Heat Exchange System for

Reforming in an Ammonia Process

Process Lead: Christin Barney
Project Engineers: Alex Penn and Sara Belledin

TABLE OF CONTENTS
Abstract
1.0 Introduction
2.0 Overall Process
3.0 Aspen Model
4.0 Matlab Model
5.0 Cost Analysis and Future Considerations
6.0 Conclusions
References
Appendices
Appendix A- PFD for Reforming in an Ammonia Plant
Appendix B- Stream Compositions
Appendix C- Utility Heat Exchangers Model

Abstract
In this project, the heat exchange system for the reforming section of an ammonia
plant was optimized. The system consists of a single shell and tube process/process
exchanger followed by a secondary cooling water exchanger. The primary
exchanger heats the main feed before it enters the primary reformer, from 231.1 C
to 600 C. It is exchanged with the hot stream from the secondary reformer which is
cooled from 995.8 C to 741 C. The secondary heat exchanger is used to further
cool the hot stream from 741 C to 250 C.The exchanger system was modeled in
Aspen using the Peng Robinson - Boston Mathias property set and the HeatX
module. The primary heat exchanger transfers 19.8 MMKcal/hr, and the heater uses
35.7 MMKcal/hr. Rigorous analysis in Aspen was performed on the primary
exchanger specified as TEMA type CFU, class R. The heat exchanger was costed by
Aspen at $151,400, with the shell and tube constructed of Incoloy, 800 series.
Introduction
Ammonia production involves two primary operations, the reforming and the
synthesis processes. Ammonia reforming takes a feed of natural gas and steam. The
typical units for this process, as discussed in class and the literature, are the
desulfurization unit, primary reformer, secondary reformer, high temperature water

gas shift, low temperature water gas shift, carbon dioxide absorber, water
condenser, methanator, and a second water condenser. A diagram of the overall
process, obtained from the reactors group, can be found in Appendix A. The reaction
in the primary reformer is very endothermic, so the feed to this unit must be heated
before entry. The secondary reformer is operated adiabatically and further heats the
stream. This stream must be cooled before continuing on to the other units in the
plant, such as the carbon dioxide absorber. There is a rather significant range of
temperatures required for this complex process, making efficient heat exchange a
primary concern. Special considerations for materials and exchanger class were
necessary in the detailed design of the primary heat exchanger due to the high
temperatures and pressures in this system.
Overall Process
Overall Process The primary focus of this project was to design an efficient and cost
effective heat exchange system for the reforming end of an ammonia plant.
Comparison between the optimum system and a pure utility-based heating and
cooling design was also completed. The guidelines for the project required the
combined use of the previous two projects detailing the reactors and the separation
system. Utilizing these designs, a somewhat simplified system was agreed upon for
the project scope.
The system under consideration has two streams in need of heating and cooling.
The hot stream runs from the secondary reformer to the absorber at a pressure of
35.29 bar. It is a vapor stream consisting primarily of steam, H2, and N2, with small
amounts of CO, CO2, CH4 and Ar. It requires cooling from 995.8 C to 250 C. The
cold stream is the combined feed of methane and steam that needs to be heated
before entering the primary reformer. Its primary constituents are steam and CH4,
with traces of CO2 and N2, and it must be heated from 231.1 C to 600 C, at 39.22
bar. The actual compositions of the streams from the previous projects used in this
system are given in Appendix B. The temperature requirement for the stream going
to the absorber was taken from the separators project, and the remaining stream
specifications were from the reactors project.
In choosing a property set for simulation, the NRTL equation was considered initially
because it is commonly used in industry and acedemia. However, the recommended
conditions for its use were not applicable to the system under consideration. After
researching other available property sets in Aspen, it was determined that the Peng
Robinson - Boston Mathias (PR-BM) property set best suited the needs of the
system. The PR-BM property set is commonly used for gas processing, especially for
mixtures of light gases, such as H2 and CO2. Reasonable results are expected at all
temperatures and pressures with the PR-BM property set, an important
consideration given the extreme temperatures and pressures of the reforming
system.

Aspen Model
The heat exchange needs for the system and the optimum system design were
considered using Aspen's simulation capabilities. The first task completed in Aspen
was the analysis of the two individual streams in the process that needed to be
heated and cooled. As shown in Appendix C, two heater modules were used. The
first cooled the hot stream from 995.8 C to 250 C with a heat duty of 19.79
MMKcal/mol. The second heated the cold stream from 231.1 C to 600 C using
55.66 MMKcal/mol. A sensitivity run was utilized to determine the enthalpy of each
system over the appropriate temperature range. This data was then analyzed in
Matlab; see the next section for details. There were no pinch points and no stream
crossings, so the system is relatively simple thermodynamically.
There was not enough duty available in the cold stream to cool the hot stream to
the necessary 250 C. A cooler needed to be added to the system, either prior to
the heat exchanger to start the cooling process, or following the heat exchanger to
complete the cooling of the hot stream. The latter was chosen because the
temperature difference between the hot and the cold streams was much less than
that of the cooling water and the hot stream. The lower temperature difference is
desired to reduce wear on the exchanger. Figure 1 shows the diagram of these two
exchangers as modeled.

