A Review of the Basics for Superior Design

By: Hazem Haddad, Ph.D.

Senior Process Engineer
and
Jorge Foglietta, PE
Director – Technology & Process Engineering
Randall Gas Technologies – ABB Lummus Global Inc.

ABSTRACT
From the thermodynamic point of view, cryogenic gas plants are open refrigeration cycles. A review of the
concepts regarding the efficient use of energy leads us to the heart of the problem. Lost work, exergy
analysis, and pinch technology, all revolve around the same concept of irreversibility, which results in
thermodynamic lost work.

Before the computer age, the use of these abstract concepts was left to the academic world. With today’s
computer speed, the flexibility of process simulators and the link to pinch technology software,
thermodynamic analysis of a process is much easier, and now plays a vital role in process design.

In this paper we will show how calculations of ideal work, actual work, lost work, and overall process
efficiency and equipment efficiencies help in the design of new process concepts or the comparison of
options.

The review will include estimates of lost work inside distillation columns, how it may be reduced, and how
column targeting can be used for optimum heat integration of the process.

When applied to a cryogenic gas plant, the analysis shows that the largest lost work is in recompression,
which reemphasizes the need to run the column at as high of a pressure as possible. This is what led us to
conceptualize the new High Pressure Absorber (HPA) process. A numerical and graphical comparison of
different processes will be shown.
 A Review of the Basics for Superior Design

INTRODUCTION/REVIEW OF FUNDAMENTALS
Although not frequently done because of the laborious calculations, thermodynamic analysis of a process
can give insights which can guide the process engineer when process development and improvements are
needed. This paper intends to review modestly the fundamentals of thermodynamics to instill the use of
these concepts in process design.

Thermodynamic analysis of a process can give the minimum work that is required for a given process.
With the actual work known, lost work and the process efficiency can be calculated. This may inspire the
process engineer to focus on areas with large lost work for process improvement.

Before proceeding further it is helpful to review some concepts and definitions such as reversible process,
ideal work, lost work, etc.

Consider a system at equilibrium. For a change to be reversible the system must undergo the change in
infinitesimally small steps such that, at all times, the system remains at equilibrium or just infinitesimally
away from equilibrium. If there is heat transfer then all heat transfer must be from or to the environment
via a Carnot engine which is reversible. A reversible process has no lost work, thus a reversible process
must not only produce useful work but it must produce the maximum amount of useful work. If it is a
work requiring process, then it must require a minimum amount of work.

For a chemical process to be reversible then all unit operations or steps within a unit operation must be
reversible. In chemical plants and due to various types of unit operations, work can be lost in several ways
as follows:

Chemical Lost Work is the type of lost work that results from irreversible reactions; the most common of
which is probably combustion.

Heat Transfer Lost Work is the lost work that results due to heat transfer across a finite temperature
gradient and in the absence of a Carnot engine.

Mass Transfer Lost Work is lost work that results in the increase in entropy when mixing fluids where the
components have different chemical potential.

Momentum Lost Work is the lost work caused by pressure drop across lines and valves.

Ideal Work is the work required or produced by a process if the process is reversible. Thus, for a work
requiring process, this is the minimum work needed for the process. For a work producing process, it is the
maximum work that it can produce. Ideal work can be calculated as follows:

Wideal = TeDS - DH
where S is the entropy, H is the enthalpy and Te is the environment temperature. In this study, the
environment temperature is assumed to be 80°F (540 R). If this term is positive, it indicates the maximum
work that can be produced by the process. If this term is negative, then it is the minimum work required by
the process. When applied to a non-adiabatic process, the above equation assumes that all heat transfer
from and to the environment took place reversibly via a Carnot engine.

Shaft work: The shaft work applies to rotating equipment and is the actual work produced or done by the
equipment. In the case of a compressor the shaft work is negative because the work is done on the system.
In the case of an expander, the shaft work is positive because the work is done by the system. The shaft
work is dependent on the efficiency of the machine. For a hypothetical rotating machine with 100%
efficiency, the shaft work will equal the ideal work and the lost work will be zero.

