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THERMODYNAMIC ANALYSIS OF STEAM

AND CO2 REFORMING OF METHANE

José F. Cancino and Miguel Bagajewicz†

Department of Chemical Engineering and Materials Science
University of Oklahoma
Norman, OK, USA

† To whom all the correspondences should be addressed. (bagajewicz@ou.edu)

Abstract
A process thermodynamics analysis of natural gas reforming is performed to identify
optimal processing conditions. Two types of natural gases, one with almost no CO2 and
the other with a high content of CO2 were chosen as representative raw materials. When
H2/CO syngas ratios of 2/1 or smaller are desired, addition of water and CO2 are required.
The paper investigates the use of CO2 recycles, single, series, and parallel reactors on top
of temperature and pressures to establish optimal conditions.

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Introduction
Steam reforming of methane is the most common process to produce Syngas. Table 1,
summarizes some of the commercial plants recently built. In turn, dry reforming that is,
reforming using CO2, has been claimed to be a viable economical alternative route for the
production of Syngas1,2,3. Based on such claims a large number of investigators have
started research programs to identify good catalysts and appropriate operating conditions
under which dry reforming reactions would proceed for a variety of applications. Such
typical processes requiring different H2/CO feed ratios are shown in Table 2. Finally, a
short summary of temperature and pressure conditions of these processes is given in
Table 3.

Table 1: Industrial production of Hydrogen and Syngas through steam reforming [1,2]
Plant/Location Main product Capacity, MMSCFD Year
Pernis, Rotterdam, Netherlands H2/CO 80 994
New Orleans H2 Plant, LA H2 70 1994
Pasadena Hydrogen Plant H2 80 1996
Houston, TX
Wilton Hydrogen Plant H2 18 1997
Teekside, UK
Paraguana H2 Plant, Venezuela H2 50 1997
Amuay H2 Plant, Venezuela H2 50 1997
Geismar HYCO Plant H2+CO+ Syngas 45 1999
Geismar, LA
Convent, LA, USA Direct reduction 1.2 MT/yr 1998
Iron (DRI)
ANSDK I, El-Dikheila, Egypt DRI 0.80 2000
ISPAT DR3 DRI 1.36 1999
Point Lisas, Trinidad & Tobago
Saldanha Steel, Saldanha Bay, DRI 0.804 1999
South Africa

Table 2: Typical applications for Syngas production
H2/CO Application Process Used/Proposed
>3 Hydrogen, Ammonia Steam reforming and water gas shift
2-3 Methanol Steam reforming
2-2.5 Fischer Tropsch (gasoline and light Partial oxidation, steam reforming
olefins)
1.7-2 Fischer Tropsch (Fixed Bed, for waxes or Steam reforming –Partial Oxidation
diesel)
1.5 Aldehydes, Isobutane, Isobutanol, Higher Hydroformylation
Alcohols (C1-C6)
1 Acetic Acid Autothermal Reforming
<1 Polycarbonates CO2/CH4 (dry) reforming

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Table 3: Typical Conditions of Downstream Processes 4,5
Process Hydrogen Ammonia Methanol Fischer Tropsch Hydro-
generation Synthesis Synthesis Fix Bed Synthol formylation
T (°C) 815-870 775-835 350-420 215-250 355-415 160-200
P (MPa) 2.5 9.7-24.9 11.8-16.0 2.72 2.3 4.92-10.24

In addition, some conditions such as residual methane are also important because
they dictate lower limits on conversion for the reforming stage. For example, a few
reports indicate that some CH4 (e.g. up to 2 percent) may be economically advantageous
for ammonia synthesis. Likewise, the presence of CO2 can be tolerated and even desired
in some cases 6. For example, in methanol synthesis, some CO2 in the feed is allowed
(9% vol. is typical) 5. However, in ammonia synthesis the removal of CO2, H2O, and CO
(compounds that contain oxygen) are of critical importance. Table 4 summarizes the
maximum level of CO2 allowed in different Syngas uses.