Figure 1: Optimum Exchanger Model

A tube and shell heat exchanger was chosen for the primary exchanger. Tube and
shell is the most commonly used type (Perry 11-33). The two streams were crossed,
the hot stream in the shell, and the cold stream in the tubes. This decision was
made because tubes are easier to clean than the shell, and the cold stream contains
an appreciable amount of methane which could coke at these high temperatures.
Once the exchanger system was decided upon, a rigorous analysis of the primary
heat exchanger was necessary. The exchanger was specified as TEMA type CFU,
class R. Type C allows for a removable tube bundle, type F specifies a two pass
shell, and type U specifies a U-tube bundle (Gas 9-15). A diagram of what this
exchanger might look like is included in Figure 2. Class R allows for extreme
conditions, such as the high temperatures and pressures of this system, by
designating conservative calculations (Branan 22). The removable tube bundle
allows the tubes to be cleaned easily, which would most likely be done by
hydroblasting. Access for cleaning is essential to the function of the system. U-tubes
were chosen because they allow for expansion of the tube bundle. Material
expansion is an important consideration in our system given the large temperature

difference between the hot and cold streams (Branan 24). If a fixed tube sheet were
used, an expansion joint would be necessary (Branan 25). Expansion joints are
costly and a potential source of hazardous leaks. The two pass shell design is most
common and delivers higher efficiency in heat exchange. In order to minimize the
necessary utility costs, maximum cooling must occur in the exchanger, and this is
assured with the two pass shell design.

Figure 2: CFU Type Exchanger Drawing

The exchanger was defined as vertical, hot shell-cold tube exchanger constructed of
Incoloy, 800 series. Incoloy 800 is a 21:32:47 Cr:Ni:Fe alloy (Perry 28-64). It is one of
few materials that can withstand temperatures up to 1100 C (Perry 28-50). In
addition to its high temperature tolerance, incoloy should be used in this system
because it is resistant to hydrogen attack. Hydrogen pitting could lead to
embrittlement and possible process stream contamination or material failure in
many other common materials at the high pressure of H2 present in the hot stream
of this system (Branan 231-232, 235). The tubes will also be thicker-walled than
standard to contain the high pressures in both streams.
The surface area necessary for this exchange was calculated by Aspen to be 120.2
m2. Then, the number and size of the tubes was calculated to support the required
heat exchange area. The optimal system consisted of a tube sheet of 100, 1.5 inch
diameter, 36 foot long tubes with a 4.5 inch pitch and arranged in a triangular
pattern. The 4.5 inch pitch is slightly greater than minimum, because the shell-side
flow is large (Branan 29). The baffles were placed 2 feet apart to allow for optimal
flow on the shell side and adequate tube bundle support (Perry 11-42). The nozzle
sizes were determined to be 12" shell side and 10" tube side by finding the smallest
nominal size which gave reasonably low pressure drops and fluid velocities (Branan
26-29). The pressure drop data can be found in Appendix B. These specifications

lead to a heat exchanger that is 52 inches in diameter and 36 feet in length, with
additional length required for the channel end (the left side of Figure 2).
Matlab Model
Matlab was used to get a basic understanding of the system, plan a heat exchanger
solution, and verify the results from Aspen. First, sensitivity runs from Aspen were
used to get the enthalpies at the full range of temperatures for each stream. Then
that data was exported into Matlab where the curves were plotted and the cold
stream shifted so that its high enthalpy end would be flush with the high enthalpy
end of the hot stream. That kept the lines from intersecting, gave a maximum
temperature difference between the two streams, and required only one utility heat
exchanger. Next, the curves were approximated with straight lines of slopes equal
to the average of the end slopes, and figure 3 shows that these are very close
approximations.