Lost Work: For a work producing irreversible process, the lost work represents the work or the additional
work that could have been produced by the system if the process was reversible. For a work requiring
process, it represents the work or additional work that had to be expended due to the irreversibility. Thus,
the following equation always holds true:

Wlost = Wideal - Wshaft

This term is always positive and is equal to zero for a reversible process.

The process efficiency can also be calculated. For work requiring process the efficiency is given by

h = Wideal / Wshaft

Use the reciprocal for work producing processes.

CALCULATIONS OF IDEAL AND LOST WORK FOR AN NGL

PLANT
We will now show how to calculate the ideal and lost work for the overall process and calculate the process
efficiency. The process that will be analyzed is a C3 recovery NGL plant shown in Figure 1 with stream
data given in Table 1.

The Overall Process: Identify the process feeds and products and apply the ideal work equation:

Wideal = TeDS - DH

where DH is the sum of the enthalpies of all product streams minus the sum of enthalpies of all feed
streams. Apply the same calculation to the DS term.
Table 1. Stream Thermodynamic Properties
Stream Temperature Pressure Flow H S
Name °F Psia Lb mole/Hr MM Btu/Hr MM Btu/Hr-R
1 68.0 1290 124400 -4474 4.28
2 -9.5 1285 124400 -4625 3.97
20 -75.0 470.0 10460 -494.7 0.27
21 660.0 465.0 10460 -447.7 0.37
16 -69.5 435.0 119800 -4335 4.11
51 14.9 430.0 119800 -4231 4.36
7 -92.7 450.0 124400 -4674 4.01
8 -93.6 445.0 18040 -864.8 0.43
10 -102.5 440.0 119800 -4382 3.99
17 -88.2 450 13440 -572.5 0.40
9 -93.2 475.0 18040 -864.7 0.43
15 -75.0 470.0 18040 -852.9 0.46
16 -69.5 435.0 119800 -4335 4.11
11 -37.6 455.0 13440 -541.3 0.48
OV1 -14.82 460.0 198600 -810.0 0.73
OV2 -37.6 455.0 198600 -837.7 0.67
19 -75.0 470.0 7577 -358.2 0.19
21 60.0 465.0 10460 -447.7 0.37
13 202.2 460.0 4598 -234.8 0.13
5 69.8 624.8 119800 -4182 4.38
18 188.0 1295.0 119800 -4070 4.41
3 100.0 1290.0 119,800 -4189 4.21

A typical gas plant has one feed, a residue gas product stream and an NGL product stream (the deethanizer
bottoms). Thus, drawing an envelope around this process and considering it as the "system",
thermodynamically speaking, ought to be easy.

For the overall process,

Wideal = Te( Sout - Sin ) - ( Hout - Hin ) = Te ( S 3 + S 13 - S 1) - ( H 3 +H 13 - H 1)

Wideal = -5,900 HP

The negative sign indicates that the work needs to be done on the system.

The actual work or shaft work (residue compressor work and refrigeration compressor work when
applicable) is the sum of all the work given by and done by the expander(s), compressor(s) and pump(s)
respectively. The work produced by an expander is positive and the work done by the compressor or pump
is negative. The signs must be applied carefully to arrive at the correct shaft work. Pumps may be
neglected since they are very small.

Wshaft = -42,299 HP

Note that by common terminology, the actual work is never reported as a negative number, but
thermodynamically speaking it is negative because it is done on the system.

The lost work can now be calculated as the difference between the ideal work and the shaft work.

Wlost = -5,900 – (-42,299) = 38,399 HP

The efficiency for this work requiring process is:

h = 5,900/42,299 = 0.139 or 13.9%

The quantity of the actual work is almost seven times the quantity of the minimum/ideal work. It is of
interest to determine how the lost work is distributed throughout this process. In other words, is the lost
work concentrated in one unit operation? To answer this question, all unit operations in the plant are
analyzed one by one.