Table 4: Maximum content of CO2 allowed in the synthesis step
H2/CO Application Maximum CO2 Currently allowed
>3 Hydrogen, Ammonia Total carbon oxides (CO+ CO2) must be reduced
to less than 15 ppm. 7
2-3 Methanol 2-8 % vol.
2-2.5 Fischer-Tropsch synthesis Removed in previous stages
1.7-2 Fischer Tropsch (Fixed Bed) Removed in previous stages
1.5 Aldehydes, alcohols CO2/CH4 = 2.2/1.0 5
1 Acetic Acid CO2/CH4 = 0.54/1.0 5
<1 Polycarbonates 1-300 ppm 8

With the exception of the SPARG process, the removal of sulfur compounds is
essential for downstream processes because they poison the catalysts. For example, in the
case of methanol synthesis, the maximum allowable sulfur level is 1 to 2 ppm by
volume5. In this study, the issue of sulfur will not be discussed.

To a great extent, all existing research aimed at the identification of catalysts is
mostly concerned with activity and stability of the catalyst and it has been seldom linked
with temperature, pressure and feed composition conditions for optimal process
economics. This article aims at the identification of optimal processes conditions that are
rooted on economical considerations. To do so, it is assumed that industrial reactors are
operated in such a way that equilibrium holds in the outlet (one practical exception for
this are fluidized reactors). Finally, a link between inlet and outlet conditions, as well as
the corresponding energy requirements for the process provides target-operating
conditions (temperatures, inlet compositions, etc) for fundamental catalytic studies.

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Goals and Constraints of this Study
The purpose of this study is to identify under which conditions (pressure,
temperature, amount of water in the feedstock, and reactors scheme) the reforming of
natural gas using steam and/or CO2 is thermodynamically and economically optimal. The
constraints are:

• High methane conversion.
• The lowest possible CO2 content in the product.
• The highest possible Syngas production rate.
• A low usage of steam is preferred.

Although the results of this study can be used for any feedstock, two different types
of gases are picked to illustrate certain points. Table 5 shows the composition of these
two gases, one with a high content of CO2 (Terrell, TX) and the other corresponds to a
typical natural gas with almost no CO2 (California). The latter contains a high amount of
ethane, and it was assumed that it could be removed prior to reforming.
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Table 5: Natural Gas Composition
Comp. Terrell Gas California Gas California Gas after
Composition composition ethane removal
CH4 45.7 % 89.4 % 98.0 %
CO2 53.9 % 0.8 % 0.9 %
C2H6 0.2 % 9.8 % 1.1 %
N2 0.2 % --- ---

Single reactor and multiple reactor configurations in series and parallel arrangements
are considered. Addition/removal of CO2 and water to/from the inlet and intermediate
streams is also considered.

Preliminary Equilibrium Considerations
To a great extent, most papers related to CO2 reforming focused on finding a suitable
catalyst with high activity and able to prevent carbon formation. When dealing with
kinetics rate expressions, reaction mechanism is important to establish the rate limiting
step and which reaction is predominant. When using equilibrium data, reactions are not
important. Because calculations are based on the minimization of the Gibbs free energy,
distinctions between steam and dry reforming are therefore confined to determine how
much water and CO2 are present in the feed. In the presence of both water and CO2 in the
initial mixture, the distinction becomes a little harder.

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The set of reactions involved in reforming are: CO2 reforming reaction: (1) CO2 + CH4 Æ 2 CO +2 H2 Reverse water gas shift (RWGS) reaction: (2) CO2 + H2 Æ H2O (g) + CO Steam reforming reaction: (3) H2O + CH4 Æ CO + 3 H2 The steam reforming reaction is a linear combination of the other two. 6 . the reactions considered for carbon forming are: Boudouard reaction: (4) 2 CO Æ CO2 + C(S) Methane cracking reaction: (5) CH4 Æ 2 H2 + C(S) Although charts showing explicitly equilibrium composition have been published elsewhere1. on the yield of Syngas is investigated first. as well as the H2/CO ratio decreases when increasing the pressure for different ratios of CO2/CH4 in the feed.2. In turn. Thus atmospheric pressure should be the preferred condition for both dry and steam reforming. for completeness such plots are included as a function of initial composition. The effect of pressure and temperature on the equilibrium and consequently. From this graph. Effect of Pressure: Figure 1 shows the equilibrium conditions as a function of the CO2/CH4 ratio and parametric in pressure. On the other hand.10. it can be seen that the methane conversion. the CO2 content in the outlet stream is lower at lower pressure.

