia. Then:


= 169.0+ 34.1 = 203.1 B t ~ l l b

T, = (6 101657)= 0.93

P, = 4 141667 = 0.62

From the enthalpy correction chart for gases and vapors:

(H' - H)/T, = 3.0 callgm mo1.O K = 3.0 Btullb mol O R

and:

OF

Vapor pressure, psia


132 41 4

H SI
0 56.7

1
'

H SV
149.5 156.3

H*
169.0 203.1

60 150

Problem #8 From chart RE-C-lc, determine the heats of combustion for the reactants and product in terms of benzene:.

and:
AH, = -4725.6-17992-(-21589.6)=-1128Bt~llbBz

Problem #9

First, calculate the heat of reaction,


C5 + Benzene + lsopropylbenzene(cumene)

Look up the heats of combustion for the reactants and product from chart RE-C-lc. Note that the heat of combustion for propylene is for the gas phase. Since the UOP enthalpy base state for propylene is liquid, the latent heat of vaporization must be added to the heat of combustion of the gas to get the heat of combustion of the liquid. The latent heat of vaporization of propylene was determined to be 150 Btutlb at 60F in Problem 7.

AHcBBz = (-1 7992)Btu/lbBz(78.108)lb Bzllb mol

(1/42.078)1bmol ~ ; / l b ( l ) m o ~ t z / m oC; l

= -533 12 Btullb Cz

AH, = (-33398)

+ (-20897) - (-53312) = -983 B t ~ / l C b ;


(-983)Btullb

AH; = (100 - 60)mol c ; / h (42.078)lb/lb mol

= - 1.65 x

lo6 Btu/h (exothermic)

Estimate the enthalpy of the feed from the given information,

mol /h Propylene Benzene Total 100 800 900

Iblh

~ Btullb ~
31 5 300 30 1

~ Tc, O ~f 3
657 1013 973

, P , psia
667 71 4 709

4208 62486 66694

From the enthalpy correction chart for gases,

(H* - H ) F c = 2.6 Btullb mol.'R

Since the reaction is exothermic, the enthalpy of the products will be greater than the enthalpy of the feeds. Then:

Finding the temperature of the reactor effluent is now a trial-and-error solution. Trial 1 at 450F and 350 psia,

From the enthalpy correction chart for gases,

(H* - H)/T, = 2.4Btullb mol.OR

This is close enough to the required enthalpy of 19.45 x lo6 Btu/h to say that the outlet temperature is

450F.
Calculate the API gravity of the liquid feed and product,
C ; = 139.6"API

BZ =28.5"API

IPB = 31.8"API

A PIhed = [(4208)(139.6)+ (62486)(28.5)Y66694= 35.5


APIprod= [(2525)(139.6) + (59362)(28.5)+ (4807)(31.8)y66694= 32.9

Calculate the UOP K of the feed and product in a similar manner,

Cg = 14.18UOPK

Bz =9.72 UOPK

IPB = 10.56 UOPK

Calculate the molecular weight of the feed and product,


mol wtfeed = 66694/900 = 74.1

Calculate the flowing vapor density for the reactor feed and effluent,
pv = (rnol wt)(P)/zRT

Where:
pv = vapor density, lb/ft3

mol wt = molecular weight, Ib/lb mol

P = pressure, psia R = gasconstant = 10.71


T = temperature," R

The compressibility factor z may be determined from chart RE-E-3 as a function of the reduced temperature and pressure.

Feed

Effluent

Tr
Pr

0.88 0.49 0.62

0.92 0.50 0.67

ft3/sen= 66694/(3600x 4.16) = 4.5 ff3/s

Calculate the BPSD (at 60'F) of the feed and product using charts RE-C-lc and RE-C-1b,

BPSDlrnph
Propylene Benzene IPB Total
5.525 6.052 9.507

Feed, mol/h
100 800 0 900

Feed, BPSD
552.5 4841.6 0 5394.1

Product, rnol /h
60 760 40 860

Product, BPSD
331.5 4599.5 380.3 531 1.3

Calculate the flowing gpm of the liquid feed and product from the BPSD calculated above,
gpmfeed= (5394.1) BPSD(42)gal/bb1(1/24) d/h(1/60)hlmin
= 157.3

gpmpmd= (531 1.3)BPSD(42)gal/bb-(1124)d/h(1/60) h/min


= 154.9

Calculate the flowing specific gravity of the liquid feed and product,
sp.
= 66694/[(157.3)(500)] = 0.848

sp.gr.p,d

= 66694/[(154.9)(500)] = 0.861

Finally, calculate the

l o 6 std ft3/d of reactor feed and effluent,


lo6 std ff3/dfeed= (900)(24)(379)/106 = 8.19
lo6 std ff3/dprod = (860)(24)(379)/106= 7.82

HEAT AND WEIGHT BALANCES

Engineering Design Seminar Energy Balance Problems Cumene Unit

Stream Feed To Heater

API (Ibtgal) UOP K


35.5 10.0

mol wt
74.1

Flowing sp.gr. (1b/ft3)


0.848

O F
60

psia (mmHg)
350

BPSD (106std ft3/d)


5394.0

Flowing GPM (ft3/s)


157

mollh
900

Ibth
66694

Btullb
0

106 0tu/h 0.00 17.80

Feed to Reactor
10.0 74.1 (4.54) 400 335 (8.19) (4.1) 900 66694 267
17.80

Heat of Reaction
1.65

Reactor Effluent
9.95 77.6 (4.16) 450 335 (7.82) (4.5) 860 66694 292 19.45 19.45

Cooler Duty Product From Unit (Liquid)

I I I

32.9

9.95

77.6

0.861

60

320

5311.O

155

860

66694

0.00

Problem #10

Using the API gravity and UOP K, obtain the linear specific heat of the liquid at 60F and the normal boiling point (NBP) from chart RE F-1.

