McGill University

CHEE 204 Chemical Engineering Principles II

Feb. 7, 2014

CHEE 204
1st Mid-term
1. Natural Gas (NG) is mixed with steam and sent into a reforming reactor to produce syngas. The inlet
temperature is 550 K and the outlet temperature of the reformer is 1200 K.
NG composition: CH4 (80 vol%), C2H6 (10 vol%), CO2 (5 vol%) and N2 (5 vol%).
a. Calculate the higher heating value (HHV in MJ/m3) of the natural gas. (Tip: Pay attention to the
state/phase of water).
b. What is the difference between lower and higher heating value?
c. Draw the process flow diagram with the following specifications:
NG is pumped via a gas compressor
Water is pumped via liquid pump and then evaporated in a heat exchanger (steam generator).
NG and steam are mixed and fed to the reformer, which is a vessel with heating jackets. The outlet
stream (i.e., Syngas) is cooled with the same heat exchanger which is used to evaporate the water.
d. Calculate the necessary amount of heat (Q in MW) to run the steam reformer at a 100% conversion
of 100 mol/s natural gas. Reference temperature is 298 K and use heat of reaction method.
Balance the chemical equations!
CH4 (g) + _ H2O (g) _ CO (g) + _ H2 (g)
C2H6 (g) + _ H2O (g) _ CO (g) + _ H2 (g)
How much steam is needed and how much CO and H2 are produced (mol/s)?
Calculate standard heat of reaction for the two reforming reactions. Are these reactions
endothermic or exothermic?
Prepare a stream table with inlet and outlet molar flows and enthalpies for the reformer.

2.

What is the difference between combustion and gasification?

3.

Biomass has the following CHNSO composition on a dry-ash-free basis: C = 50 wt%daf ; H = 6 wt%daf; N =
0.5 wt%daf; S = 0 wt%daf; O = 43.5 wt%daf. The ash content of the dry biomass is 5 wt%.
a. Calculated the higher heating value based on the empirical BOIE equation [HHVdry in MJ/kgdry].
b. Why has the oxygen a negative value in the BOIE equation?
c. 1 g of that biomass is burned in a Bomb-Calorimeter filled with 0.5 liter of water. How much does
the temperature increase if the empty calorimeter has a heat capacity of 1.5 kJ/K and the initial
temperature is 25C.
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McGill University
CHEE 204 Chemical Engineering Principles II

Feb. 7, 2014

Notes:
Table 1 Thermodynamic properties

Species

Hf0

Specific enthalpies H [kJ/mol]

[kJ/mol]

298 K

500 K

600 K

700 K

800 K

900 K

1000 K

1100 K

1200 K

CH4 (g)

-74.5

8.23

13.18

18.72

24.80

31.40

38.46

45.94

53.81

C2H6 (g)

-84.7

12.67

19.94

27.39

34.82

42.14

49.30

56.30

63.13

H2O (g)

-241.8

6.92

10.50

14.19

18.00

21.94

26.00

30.19

34.50

CO (g)

-110.5

5.93

8.94

12.02

15.18

18.40

21.69

25.03

28.43

H2 (g)

5.88

8.82

11.75

14.70

17.67

20.67

23.71

26.79

CO2 (g)

-393.5

8.36

12.95

17.78

22.80

28.00

33.35

38.83

44.42

N2 (g)

5.91

8.89

11.94

15.05

18.22

21.46

24.76

28.11

Water at 298 K in liquid state:

H2O (l):
Hf0 = -285.8 kJ/mol
Heat capacity: cP = 4.18 J/(gK)
Molar Volume:
VM = 22.414 l/mol
BOIE equation:
HHVdaf = 35.16C + 116.225H + 6.28N 11.09O + 10.47S [MJ/kgdaf]

McGill University
CHEE 204 Chemical Engineering Principles II

Feb. 7, 2014

Solution:
1.
a.

Natural Gas
Higher Heating Value [MJ/m3]
Heat of combustion CH4: CH4 + 2 O2 CO2 + 2 H2O (l)
HC0 = iHf0
HC0 = -(-74.5) - 2(0) + (-393.5) + 2(-285.8) = -890.6 kJ/mol
HHVCH4 = - HC01/VM
HHVCH4 = - (-890.6)/22.414 = 39.7 MJ/m3
Heat of combustion C2H6: C2H6 + 3.5 O2 2 CO2 + 3 H2O (l)
HC0 = -(-84.7) 3.5(0) + 2(-393.5) + 3(-285.8) = -1559.7 kJ/mol
HHVCH4 = - (-1559.7)/22.414 = 69.6 MJ/m3
Heat of combustion of CO2 and N2 is zero (HC,CO2 = 0, HC,N2 = 0),
Higher heating value
HHVmix = xiHHVi
xi mol fractions
Volume fractions = mole fractions (Ideal gas)
HHVmix = 0.8 39.7 + 0.1 69.6 = 38.7 MJ/m3
Higher heating value of the natural gas is 38.7 MJ/m3.

b.