2 CH4 CO2 CO2 H2O 0.25 2.00 1.25 3.50 2.2 CH4 CH4 H2O 0.75 4.25 1.50 0.3 H2 CO2 CH4 CO2 H2 0.75 2.75 2. T= 800°C Effect of temperature: Figure 2 shows the equilibrium conditions at atmospheric pressure as a function of the CO2/CH4 ratio and parametric in temperature.00 CO2/CH4 ratio Figure 2: Effect of Temperature on equilibrium compositions.4 H2 H2 0.00 2.25 1.00 3.3 CH4 0.00 2.75 1.75 1.25 0.00 0.1 H2O 0 0.75 3.4 CO H2 CO2 0.75 4.5 CO 700°C CO Equilibrium composition 0. 0.25 0.00 1.00 0.50 1.00 3.1 H2O 0 0.00 CO2/CH4 ratio Figure 1: Effect of pressure on equilibrium compositions.50 0. high temperatures favor a higher methane conversion and a lower amount of CO2 in the outlet stream.6 1 atm 10 atm CO 0.25 2.25 3.50 1.5 25 atm CO Equilibrium composition 0.50 3.75 3.50 2. P =1 atm 7 .6 900°C 800°C 0.50 3. 0. Clearly.

0 carbon deposition 1. This determination is performed later in connection with a specific set of reactors. it is desirable to predict temperature.5 0. Instead of looking at the affinity in each reaction independently.5 1 atm 10 atm 25 atm 4.While all these charts are useful to make general conclusions.0 1/2 CO2/CH4 ratio 2. Therefore. there is a temperature Tb below which there is a thermodynamic affinity for the exothermic Boudouard reaction. and 25 atmospheres and temperatures ranging between 500°C and 1300°C.5 1/1 No carbon deposition 2.0 3. Rostrup-Nielsen11 analyzed conditions for carbon-free operation considering the Boudouard and the methane cracking as reversible reactions. Thus. but on a whisker-like structure of the carbon deposited on the catalyst.5 region 1. The real ∆G of reaction is not based on graphite. °C Figure 3: Carbon deposition regime for dry reforming 8 . the predictions using graphite are conservative.5 1/3 3. 4. For any gas of fixed composition. This procedure was performed for CO2/CH4 feed ratios ranging from 1/1 to 4/1 and evaluated at pressures of 1. the identification of water and CO2 inlet concentration to achieve desired outlet conditions is not straight forward.0 Terrell gas 0. Carbon Formation Carbon formation can easily plug catalyst beds and heat exchangers and cause cracking of high-pressure fittings even by penetrating through tiny crevices. and composition conditions under which carbon precipitation is not thermodynamically favorable. one can obtain equilibrium compositions using the degree of advance of each reaction (ξi) and predict favorable conditions for carbon formation more accurately. and a temperature Tm above which the endothermic methane cracking reaction is favored. The results are shown in Figure 3 and show good agreement with previous work 2.0 500 600 700 800 900 1000 1100 1200 1300 Tem perature. pressure. 10.

Figure 3 shows the minimum temperature at which one can operate without having thermodynamic affinity for carbon deposition on the catalyst. CO2 and H2O). Carbides formation temperatures are shown in Figure 4. 9 .0 2. While the above curves are informative. Adapted from Wang and Lu 1 For example. Feed compositions (with a high amount of methane) like in most natural gas are located in the diagram where the carbon formation is present at any temperature.0 carbon deposition 1.0 750 800 850 900 950 1000 1050 1100 1150 Tem perature. K Figure 4: Carbon deposition and carbide formation on Ni catalysts. feedstock with CO2/CH4 ratios ranging from 2:1 to 1:1 require temperature conditions higher that 720°C to 1000°C to avoid carbon formation conditions.0 formation 3.840°C.0 carbide CO2/CH4 feed ratio 4.0 0. they do not take into account the initial composition of all three components (CH4.0 5. 6. Temperature conditions to the right of the curve for a fixed CO2/CH4 ratio mean working on a region where there is no carbon formation. Rostrup-Nielsen developed such a graph (Figure 5). This temperature increases up to 1000°C when the pressure is increased to 10 atm. Conditions to the left of each curve indicate the region at which carbon deposition is favored. Using Terrell gas as feedstock at atmospheric pressure. the temperature below which carbon formation is favored is between 820°C .