Note that the correction factor to be used is equal to 1.0.

The saturated liquid enthalpy at the normal boiling point can then be calculated as follows:

Using the molecular weight and normal boiling point, obtain the latent heat of vaporization at the normal boiling point from chart RE F-3.

Then, add the latent heat to the saturated liquid enthalpy to get the saturated vapor enthalpy at the normal boiling point.

Calculate the enthalpy correction at the normal boiling point due lo lack of ideal behavior from the Enthalpy Correction for Gases and Vapors chart. Then,

Then:

This is then o n e of the t w o points required t o d e f i n e t h e ideal vapor enthalpy c u r v e for t h e mixture.
Using the reduced temperature for the naphtha at its normal boiling point, calculate "n" for water, and the latent heat of water

(A,)

at this temperature.

Now, calculate the latent heat of water,

A ,

= 970.3[(1- 0.699)/(0.4235)] 0.3305

= 860 Btullb

Calculate 'the latent heat ratio, q, for the naphtha from the following:

9= ; l ~ ~ ~ / A w
= 124.51860 = 0.1448

Calculate the reduced temperature of the naphtha at the datum temperature, 60F, from the following:

T,,,,

= 519.7/TC

= 519.7/1104=0.471

Again, calculate "n" for water using this reduced temperature. Then, compute the latent heat of for this reduced temperature. vaporization of water (hw,60)

Now, calculate the latent heat of water,

A, = 970.3[(1- 0.471)/(0.4235)]

0.327

Compute the latent heat of vaporization of the naphtha at 60F from the following:

;160

=q(~w.60)

= (0.1448)(1043) = 151.0Btu/lb

Since the datum liquid has zero enthalpy at 60F, the enthalpy of the saturated vapor at 60'F is equal to the latent heat of vaporization at 60'F.

At 6 0 ' F , calculate the reduced vapor pressure.

Use this to calculate the enthalpy correction at 60F due to lack of ideal behavior from the Enthalpy Correction for Gases and Vapors chart. Since this point is off the low end of the chart, assume the correction is negligibly small.

Then:

This is then the second point required to fix the ideal vapor enthalpy at any temperature.

At each of the reduced temperatures for the naphtha, calculate the corresponding temperature for normal

hexane from the following:

For each of the above temperatures calculated for normal hexane, calculate the ideal vapor enthalpy of normal hexane from the equation given in Table 2 of the notes.

The ideal vapor enthalpy of the naphtha is linearly related to the ideal vapor enthalpy of normal hexane at equal reduced temperature (see Figure 2 in the notes). Compute the slope "B" and intercept "A" of a straight line through the two points from the following:

Solving:

and:

450r . .
A .

. d . . . -

-- . . ...... -- . .. - -. . -- -- - - .--.. - -- . .- . -.- .- - - - -- - . -NORMAL HEXANE'.

UOP PROCESS DIVISION . . . ....................... ...-............ ... - . .- .... ..... ENTHAtpy . . . . . . . .


--.

.......

0 PSIG

....

1 ..

............

----

.
-.
--

. -

........

-- .--- -..- - -- .- ...... -........ -.-..-- .. -. ... - . . . . - . . . . . .......... - ....... --.. .- ............ .-. - ..-.- . ---- - -. .- - -..- . . - ..- - . -- ....-. - - - - - - - .-- -. - -- - - - . - - . ..-... --.-.-- .... - -.. .-. .. -- . . . . . . . . . . . . . . . -- .... ---... -. -.-- - -... -. . . . . -. . . . . -- ............
..A.

. .

.......-

. . . . . . .

...-...

. . .

..............
.........

IS0

'.

. . . . . . . .

. . . . . . . . .
. . . . . . . . . . . . .

.............

--

...

-.-

.- . . . . . . ....... . . . .- .- - . . .

. . . .

..

81.6
12.81

- 86.172 155.7 .- LATENT- HEAT AT N6P , . BTU/CB 1 43.96 CR I T I CAL-'TEMPERATURE , "R. 914.1
. --BPD/PlOL;rHR.-. . . . . . ..... . . . . . . -.
. . .
.-. ... -.... - .- . - . .... . ..................... ....... ......... ... ...............
,

. 8.695

NORMAL HEXANE

TEMPERATURE,

Nonnal Boiling P o i n t 155,7"F Latent Heat a t 155.7"~--1hh.O Btu/Lb. C r i t i c a l Temperature 45h. S0F C r i t i c a l Pressure 439.7 Psia Reference: A.1.Ch.E. J. 2, (1956)

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