Module 9001 Energy Balance

Paul Ashall, 2008

Paul Ashall, 2008

Concerned with energy changes and energy flow in a chemical process. Conservation of energy first law of thermodynamics i.e. accumulation of energy in a system = energy input energy output

Paul Ashall, 2008

Forms of energy

Potential energy (mgh) Kinetic energy (1/2 mv2) Thermal energy heat (Q) supplied to or removed from a process Work energy e.g. work done by a pump (W) to transport fluids Internal energy (U) of molecules

m mass (kg) g gravitational constant, 9.81 ms-2 v velocity, ms-1

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Energy balance
W

mass in

mass out

system
Hin Q Hout

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IUPAC convention
- heat transferred to a system is +ve and heat transferred from a system is ve - work done on a system is+ve and work done by a system is -ve

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Steady state/non-steady state

Non steady state accumulation/depletion of energy in system

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Uses

Heat required for a process Rate of heat removal from a process Heat transfer/design of heat exchangers Process design to determine energy requirements of a process Pump power requirements (mechanical energy balance) Pattern of energy usage in operation Process control Process design &Paul Ashall, 2008 development etc

Enthalpy balance
p.e., k.e., W terms = 0 Q = H2 H1 or Q = H

, where H2 is the total enthalpy of output streams and H1is the total enthalpy of input streams, Q is the difference in total enthalpy i.e. the enthalpy (heat) transferred to or from the system
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continued
Q ve (H1>H2), heat removed from system Q +ve (H2>H1), heat supplied to system.

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Example steam boiler

Two input streams: stream 1- 120 kg/min. water, 30 deg cent., H = 125.7 kJ/kg; stream 2 175 kg/min, 65 deg cent, H= 272 kJ/kg One output stream: 295 kg/min. saturated steam(17 atm., 204 deg cent.), H = 2793.4 kJ/kg
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continued
Ignore k.e. and p.e. terms relative to enthalpy changes for processes involving phase changes, chemical reactions, large temperature changes etc Q = H (enthalpy balance) Basis for calculation 1 min. Steady state Q = Hout Hin
Q = [295 x 2793.4] [(120 x 125.7) + (175 x 272)]

Q = + 7.67 x 105 kJ/min

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Steam tables

Enthalpy values (H kJ/kg) at various P, T

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Enthalpy changes
Change of T at constant P Change of P at constant T Change of phase Solution Mixing Chemical reaction crystallisation

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Latent heats (phase changes)

Vapourisation (L to V) Melting (S to L) Sublimation (S to V)

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Mechanical energy balance

Consider mechanical energy terms only Application to flow of liquids P + v2 + g h +F = W 2 where W is work done on system by a pump and F is frictional energy loss in system (J/kg) P = P2 P1; v2 = v22 v12; h = h2 h1

Bernoulli equation (F=0, W=0)

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Example - Bernoulli eqtn.

Water flows between two points 1,2. The volumetric flow rate is 20 litres/min. Point 2 is 50 m higher than point 1. The pipe internal diameters are 0.5 cm at point 1 and 1 cm at point 2. The pressure at point 2 is 1 atm.. Calculate the pressure at point 2.
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continued
P/ + v2/2 + gh +F = W
P = P2 P1 (Pa) v2 = v22 v12 h = h2 - h1 (m) F= frictional energy loss (mechanical energy loss to system) (J/kg) W = work done on system by pump (J/kg) = 1000 kg/m3
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continued
Volumetric flow is 20/(1000.60) m3/s = 0.000333 m3/s v1 = 0.000333/((0.0025)2) = 16.97 m/s v2 = 0.000333/ ((0.005)2) = 4.24 m/s
(101325 - P1)/1000 + [(4.24)2 (16.97)2]/2 + 9.81.50 = 0 P1 = 456825 Pa (4.6 bar)

Paul Ashall, 2008

Sensible heat/enthalpy calculations

Sensible heat heat/enthalpy that must be transferred to raise or lower the temperature of a substance or mixture of substances. Heat capacities/specific heats (solids, liquids, gases,vapours) Heat capacity/specific heat at constant P, Cp(T) = dH/dT or H = integral Cp(T)dT between limits T2 and T1 Use of mean heat capacities/specific heats over a temperature range Use of simple empirical equations to describe the variation of Cp with T
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continued
e.g. Cp = a + bT + cT2 + dT3 ,where a, b, c, d are coefficients H = integralCpdT between limits T2, T1
H = [aT + bT2 + cT3 + dT4] 2 3 4 Calculate values for T = T2, T1 and subtract Note: T may be in deg cent or K - check units for Cp!
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Example
Calculate the enthalpy required to heat a stream of nitrogen gas flowing at 100 mole/min., through a gas heater from 20 to 100 deg. cent. (use mean Cp value 29.1J mol-1 K-1 or Cp = 29 + 0.22 x 10-2T + 0.572 x 10-5T2 2.87 x 10-9 T3, where T is in deg cent)
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Heat capacity/specific heat data

Felder & Rousseau pp372/373 and Table B10 Perrys Chemical Engineers Handbook The properties of gases and liquids, R. Reid et al, 4th edition, McGraw Hill, 1987 Estimating thermochemical properties of liquids part 7- heat capacity, P. Gold & G.Ogle, Chem. Eng., 1969, p130 Coulson & Richardson Chem. Eng., Vol. 6, 3rd edition, ch. 8, pp321-324 PhysProps
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Example change of phase

A feed stream to a distillation unit contains an equimolar mixture of benzene and toluene at 10 deg cent.The vapour stream from the top of the column contains 68.4 mol % benzene at 50 deg cent. and the liquid stream from the bottom of the column contains 40 mol% benzene at 50 deg cent.
[Need Cp (benzene, liquid), Cp (toluene, liquid), Cp (benzene, vapour), Cp (toluene, vapour), latent heat of vapourisation benzene, latent heat of vapourisation toluene.]
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Energy balances on systems involving chemical reaction

Standard heat of formation (Hof) heat of reaction when product is formed from its elements in their standard states at 298 K, 1 atm. (kJ/mol)

aA + bB cC + dD -a -b +c +d (stoichiometric coefficients, i) HofA, HofB, HofC, HofD (heats of formation) HoR = c HofC + d HofD - a HofA - bHofB
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Heat (enthalpy) of reaction

HoR ve (exothermic reaction) HoR +ve (endothermic reaction)

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Enthalpy balance equation reactor

Qp = Hproducts Hreactants + Qr
Qp heat transferred to or from process Qr reaction heat ( HoR), where is extent of reaction and is equal to [moles component,i, out moles component i, in]/ i
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Hreactants

Hproducts

system Qr
+ve Qp -ve Note: enthalpy values must be calculated with reference to a Paul Ashall, 2008 temperature of 25 deg cent

Energy balance techniques

Complete mass balance/molar balance Calculate all enthalpy changes between process conditions and standard/reference conditions for all components at start (input) and finish (output). Consider any additional enthalpy changes Solve enthalpy balance equation

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Energy balance techniques

Adiabatic temperature: Qp = 0

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Examples
Reactor Crystalliser Drier Distillation

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References
The Properties of Gases and Liquids, R. Reid Elementary Principles of Chemical Processes, R.M.Felder and R.W.Rousseau

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