what is the conversion in such case? To answer the question. H/C O/C Figure 5: Temperatures for carbon limits on Ni catalyst. steam reforming is used to produce hydrogen using natural gas with very low CO2 content. However. Each curve 10 .2 to 3. for several feed ratios of CO2/CH4 from 0. H2/CO=1:1. never including both water and CO2. Moreover. pure steam reforming produces excess hydrogen. for the case of a composition close to Terrell natural gas (1. the amount of water needed to achieve the H2/CO ratio of 1/1 is depicted in Figure 6. Role of Water Typically. what is the amount of water needed to achieve a Syngas with a given ratio. or acetic acid production.2/1 CO2/CH4). the question is: given a certain gas. and that amount of water increases as the ratio of CO2/CH4 increases. ( Rostrup Nielsen 11) All the equilibrium studies on reforming are focused on initial conditions of the mixture that exclude water or CO2.0. with a particular CH4/CO2 ratio. Thus. etc). In this article such conditions are explored. For example. one can obtain the desired ratio of H2/CO of 1/1 using in the feed a percentage of water in the feed up to 10%. to obtain Syngas with higher content of CO (for Fischer- Tropsch. H2/CO=2:1.

50 0. However. 11 .60 0.0 2. The straight line that connects the point H/C=4. 0.5 3.0. and H2O. almost no water is needed. At higher temperatures the amount of water needed also increases.0 0.0 CO2/CH4 feed ratio 800 °C 900 °C 1000°C 1100 °C Figure 6: Water requirements for CO2 reforming at 1 atm. represents all feed mixtures of CH4 and CO2 (no water).10 0. O/C=2. CH4. It has the atomic ratios of O/C in the abscissa and the atomic ratio H/C in the ordinate. Handling so many variables at the same time motivates the search for a different type of diagram to represent a feedstock defined by the composition of CO2. which has very little CO2. Syngas yield.0 (which represents CO2 component).20 0. Equilibrium Chart Rostrup-Nielsen11 proposed the diagram shown in Figure 7.0 1. while the one starting at methane and increasing represent all feed mixtures steam-methane (no CO2). For a typical composition of natural gas (close to California natural gas). methane conversions obtained are very low. due to the low amount of CO2 present.5 1.00 0. and CO2 content in the outlet stream.40 H2O/feed ratio 0. O/C=0 (which represents methane component) with the point H/C=0.represents one temperature.5 2. duty.30 0. which at the same time would give information on methane conversion.

This equilibrium diagram was originally plotted at a fixed temperature of 900°C (1650°F) and a pressure of 6 atm (72 psig). etc) built to indicate what feed composition leads to this desired H2/CO ratio.5 7 H2:CO 3:1 1. 2:1.5 9 Carbon formation 2. It is important to note that the same point represents initial and final equilibrium conditions in this diagram. Rostrup-Nielsen11 at different temperatures.0 A 1.0 CO2/CH4 3. 3.2 3 0. The carbon formation line was obtained from early work of J. since atmospheric pressure has been set as the best condition.0 2.5 3.5 1 2.0 O/C ratio Figure 7: Equilibrium Chart at 1 atm 12 . Initial equilibrium conditions (corresponding to feed compositions) are read on the non-rectangular axis.0 0 0. The figure contains the lines of constant Syngas ratio (3:1.5 2.0 5.0 1.5:1 0.7 H2:CO 2.0 0. 1:1. 1 atm 1.5:1 H/C ratio 5 0. Here.5 H2:CO 1:1 2 0.75 1. Thus no trajectories in a reactor can be constructed. Figure 7 has been built at 1 atm and 850°C (1562°F). while final equilibrium conditions are read on the O/C and H/C axis.The points inside the region defined by these lines represent different mixtures with the ratios H2O/CH4 and CO2/CH4.4 H2:CO 2:1 4 B H2:CO 1.R.5 1.0 6 0.0 10 H2O/CH4 2.0 8 curve.