Difference between Higher and Lower Heating Value [MJ/m3]

The higher heating value is equal to the negative standard heat of combustion in which the product
water is assume to be liquid. In contrast, the lower heating value is equal to the negative standard heat
of combustion in which the product water is assumed to be vapor. Thus, the difference between HHV
and LHV is the evaporation enthalpy of water. HHV = LHV + nH2O HV0

c.

Process flow diagram

NG-Reformer
1200 K

NG

Q
Water

550 K
Syngas

McGill University
CHEE 204 Chemical Engineering Principles II
d.

Feb. 7, 2014

Calculation of Q [MW]
Balance equation

(1)

CH4 (g) + 1 H2O (g) CO (g) + 3 H2 (g)

(2)

C2H6 (g) + 2 H2O (g) 2 CO (g) + 5 H2 (g)

Mol balance: 100 mol/s NG

80 mol/s CH4

80 mol/s H2O needed 80 mol/s CO and 240 mol/s H2 produced

10 mol/s C2H6 20 mol/s H2O needed 20 mol/s CO and 50 mol/s H2 produced

Total

100 mol/s H2O needed 100 mol/s CO and 290 mol/s H2 produced

Standard Heat of Reaction

HR0 = iHf0
(1)
(2)

HR0 = - (-74.5) - (-241.8) + (-110.5) + 3(0) = 205.8 kJ/mol

HR0 = - (-84.7) - 2(-241.8) + 2(-110.5) + 5(0) = 347.3 kJ/mol

The standard heat of reaction of CH4 reforming is 205.8 kJ/mol and for C2H6 reforming 347.3
kJ/mol. Both reactions are endothermic.

Stream Table
Inlet at 550 K
Species

Outlet 1200 K

ni [mol/s]

Hi [kJ/mol]

ni [mol/s]

Hi [kJ/mol]

CH4

80

10.71

C2H6

10

16.31

H2O

100

8.71

CO

100

28.43

H2

290

26.79

CO2

10.66

44.42

N2

7.40

28.11

Inlet: Interpolation between 500 and 600 K from Table

CH4: HCH4 (550 K) = 8.23 + 50

= (13.18-8.23)/100

C2H6: HC2H4 (550 K) = 12.67 + 50

= (19.94-12.67)/100 HC2H4 (550 K) = 16.31 kJ/mol

H2O: HH2O (550 K) = 6.92 + 50

= (10.50-6.92)/100

HH2O (550 K) = 8.71 kJ/mol

CO2: HCO2 (550 K) = 8.36 + 50

= (12.95-8.36)/100

HCO2 (550 K) = 10.66 kJ/mol

= (8.89-5.91)/100

HN2 (550 K) = 7.40 kJ/mol

N2:

HN2 (550 K) = 5.91 + 50

HCH4 (550 K) = 10.71 kJ/mol

McGill University
CHEE 204 Chemical Engineering Principles II

Feb. 7, 2014

Outlet:
Enthalpies taken from the table.

Energy balance
Q = iHR0 + ni,outHi,out - ni,inHi,in
Q = (80 205.8 + 10 347.3) + (100 28.43 + 290 26.79 + 5 44.42 + 5 28.11) - 80 10.71 - 10
16.31 - 100 8.71 - 5 10.66- 5 7.4
Q = 19937.0 + 10974.75 - 1981.2
Q = 28930.55 kJ/s
Q = 28.9 MW
28.9 MW of heat must be supplied to the reformer to maintain the temperature of 1200 K.

2.

Difference between combustion and gasification

During combustion, the fuel is completed burned with Air or oxygen to CO2 and H2O. Combustion is a
highly exothermic reaction and the released heat can be used to run a steam cycle to generate
electricity. However, product gas of the combustion process (CO2, H2O) has no heating value. During
gasification, the fuel reacts with sub-stoichiometric amount of oxygen in form of Air, CO2 or H2O. The
product gas is mainly CO and H2, which has a high heating value. Gasification is an endothermic process
and requires heat, which can be supplied via partially combustion of the fuel. Thus, H of the overall
gasification process can be zero.

3.

Biomass
a.
Higher heating value based in BOIE
HHVdaf = 35.16 0.5 + 116.225 0.06 + 6.28 0.005 11.09 0.435
HHVdaf = 19.76 MJ/kgdaf
HHVdry = 19.76 (1-a) with a = 0.05
HHVdry = 18.77 MJ/kgdry
Biomass has a higher heating value of 18.77 MJ/kg dry fuel.
b.

Why has oxygen a negative value?

Because oxygen has no heating value, thus the amount of oxygen inside the fuel reduces the
relative amounts of the combustible such as carbon, hydrogen, sulfur and nitrogen per mass of
the fuel. Heating value is defined either per kilogram dry or dry-ash-free sample.

c.

Calorimeter in which 1 g of biomass is burned.

Q = m cp dT + C dT
18.77 kJ/gdry 1 g = 18.77 kJ
18.77 kJ = 500 g 4.18 J/(gK) (T - 298 K) + 1.5 kJ/K (T 298.15 K)
18.77 kJ = (500 g 4.18 J/(gK) + 1.5 kJ/K) (T 298.15 K)
T = 18770/ (500 4.18 + 1500) + 298.15
T = 303.38 K T = 30.23C
The temperature increase by 5.23 K from 25C to 30.23C.
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