To ease and clarify a unit-by-unit analysis, the process is disconnected into individual unit operations as
shown in Figure 2. There are several ways to do that, but it is easier if the plant is disconnected into
adiabatic steps whenever possible.

To make the distillation column adiabatic, it is disconnected from its condenser and reboiler making it easy
to analyze. The column condenser is also adiabatic and is easy to analyze.

When applying the ideal work equation on a non-adiabatic heat source above the ambient temperature such
as the air cooler, the calculated ideal work would be the maximum work that would have been generated if
the heat transfer to the environment is done reversibly with a Carnot engine. If the heat exchanger is a sink
and is above ambient temperature, such as the deethanizer reboiler which is at 202°F, then applying the
ideal work equation on the process side only (non-adiabatic) would result in the minimum amount of work
that needs to be done to pump heat from the environment to the reboiler.

Heat Exchangers

The ideal work for a heat exchanger is also given by:

Wideal = TeDS - DH

When applied around a heat exchanger, the DS term is the sum of the entropy of the outlet streams minus
the sum of the entropy of the inlet streams. This is also applicable to plate fin heat exchangers with
multiple hot and cold streams.

The DH term, however, is zero since the heat given by the hot stream(s) equals the heat absorbed by the
cold stream(s). Thus, the ideal work is simply:

Wideal = TeDS
Since the shaft work is zero, then the lost work equals the ideal work. This may seem confusing at first, but
what that means is that the lost work could be zero if, instead of transferring the heat from the hot steam to
the cold stream, the heat would be transferred to the environment first via a Carnot engine, then return from
the environment to the other stream also via a Carnot engine.

Compressors (also applies to pumps)

The ideal work for a compressor is also given by:

Wideal = TeDS - DH

The DH term is not zero and is equal to the compressor brake horse power (but it is negative because this
is work done on the system) which is also the shaft work. Thus the compressor lost work is:

Wlost = Wideal - Wshaft

Expanders

The ideal work for an expander is also given by:

Wideal = TeDS - DH

The DH term is not zero and is equal to the expander brake horse power (positive because work is done by
the system) which is also the shaft work. Thus the expander lost work is:

Wlost = Wideal - Wshaft

Valves

The ideal work for a valve is also given by:

Wideal = TeDS - DH

The DH term, however, is zero and since the shaft work is zero, then the lost work equals the ideal work
and is simply Wideal = TeDS .

Note that the quantity of lost work calculated here is not the amount of work that would be obtained if the
valve is replaced by a 100% reversible turbine. If the valve is replaced by a 100% efficient turbine and the
outlet temperature is changed reversibly to the temperature at the discharge of the valve, then the actual
work of the 100% reversible turbine and the Carnot work would add up to the ideal work calculated around
the valve.

Distillation Columns

The ideal work for a distillation column is also given by:

Wideal = TeDS - DH
As discussed earlier, it is easier to disconnect the heat exchangers from the column and treat the streams
entering the heat exchangers as product streams and the streams returning from the heat exchangers as feed
streams. This makes the column adiabatic.

If analyzed this way, the DH term around the column becomes zero and only the entropy balance needs to
be done. The entropy balance would be the sum of the entropy of all products minus the sum of the
entropy of all feeds.

Care must be taken at the bottom reboiler because simulation-wise very often the product stream actually
exits from the reboiler not from the column; thus, the stream entering the bottom reboiler includes the
bottoms product but the stream returning to the column is only the vapor. In this case, for the correct
calculation of DS , the product streams are the overhead product and the streams entering the heat
exchangers. The bottom NGL product should not be included.

Since there is no shaft work, the ideal work of a distillation column is equal to the lost work.

To ensure an accurate analysis, when taking the entropy of the feed streams, the pressure of the feed
streams should be equal to the pressure of the stage they feed. Otherwise, the calculated lost work would
include some momentum lost work which is not due to the column itself.
 Summary of Results and Discussion
The results of the unit-by-unit analysis are given in Table 2. Note that when the ideal work for every
operation is summed, it corresponds to the ideal work calculated for the overall process. The same applies
to the shaft and lost work.