and CO2 content at the outlet stream curves were added to the equilibrium chart to complete the information required to define a reactor performance. the thermodynamics packages suitable for this system are: SRK (Soave. Therefore. For example. which is outside the carbon formation region. when using Terrell gas to produce a Syngas H2/CO ratio of 2:1. first the feed has to be located in the graph (Point A). water needs to be added to the feed to reach two objectives: to move the feed location point to reach a desired line of H2/CO and to work outside of the region favorable for carbon formation. The lines were obtained by changing the CO2/CH4 ration in the feed and adding water to reach a constant Syngas yield expressed as moles of Syngas per mole of methane. if a ratio of 2:1 is desired. which was obtained changing the ratio of CO2/CH4 in the feed and adding water until reaching the desired fixed methane conversion or the fixed yield of Syngas (H2+CO). According to recommendations for natural gas systems at high temperatures and low pressures. Figure 8 shows the constant conversion lines. Figure 9 shows the constant yield (moles of Syngas/mole of methane). which give good accuracy in the calculations performed. Constant methane conversion. the diagram of figure 7 can be used to completely characterize reactor conditions and to make an analysis of a variety of alternatives. reactor duty.65 moles of H2O per mole of CH4 is added to reach point B. As it is shown in the rest of this article. yield. 2. The simulator ProII TM (Simulation Sciences Inc. PR (Peng Robinson).) was used to perform the calculations using an equilibrium reactor. The SRK equation of state was chosen to perform the equilibrium calculations. 13 . For example. Since the same point represents the equilibrium Syngas. Redlich & Kwong). or BWRS (Bennedict-Webb-Rubin-Starling). it is seen that the H2/CO ratio obtained is lower than 1:1 and that the point is located inside the region favorable for carbon formation (at the left of the carbon formation curve).

5 1 2.0 1.5:1 30% 4 H2:CO 2:1 3 0.0 0.5:1 0.5% 7 99% 1.8% 8 carbon form ation line 99.5 2.5 3.5 99.7 80% H/C ratio 50% 5 0.4 H2:CO 2.5 1.0 0 0.0 1. 10 3.0 2.2 H2:CO 1.0 99.0 O/C ratio Figure 8: Constant methane conversion lines at 850°C and 1 atm 14 .5 2 0.5 H 2O/CH 4 9 Methane Conversion 2.75 H2:CO 1:1 1.0 97% 95% H2:CO 3:1 6 0.0 CO2/CH 4 3.0 5.95% 1.0 2.

5 2. They were calculated by changing the CO2/CH4 feed ratio and adding water to the feed to reach the desired fixed CO2 content in the outlet steam. One of the most important economic indicators is the duty.5 1.7 3 H 2 :C O 2 .4 2 5 H 2 :C O 2 :1 4 H 2 :C O 1.0 1. Figure 10 shows lines of constant CO2 in the outlet stream (expressed as moles CO2 at the outlet stream per mole of CH4 in the feed).0 5.0 O/C ratio Figure 9: Constant yield at 850°C and 1 atm.0 10 2.99 per mole CH4 1.Figure 12 shows the constant duty lines. the net amount of heat that needs to be supplied to the equilibrium reactor was calculated.5 1 2.5 H 2 :C O 1:1 2 0.5 H2O/CH 4 9 3.0 0 0.0 1. which is an important value that gives information on the amount of CO2 that can eventually be recycled to the reactor. It was assumed that most of the energy requirements for the reactor are recovered through steam generation and preheating of the feed.5 0. Figure 11 shows schematically the flow sheet used and.0 0.95 H 2 :C O 3 :1 1.999 2. using a minimum approach temperature of 30°F in all heat exchange. 15 .98 7 3.75 1. 3.0 Constant Yield 8 mole Syngas 3.5 :1 3 0.5 :1 2.0 2. To make a value of duty meaningful.5 H/C ratio 0.8 6 3.5 3.0 3.2 0.0 CO2/CH4 3.5 3.

