SYNTHESIS GAS REFORMERS

Megan Strait, Glenda Allum, Nisha Gidwani

TABLE OF CONTENTS

ABSTRACT
TABLE OF CONTENTS
1.0 INTRODUCTION
2.0 OPTIMUM PROCESS
2.1 STEAM/CARBON SENSITIVITY
2.2 OXYGEN SENSITIVITY
2.3 PRESSURE SENSITIVITY
2.4 TEMPERATURE SENSITIVITY
3.0 REACTOR SIZING
4.0 PROCESS ECONOMICS
5.0 CONCLUSIONS AND RECOMMENDATIONS
REFERENCES
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 are 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 monitered in this design
include temperature, pressure, steam to carbon ratio, and percent oxyegen 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 flowrate 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 RGibbs 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 RGibbs 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 projec these processes were assumed to
operate ideally at equilibrium.
FIGURE 1:


TABLE 1:


2.1 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
occurence 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:

2.2 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


2.3 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


2.4 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 senstivity 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 fixed-bed 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 refomer 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].

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.