Synthesis

Gas
Reformers

Synthesis gas reformers plays

important role in the production of
ammonia. By optimizing the feed
flow rate, temperature, oxygen and
steam to carbon ratio to a
particular range of operating we
can obtain 3:1 ratio of Nitrogen and
Hydrogen for producing ammonia.
This also has to include cost in
optimizing
which is discussed in
A briefy
report
detail.

Paranthaman Rajasekar
2013HT61007
Technical communication assignment

Abstra
ct

TABLE OF CONTENTS

1.0

INTRODUCTION.................................................................................................... 3

2.0

OPTIMUM PROCESS.............................................................................................. 3
a. STEAM/ CARBON SENSITIVITY...........................................................................5
b. OXYGEN SENSITIVITY....................................................................................... 6
c. PRESSURE SENSITIVITY..................................................................................... 6
d. TEMPERATURE SENSITIVITY.............................................................................7

3.0

REACTOR SIZING.................................................................................................. 8

4.0

PROCESS ECONOMICS.......................................................................................... 8

5.0

CONCLUSIONS AND RECOMMENDATIONS.............................................................9

6.0

REFERENCES...................................................................................................... 10

1.0 INTRODUCTION
Primary and secondary reformers play an important role in the production of ammonia. The
goal of reforming is to prepare as pure as possible a gas mixture of nitrogen and hydrogen
in a 3:1 stoichiometric ratio from the raw materials of water, air, and natural gas. The
reactions by which this ratio is achieved are given as follows:

Reaction 1, the steam reforming reaction, and reaction 2, the water gas shift reaction, are
endothermic and occur in the primary reformer. Reaction 3, the combustion reaction, is
exothermic and occurs along with reactions 1 and 2 in the secondary reformer [1].
Optimization of the reforming process involves the manipulation of parameters to achieve
high process yield while maintaining low operating and installed costs. The parameters
which are monitored in this design include temperature, pressure, steam to carbon ratio,
and percent oxygen in the air feed.
2.0 OPTIMUM PROCESS
The focus of this project is on the design of the primary and secondary reformers. There
are, however, several other reactors necessary in any ammonia production process. These
reactors can be seen in the Process Flow Diagram (PFD) in Figure 1. A brief overview of
these other processes as well as the assumptions NGM Reformers made in considering the
effects of these processes on the primary and secondary reformers will be discussed here.
As seen in Figure 1, ammonia production begins with inlet streams of natural gas and
steam. For the optimum process, NGM chose a 20225.902 kg/hr natural gas feed stream
composed of 99% methane
entering at a pressure of 35.29 bar. A 3:1 molar steam to carbon ratio was chosen for the
feed streams. The steam stream enters with a flow rate of 67557.297 kg/hr [2]. The
methane feed is first passed through a desulfurizer and then mixed with the steam feed.
This mixed stream, the primary reformer inlet stream of Table 1, next passes through a heat
exchanger where it is heated to a temperature of 600 C. From here the primary reformer
inlet stream enters the primary reformer.
The primary reformer is modeled in ASPEN as an Gibbs reactor with RK Soave equations
of state. An operating temperature of 800 C and an operating pressure of 35.29 bar are
found to yield the optimum process based on an analysis of sensitivity runs and industry
standards. The primary reformer is heat flux limited. Thus, based on a calculated reformer
heat duty of 50 MMkcal/hr, the reformer is sized to contain 230 catalyst tubes with 4" inner
diameter and a length of 35'.

From the primary reformer, the primary outlet stream is mixed with a 600 C, 35.29 bar air
stream. This mixed stream constitutes the secondary inlet stream in Table 1.
The secondary reformer is also modeled in ASPEN as an Gibbs reactor with RK Soave
equations of state. An operating temperature of 996.2 C and operating pressure of 35.29 bar
are found to best optimize the process. Based on these process conditions the secondary
outlet stream flows of hydrogen, carbon monoxide and nitrogen were found to be 3375.48
kmol/hr, 814.378 kmol/hr, and 1350.593 kmol/hr respectively. These numbers are critical
to the production of 1000 metric tons per day of ammonia in the correct 3:1 stoichiometric
ratio. Based on the assumption that all downstream processes are ideal, all the carbon
monoxide found in the secondary reformer outlet stream will be converted to hydrogen.
Therefore, the addition of the hydrogen and carbon monoxide should be in at least a 3:1
ratio with nitrogen upon exiting the secondary reformer. This result is accomplished and is
evident in Table 1.
From the secondary reformer, the secondary effluent flows through a heat exchanger where
it heats the primary reformer inlet stream. From the heat exchanger it passes through a high
temperature shift converter, low temperature shift converter, and methanator. For this
project these processes were assumed to operate ideally at equilibrium.
FIGURE 1:

TABLE 1:

a.