Figure 3: Composite Curves

The inverse of these slopes then became the F*Cp's for use in later parts of the
Matlab program. Then the htxcc1 program was used with the overall heat
coefficient, U, from the Aspen short cut method to double check the accuracy of the

Aspen result. Matlab gave a surface area very close to Aspen's calculation.
Unfortunately, the U provided by Aspen is not considered very accurate, so another
program was written to estimate an overall heat transfer coefficient separately from
Aspen. Since a rough approximation was desired, most values were taken to be
average or bulk values, and the following equation was used to find the heat
transfer coefficients of each stream (Bird 399):

The temperatures used to find the various stream properties were the average
temperatures of each stream. The thermal conductivities, k, were from the mixkt
program, the viscosities from the mixmu program and the Prandtl numbers from the
mixpr program. We were unable to find the thermal conductivity of the Incoloy
metal, so we guessed a value based on similar metals. Considering these
approximations, Matlab's value for U being within a factor of three from that gotten
by the rigorous model in Aspen, allowed more confidence in the rigorous model
calculation (unlike the short-cut method which was over an order of magnitude off).
Lastly, the first program was run again using the U from the rigorous Aspen model
to find a surface area of 114.7 m2 (which closely matches Aspen's value) and the
following graph for a one-pass heat exchanger.

Figure 4: Temperature Profile

Cost Analysis and Future Considerations
The primary heat exchanger in this system was costed by Aspen at $151,400. The
area predicted by Aspen using this exchanger was rather large, so alternate
systems were explored. A system of two, serial shell and tube heat exchangers was
simulated. The division of the heat duty among the two exchangers was difficult to
determine, but a few simple variations (50/50, 75/25, etc.) were tried. With a half
and half division of duty, the cost of the two exchangers was given by Aspen as
$165,200 which is 9% more than the single exchanger. When considering space
availability and layout in individual plants, this system should definitely be explored
further.
Various tube number and length combinations were simulated. Fewer, longer tubes
created an excessively long exchanger and increased the cost of the unit, while a
greater number of shorter tubes led to pressure drops and velocities that were too
high in the tubes. Once again, given the specific space requirements of the
individual plant, these alternate systems should be considered further. Whether the
exchanger should be vertical or horizontal is also a decision that should be made

later when the plant plot arrangement and available support/access structures
around the unit are known.
For cost analysis purposes, the cost of purely utility supported heating and cooling
systems was compared to the optimum exchanger system design. Heating the cold
stream from 231.1 C to 600 C requires 19.79 MMKcal of duty which costs $180 per
hour ($1,578,966 per year) in steam. This estimate comes from Dupont's Victoria
plant steam cost of $2.30 per million Btu. There are some cooling water
requirements in the optimum design for the final cooling of the hot stream, but the
cost of cooling water is insignificant in comparison to steam. Essentially it is only
the cost of the treatment and the pumping. The amount of cooling water required
has been reduced through the integration of the heat system.
Conclusions
This optimum heat exchange system was designed with many important
considerations. The system was based on efficiency of design. Operational
conditions, including materials of construction, and maintenance requirements were
also important factors. Overall, the savings just on steam justify the use of the
process/process exchanger designed by this team.
References
Bird, Stewart, and Lightfoot. Transport Phenomena. John Wiley and Sons, Inc.
New York.
1960. pp. 399.
Branan, Carl R. Rules of Thumb for Chemical Engineers. Gulf Publishing
Company.
Houston. 1994. pp. 19-30, 231-235.
Gas Processors Association. "Heat Exchangers." Engineering Data Book, Volume I.
Gas
Processors Suppliers Association. Tulsa, OK. 1987. Section 9, pp. 1-18.
Perry, Robert H. and Green, Don W. Perry's Chemical Engineer's Handbook.
McGrawHill. New York. 1997. pp. 11-33, 11-42, 28-50, 28-64.
Appendix A- PFD for Reforming in an Ammonia Plant

Appendix B- Stream Compositions

FEED

PRIM-IN SEC-OUT HOT-OUT ABS-IN

Temp (C)

231.1

600

995.8

741.0

250.0

Pressure (bar)

39.22

38.75

35.29

34.647

35.29

Vapor Fraction

1.00

1.00

1.00

1.00

1.00

Enthalpy (MMkcal/hr)

-231.935 -212.135 -154.969 -174.768

Mole Flow (kmol/hr),

total

5004.443 5004.443 8828.312 8828.312 8828.312

CH4

1250.0

1250.0

21.281

H2O

3750.0

3750.0

2832.839 2832.839 2832.839

21.281

-210.383

21.281

H2

3374.600 3374.600 3374.600

CO

814.477

814.477

814.477

CO2

3.000

3.000

417.242

417.242

417.242

N2

1.443

1.443

1350.593 1350.593 1350.593

Ar

17.280

Stream names refer back to Figure 1

Appendix C- Utility Heat Exchangers Model

* with same stream names as figure 1

17.280

17.280