Applied thermodynamics in

the refining industry

Gerardo Villamizar
Process Design & Engineering
processdesignandengineering@gmail.com

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Our work as process engineers is based on three
principles:

- Hydraulics. When the velocity of water in a pipe goes up, its pressure
goes down.

- HMB. IN-OUT+GENERATION=ACCUMULATION

- Vapor-Liquid equilibrium. A boiling liquid is at its bubble point, and a

condensing vapor is at its dew point.
Back to the basics
• Give some examples of industrial application of the so-called 1st and 2nd laws of
thermodynamics.

• Convert 40,000 tons/year flowing through the gas recycle compressor in a VGO
hydrocracking unit to MMSCFD.

• Convert 100 Nm3/h of industrial plant air to SCFM.

• A hydrogen shift reactor in a steam reforming unit is being subjected to a external

fire. This may lead to a vessel overpressure due to the gas thermal expansión. If
the vessel has a fixed volume of 65 m3. The safety valve is set at 800 psig.
Estimate if the vapor expansión may lead to an overpressure taking into account
that under normal operating conditions the vessel runs at 650 psig.

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Back to the basics
• The top of a naphtha stripper tower in a industrial hydrocracking unit
has a wáter content of 6% mole. If the normal operating pressure at
the bottom of the tower is 12 barg. Estimate how close is the
overhead system to the water condensation. Give an engineering
solution to overcome the problem. The overhead temperature is
90°C.
90°C

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C3/C4 Splitter

The most recent gas chrome from the lab

indicates that the bottom product has
composition about 2% wt propane and
98% wt n-butane. If the bottom pressure is
maintained at 188 psig, which would be
the reboiler operating temperature ?
Answer: 95.0 C

If you would have to reduce the C3 spec in

the bottom product to 0.5%, at the same
pressure, which would be the reboiler
temp?
Calculate the propane concentration in the
vapor leaving the reboiler.
Answer: 96.5 C , 1.4% mole
What about the temperature controller
behavior?
Pilot tray? How to select it?
C3/C4 Splitter
Same tower. This time we know that the
tower-top pressure is 175 psig. We also
know that the composition of the
overhead vapor is:
C3: 80% mole
n-C4: 15% mole
n-C5: 5% mole

Overhead vapor line at its dew point

(assuming that there are no flooding
problems).
As first attempt we’ll guess a temp about
140 F:

You, as chemical engineer is

kindly requested to find the
solution.

Didn’t
match!
2.5 Why Pumparounds. What about the condenser duty?
Do pumparounds
fractionate?....

The temperature difference between trays 9 and 10 (vapor to tray 8 and liquid from tray 10 downcomer)
indicates that fractionation is taking place.
2nd Law applied
• What is the meaning of Cp and Cv ?

P1 P2

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Compression paths
• Reciprocating vs. Centrifugal compressor. Which one is more efficient ?
pV ^ n = C

1. What does it mean n = 0 ?

2. What does it mean n = 1 ?
3. What does it mean n = Cp/Cv ?
4. What does it mean n > Cp/Cv ?

5. Could you give real industrial

examples for each process ?

Source: GPSA 9
Compression paths
• Exercise…
Same suction temperature, compression ratio, volumen. What
does it take more energy, to compress methane or hydrogen ?

Where is the difference ?

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 Compression paths
• Exercise…
Have you ever Heard about NORMAL and STANDARD CONDITIONS ?

They are a normal industrial standard to define capacities.

Example: new Al-Jubail Refinery in the Kingdom of Saudi Arabia is

defined with a processing capacity of 400,000 BPSD.

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Industrial Compressors
Are the industrial compressors able to handle liquids ?
• How do we overcome the problema as Process
Engineers?

To
refinery
gas
plant
Suction Atmospheric
drum Overhead
Compressor
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Applied Thermo
Isoenthalpic expansion !!
Vapor expansions…

4” 6”
P2, T2, V2
P1, T1, V1

P1 (¿=? ¿>? ¿<?) P2

T1 (¿=? ¿>? ¿<?) T2
V1 (¿=? ¿>? ¿<?) V2
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Applied Thermo
Isentropic expansion !!
Vapor expansions…

P1, T1, V1 P2, T2, V2

P1 (¿=? ¿>? ¿<?) P2

T1 (¿=? ¿>? ¿<?) T2
V1 (¿=? ¿>? ¿<?) V2
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Applied Thermo
Expansion through a Joule-Thomson
valve vs. A gas turboexpander

1,000 psia 350 psia

-40°F -150°F
DH = 20,000 HP/SCF/day

1,000 psia 350 psia

-40°F -110°F
DH = 0 HP/SCF/day
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 Applied Thermo
Cryogenic plants (gas dew point control)

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Applied Thermo
Cryogenic plant
Industrial Applications
• Steam turbines as pump driven or in power plants
• Turboexpanders in gas and cryogenic plants

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