STEAM/ CARBON SENSITIVITY

Primary reformer inlet steam-to-carbon (s/c) ratio is an important factor in reformer design.
The literature advises the maintenance of a relatively high s/c ratio to prevent mechanical
as well as economic problems during the life of the plant. Higher s/c ratios are more
effective for a number of reasons. First, because a high s/c ratio favors the products in the
reforming reaction equilibrium, it lowers the amount of unreacted methane, or methane slip,
out of the secondary reformer and increases the production of hydrogen. Second, a high s/c
ratio inhibits the occurrence of carbon-forming side reactions in the primary reformer that
result in carbon deposits on the catalyst. Carbon deposition increases the resistance to gas
flow in the primary reformer tubes and may impair catalyst activity. This impairment
lowers the rate of the reforming reaction and can cause local overheating or "hot bands" in
reformer tubes that result in premature tube wall failure. Finally, a high s/c ratio provides
the necessary steam for the shift conversion of carbon monoxide and reduces the risk of
carburization damage to the tube material [3].
Table 2 shows process sensitivity to s/c ratio. A 3.0/1.0 s/c ratio was found to be the most
optimum ratio for the purposes of this process. Sensitivity runs in Aspen showed that
4.0/1.0 s/c ratio requires a larger heat duty than a 3.0/1.0 ratio. This increases cost as more
heat has to be applied to the process. However, lowering the s/c ratio to 2.5/1.0 was found
to increase methane slip significantly, decreasing the amount of hydrogen produced. For
these reasons a 3.0/1.0 s/c ratio was chosen.

TABLE 2:

b. OXYGEN SENSITIVITY
Oxygen-enriched air is sometimes utilized in the production of syn-gas as it shifts more of
the reforming from the primary reformer to the secondary reformer. An increase in the
proportion of reforming occurring in the secondary reformer results in a higher outlet
temperature from the secondary reformer. This heat can be recycled and used to heat the
primary reformer inlet stream to reduce energy costs. On the other hand, enriched air
introduces another cost to the process by requiring that excess nitrogen be stripped from the
process downstream or that excess oxygen be purchased from a third party supplier [4].
NGM Reformers Inc. decided that this extra cost exceeded the savings gained from reducing
energy costs. Hence, pure air (21% oxygen, 78% nitrogen, 1% inerts) is used. Using
enriched air also decreases methane slip considerably, however, it decreases the production
of hydrogen to below product specifications. Table
3 shows process sensitivity to the use of an enriched air stream.
TABLE 3:

c. PRESSURE SENSITIVITY
The chemistry, economics and demands from major clients must be taken into consideration
when analyzing the effects of reactor operating pressures on the process. It is important to
note that the process is limited by a maximum pressure of 40 bar due to the metallurgy of the
material used to construct the primary reformer tubes. Table 4 demonstrates the results of
raising and lowering reformer pressure. High reformer pressures near 40 bar favor the

reactants of the reforming reaction equilibrium, therefore, the production of hydrogen

decreases while methane slip increases. To compensate for high methane slip the heat duty
must be increased, thus increasing compression and energy costs. Higher pressures also
cause the secondary reformer effluent temperature to decrease. This has an unfavorable
effect on the process as the heat from this stream is used to heat the primary reformer inlet
stream via heat exchanger. A lower pressure of 25 bar exerts a favorable effect on the
equilibrium of the reforming process. According to the chemistry involved it seems that
lower pressures afford the most advantage; they increase secondary reformer outlet
temperature, decrease methane slip to about 0.01%, and increase hydrogen production by
approximately 100 kmol/hr.

NGM Reformers, Inc. values customers in downstream ammonia synthesis and realizes that
their compression costs will be significantly increased by low presures in the front end
process. Hence, a process pressure of 35.29 bar was adopted as a fair compromise, allowing
for the maintenance of a relatively low methane slip of 0.35% and a sufficient throughput of
product while maintaining a high enough temperature in the secondary reformer outlet
stream
TABLE 4

d. TEMPERATURE SENSITIVITY
The reforming process favors high temperatures as it shifts the reforming reaction
equilibrium towards the production of hydrogen and reduces methane slip. However, it is not
advisable to operate the primary reformer above 800 C because the metallurgy of the
catalyst tubes causes them to creep and bulge under the weight of the catalyst at
approximately 850 C. Additionally, the nickel catalyst melts at 1100 C. Operating at
elevated temperatures also increases the heat duty, causing energy costs as well as
equipment costs to escalate somewhat. In contrast, operating at 700 C decreases hydrogen
production and increases methane slip out of the secondary reformer resulting in the waste
of fuel. Table 5 shows these effects. The only advantage of lowering temperature is a
decrease in heat duty, which will reduce costs somewhat.
Because of the large degree of process sensitivity to primary reformer temperature, it is
desirable to operate at a temperature as close to the metallurgical limit of 850 C as possible
in order to maximize H2 production. Therefore a temperature of 800 C in the primary
reformer was chosen. This temperature is transferred to the adiabatic secondary reformer.