The minor inconsistency in the total ideal work obtained from the overall balance on the process and that
shown as the total ideal work in Table 2 is due to round off. Minor mismatches in the duty and pressure
profile of the condenser and reboiler in the column versus those simulated in the plate fin exchanger can
also contribute to inconsistencies.

Table 2. Unit-by-Unit Analysis for a Conventional C3 Recovery Plant

Equipment Wideal Wshaft Wlost % of total
Feed Chiller 8,025 0 8,026 19.0
Condenser 3,780 0 3,780 8.9
Absorber 1,258 0 1,258 3.0
Deethanizer 5,584 0 5,584 13.2
Expander 26,510 19,347 7,163 16.9
Recompressor -15,370 -19,347 3,977 9.4
Booster -36,768 -44,243 7,475 17.6
Pump -24 -56 33 0.1
Air Cooler 5,014 0 5,013 11.8
Valve 43 0 43 0.1
Deethanizer Reboiler -4034 -4034 0.0 0.0
Total -5,981 -48,334 42,352 100.0

This may seem like a lot of tedious work with a high probability of error and this is true. However, with
today's computer technology, we have developed an Excel spreadsheet which, using Visual Basic for
Applications (VBA), is capable of tabulating all the unit operations in a Hysys simulation and calculating
the ideal, shaft and lost work.

NEW CONCEPT DEVELOPMENT

One of the benefits of the thermodynamic analysis is to identify the areas in the plant with large lost work.
In this case it turns out that 44% of the lost work is in the expansion and recompression alone. When the
air cooler is added to this sum, it increases to 56%. This is due to the excessive expansion of the gas to 450
psia because the absorber pressure rides on the deethanizer pressure which is limited to 450 psia. If the
absorber can be operated at a higher pressure, then much of this expansion and recompression power can be
reduced.

This is where we began to investigate the dual column, dual pressure process which utilizes a high-pressure
absorber (HPA) as shown in Figure 3. In this process, the absorber runs at a higher pressure which can be
as high as 700 psia and is limited only by the approach to the critical conditions. A new compressor is
added to compress the net deethanizer vapor overhead to the HPA. The discharge from the expander feeds
the HPA, thus the expansion is reduced. This reduces the recompression. The absorber bottoms pump is
no longer needed in the HPA configuration.

With the same battery limit conditions, this process has the same ideal work as the conventional process but
the lost work due to recompression is reduced. Table 3 summarizes the results.
Table 3. Conventional and HPA Schemes for Propane Recovery.
Wideal Wshaft Wlost % of Wlost
Conventional
Heat Exchangers 11,805 0 11,805 27.9
Columns 6,842 0 6,842 16.2
Valves 43 0 43 0.1
Rotating Equip. -25,652 -44,299 18,647 44.0
Air Cooler 5,014 0 5,014 11.8
Reboiler -4,034 -4,034 0 0
Total -5,981 -48,333 42,352 100.0
HPA
Heat Exchangers 7,634 0 7,634 27.0
Columns 6,051 0 6,051 21.4
Valves 1,097 0 1,097 3.9
Rotating Equip. -20,071 -30,914 10,843 38.4
Air Cooler 2,636 0 2,636 10.5
Reboiler -3,226 -3,226 0 9.3
Total -5,876 -34,140 28,264 100.0

Note that the expander and compressors lost work is reduced to 38% compared to 44% in the conventional
process. The total percent lost work for the expander and compressors with the air cooler is reduced to
49% compared to 56% in the conventional process.

THE EXTENSION TO ETHANE RECOVERY

A simple ethane recovery scheme is shown in Figure 4. When analyzed thermodynamically for lost work it
shows the same weakness as the propane recovery scheme discussed earlier. Approximately 43% of the
lost work is in expansion and recompression alone and 63% is in expansion, recompression and air cooling
combined. It is clear that if the absorber can be operated at a higher pressure, then much of this
recompression power can be reduced.

Increasing the column pressure, however, brings new challenges. The reboiler and side reboilers become
warmer and the refrigeration provided to the chilling train decreases. The bottom of the column moves
closer to the critical point.