The secondary reformer is not constrained by mechanical heat transfer surfaces; therefore, it
can operate at higher temperatures and is operated at 966 C outlet temperature.
TABLE 5

3.0 REACTOR SIZING

Primary and secondary reformer reactor sizes were calculated from industry data in order to
minimize primary reformer size and thus minimize installed cost. The primary reformer is
heat flux limited; that is, reactor size is determined based on the surface area over which the
necessary heat for reforming is transferred. A tube size of 4 inch I.D., 35 feet in length was
chosen. This tube size is consistent with industry averages [5]. The maximum conventional
heat flux through primary reformer tube walls is approximately 21,000 Btu/ft2*hr
(5,921.176 kcal/ft2*hr) [6]. Using this value and the heat duty through the reformer
calculated by Aspen, the primary reformer size was calculated as follows:
f = Maximum heat flux thorough tube walls = 5,921.176 kcal/ft2*hr
d = Heat duty through primary reformer (from Aspen) = 50.0771 x 106 kcal/hr a = Total
needed surface area of reformer tubes = d/f = 8457.28 ft2
t = a/36.7 ft2 per tube = 230 tubes needed
Catalyst volume was calculated from tube number and tube volume. The primary reformer
contains a total of 690 ft3 of catalyst.
The secondary reformer size was chosen based on industry input and a length to diameter
ratio of approximately one [5]. The reactor is 12 feet in diameter and 20 feet long. Ten feet
of reactor length are left void of catalyst so that combustion may occur away from the
catalyst.
4.0 PROCESS ECONOMICS
Approximate price ranges were obtained from M.W. Kellogg for the primary and secondary
reformers and catalyst. These prices reflect the differences in construction materials used
for each reactor. Due to the high pressures and temperatures in the primary reformer tubes, a
25% chromium-20% nickel alloy is the preferred tube material. The secondary reformer,
with its simpler design, can be priced as a large, refractory-lined vessel containing a fixedbed nickel catalyst [7]. Primary reformers cost on the order of $5 million, secondary
reformers on the order of $1 million, and primary reformer catalyst approximately $200/ft3

[5]. Therefore catalyst cost for the primary reformer is $138,000, less than three percent of
the total primary reformer installed cost. Since the primary reformer is such a major
component of the process cost, the process was optimized so as to minimize the size of the
primary reformer. Less attention was given to the amount of catalyst supplied to the primary
reformer since it becomes almost negligible when compared to the cost of the reactor itself.
5.0 CONCLUSIONS AND RECOMMENDATIONS
In this process a 3:1 stoichiometric ratio of (H2 + CO) to N2 in the secondary reformer
effluent was achieved using a 90,000 kg/hr steam plus natural gas basis feed with 3:1 steam
to carbon ratio, 35.29 bar reformer operating pressures, and 800 and 996 degrees C
operating temperatures in the primary and secondary reformers, respectively. Several other
factors may be considered, however, in designing a fully optimum process for the required
syngas output. These include catalyst type, kinetic data, and reforming heat exchange.
The process modeled and optimized here is an equilibrium model. That is, each reactor is
assumed to be operating at equilibrium. In reality however, equilibrium can not be reached,
and an approach to equilibrium model should be adopted. This involves the selection and
incorporation of the approprate kinetic data for the process. The approach to equilibrium in
the reformers is affected by choice of catalyst. Numerous catalysts of differing properties
are available to suit specific purposes. Once a catalyst is
chosen, parameters such as catalyst activity, surface area, particle size, crush strength, and
nickel content among others should be considered to more accurately model the process.
An alternative to the placement of the single heat exchanger used in this process is to
employ reforming heat exchange. This involves recycling the secondary reformer effluent
stream into the shell side of the primary reformer vessel such that the heat exchange
between this stream and the primary reformer inlet occurs physically inside the primary
reformer vessel rather than through a seperate heat exchange unit. This would require
additional mechanical considerations and an alteration of the construction of the primary
and secondary reforming vessels but is extremely thermodynamically favorable. Reforming
heat exchange may significantly reduce the size of the primary reforming furnace and
consequently decrease the cost of the unit. Thus, reforming heat exchange should be
considered as a possible alternative heat recovery mechanism [5,7].

6.0 REFERENCES
1. Gerhartz, W. et. al. Ullmann's Encyclopedia of Industrial Chemistry. 5th Edition. VCH,
Federal Republic of Germany: 1985.
2. Mii, T. Process Systems Planning & Engineering Division, Toyo
Engineering Corporation, Japan. Electronic mail correspondance.
3. Appl, M. Modern Production Technologies. British Sulphur Publishing, London: 1997.
4. Ned, Zed, and Associates and The Autobots. "Design and Economic Analysis of Ammonia
Production Plant," CENG 404 Project Report, Spring 1996.
5. Strait, R. B. Process Engineer, M.W. Kellogg Co., Houston, TX. Personal interview.
6. Strelzoff, S. Technology and Manufacture of Ammonia. John Wiley & Sons, New York:
1981
7. Kirk-Othmer. Encyclopedia of Chemical Engineering Technology. 4th Edition.
John Wiley & Sons, New York: 1992.