This is where we began to investigate extending the dual column, dual pressure concept to ethane recovery,
Figure 5. In this process, the demethanizer is divided into two sections. The top section operates at a
higher pressure and is called the High Pressure Absorber, HPA. The discharge from the expander feeds the
bottom of the HPA. Liquid from the gas subcooler feeds the top of the HPA. The bottom section is a
stripper which runs at a lower pressure. Vapor from the low-pressure stripper is compressed, condensed in
the subcooler and feeds the HPA as reflux.
Since the bottoms section of the demethanizer operates at a lower pressure, the reboiler and side reboilers
remain cold providing refrigeration to the chilling train. Recompression is reduced since the gas is
expanded into the HPA and not the low-pressure stripper.

A thermodynamic comparison between the conventional ethane recovery scheme and HPA scheme is given
in Table 4.

With the same battery limit conditions, this process has nearly the same ideal work as the single column
process, but the lost work due to recompression is reduced. The slight difference is due to different
recovery of carbon dioxide.
Note, however, that the lost work on a percentage basis remains the same due to decreases in the lost work
throughout the process. With the HPA, the lost work in rotating equipment is lower because the pressure
ratio is lower. The lost work in the air cooler is lower because there is less heat of compression to be
removed. The lost work for the valves is lower because the drop in pressure is lower. The lost work in the
heat exchangers is also lower due to an overall reduction in the driving force. The lost work in the column
was expected to be lower because part of the separation is being done at a higher pressure. At the higher
pressure, the relative volatility is low and the equilibrium line is closer to the operating line. Thus, the
vapor and liquid streams entering a stage are not as far from equilibrium as they would be at low pressure.
However, the results show a larger lost work in the column. This is likely to be due to the higher amount of
carbon dioxide condensed.

Table 4. GSP and HPA Schemes for Ethane Recovery

Wideal Wshaft Wlost % of Wlost
Conventional
Heat Exchangers 5,773 0 5,773 15.2
Columns 6,539 0 6,540 17.2
Valves 4,184 0 4,184 11.0
Rotating Equip. -30,383 -47,348 16,965 44.6
Air Cooler 4,573 0 4,573 12.0
Total -9,313 -47,348 38,035 100.0
HPA
Heat Exchangers 3,847 0 3,847 11.8
Columns 7,398 0 7,398 22.7
Valves 3,508 0 3,508 10.8
Rotating Equip. -28,707 -42,498 13,791 42.3
Air Cooler 4,058 0 4,058 12.4
Total -9,896 -42,498 32,602 100.0

COLUMN TARGETING, SIDE REBOILERS AND LOST WORK.

DO NOT BE DECEIVED.
In the design of any distillation column, the engineer typically determines the minimum reflux/stripping
conditions and then adjusts the number of stages in the column such that the column is at a given percent
above minimum reflux/stripping. Determining the minimum reflux/stripping requires simulating the
column with a number of stages that is large enough to the point that it can be assumed that the column is at
minimum reflux/stripping. This requires patience since convergence problems often occur.

The use of side exchangers in the gas processing industry is common and is key to optimum designs/low
energy consumption. Aside from determining the minimum reflux/stripping for this column, determining
the maximum amount of heat that can be added or removed by a side exchanger at a given temperature is
also a tedious process that requires multiple simulations. When convergence problems occur, the task is no
longer tedious, it becomes impossible. The column grand composite curve, CGCC, offers a solution to this
problem. It is a simple diagram that can be drawn by a Hysys/Excel VBA exchange or a Hysim calculator
and shows the minimum reflux/stripping conditions as well as the amount of heat that can be
added/removed by a side exchanger at any given temperature.

For proper heat integration between the column and the process and to avoid the use of external
refrigeration, side reboilers are added to the demethanizer column because the reboiler itself is usually
warmer than the coldest temperature in the chilling train.

For the schemes presented in this paper, the engineer would start by drawing the Column Grand Composite
Curve (CGCC) for the column (Figure 6a) which would quantify the maximum amount of heat that can be
recovered from the column at the temperature of the cold separator with some allowance for a reasonable
temperature approach.

The side reboiler is simulated and heat integrated with the chilling train. At this point, the reboiler heating
curve is compared to the remainder of the chilling train’s cooling curve. If there is a cross, then a new
CGCC curve is drawn and a new side reboiler is added. Figures 6b and 6c show a demethanizer CGCC
curve with one and two side reboilers respectively.

If, however, one side reboiler suffices, then there is no need to add another side reboiler and from a
thermodynamic point of view, there is absolutely no benefit to adding another side reboiler.

This is contrary to what a CGCC diagram or a tray-by-tray lost work analysis inside the column would say.
Both diagrams (CGCC and tray by tray lost work) would suggest that the process is more reversible and
less work is lost with more side reboilers. This is true only as far as the column is concerned. However,
any reduction in the lost work inside the column would result in additional lost work in the side
reboilers themselves due to the higher temperature driving force.

This can be seen more clearly if an envelope is drawn around the column and the side exchangers, Figure 7.
This section is adiabatic with a DH of zero and a DS obviously independent of the side reboilers.

Conclusions

Lost work/exergy analysis can locate and quantify inefficiencies in the process. Combined with convenient
computational tools, it becomes easy to analyze many processes, and the process engineer will know where
to focus development efforts.

For the C3 recovery process, 27% reduction in compression horsepower is achieved and the process
efficiency is raised from 12% to 17% once the largest source of inefficiency is identified and quantified.

For the C2 recovery process, 10% reduction in total horsepower is achieved and the process efficiency is
raised from 19.7% to 23.3%.
 PF1
Condenser

3
Air Cooler
5
10

18
T-101
X-101/C-101 Absorber 15
1290 psia Expander/
100°F Recompressor 17

OV1

51
Feed Chiller
16

11

1
Feed
7 OV2
1290 psia 2
68°F 8
-9.5°F
9

20
21
19

T-100
Deethanizer

Hot Oil

Figure 1 13
NGL Product
 PF1
Condenser

Air Cooler

T-101
X-101/C-101 Absorber
1290 psia Expander/
100°F Recompressor

Feed Chiller

Feed

1290 psia
68°F
-9.5°F

T-100
Deethanizer

Hot Oil

Figure 2
NGL Product
 PF1
Condenser

Air Cooler
T-101
Absorber
X-101/C-101
1290 psia Expander/
100°F Recompressor

Feed Chiller

Feed

1290 psia
68°F
-27.6°F

T-100
Deethanizer

Hot Oil

Figure 3
NGL Product
 Air Cooler

1290 psia
100°F X-101/C-101
T-101
Expander/ PF1
Demethanizer
Recompressor Gas Subcooler

Feed Chiller/Side reboiler

Feed 46°F

1290 psia
68°F

Figure 4 NGL Product

 Gas Gas Exchanger Gas Subcooler
Air Cooler

1290 psia
100°F
X-101/C-101
Expander/
Recompressor

Feed

1290 psia
68°F

Feed Chiller & Reboilers

T-101
Demethanizer
-22°F

Figure 5 NGL Product

 Column Grand Composite Curve
80

70

60

Duty (MMBtu/Hr) 50

40

30

20

10

0
-150 -125 -100 -75 -50 -25 0 25 50
Stage Temperature (°F)

Figure 6a CGCC for a Demethanizer with no side reboilers

Figure 6b CGCC for a Demethanizer with one side reboiler

Column Grand Composite Curve

50

45

40

35

30
Duty (MMBtu/Hr)

25

20

15

10

0
-150 -125 -100 -75 -50 -25 0 25 50
Stage Temperature (°F)

Figure 6c CGCC for a demethanizer with two side reboilers

 Air Cooler

X-101/C-101
T-101
Expander/ PF1
Gas Gas Exchanger Demethanizer
Recompressor Gas Subcooler

Feed

Feed Chiller & Reboilers

Figure 7 NGL Product