Temperature S11 Figure 11: Single reactor flow sheet for duty calculations 16 .5 H 2 :C O 1:1 2 0.0 CO2/CH4 3. OUTLET S8 F1 M1 REACTOR COOLER GAS HEAT-EXCH.1 7 line 0.0 0.75 1.5 carbon 1.0 0.5 :1 3 0.2 0. S10 CO2 S3 INLET H2O S7 Amb.2 8 0.0 0 0.5 3.5 2.3 2.05 H 2 :C O 3 :1 1.5 H2O/CH4 Constant CO2 at outlet 9 stream 0.0 1.4 m oles CO2/m ole CH4 2.4 5 H 2 :C O 2 :1 4 H 2 :C O 1.075 0. 3.0 O/C ratio Figure 10: Lines of constant CO2 in the outlet at 850°C and 1 atm.0 10 0.0 5.0 0.5 :1 H/C ratio 0.0 1.7 0.005 0.5 1 2.0 2.02 0.5 0.7 H 2 :C O 2 .9 6 0.6 form ation 0.5 1.

857) H/C ratio 0.5:1 5 80.0 1.0 3.078) 6 0.5 2 0.5 114.000 (55.5 3.4 H2:CO 2.000 (54.0 8 1.75 H2:CO 1:1 1.285) H2:CO 2:1 4 H2:CO 1. Combined with the carbon formation line these curves help identify steam or CO2 needed to get a Syngas with a specific ratio of H2/CO.000 (52.000 (54. However.0 1.5 2. for producing Syngas with H2/CO ratio 2:1.000 (38.5:1 3 0. the line is almost the same. at high pressure the region favorable to carbon formation covers a wide range 17 . 10 3.0 H2:CO 3:1 113.7 110.0 0 0. In addition.0 O/C ratio Figure 12: Constant duty lines at 850°C and 1 atm Effect of Pressure On Figure 13 the constant H2/CO ratio lines at 1 and 25 atm are shown to see the effect of pressure on the Syngas lines.0 0.0 H2O/CH4 Constant duty 115. While there are some differences in the lines at different pressures.0 CO2/CH 4 5.5 9 BTU/Lb-mol CH4 (KJ/Kg-mol CH4) 2. the main disadvantage of working at high pressure is that more water is required to reach the desired H2/CO ratios (lower than 2:1).0 2.000 (47.556) 7 1.5 1.642) 100.2 0.035) 2.5 1 2.

5:1 3 0.4 H2:CO 2:1 4 H2:CO 1.5 1 2.5 2.5 H2:CO 1:1 2 0.25 atm 1.5:1 H/C ratio 5 0. 25 atm 1 atm .0 Carbon formation 8 curve.5 3.of feed composition conditions.0 10 H2O/CH4 2. 3.0 2.0 1.5 7 H2:CO 3:1 1.0 5.75 1.0 0 0.0 6 0.0 1. At high pressure (25 atm). conversion and yield curves are shifted to the right that is they decrease with increasing pressure (Figures 14 and 15).0 CO2/CH4 3.7 H2:CO 2.5 1.0 O/C ratio Figure 13: Influence of pressure on equilibrium Syngas lines @ 850°C 18 . This is due to the increasing water requirements to reach a fixed methane conversion at higher pressure.0 0.2 0.5 9 1 atm 2.

75 1.5 9 Carbon formation 2.5 7 1.0 2.5 1.7 1 atm .0 0.0 80 % Methane 6 Conversion 0.5 3.0 0 0.0 O/C ratio Figure 14: Influence of pressure on methane conversion @ 850°C 19 .0 1. 1 atm .0 3.0 10 H2O/CH4 2.25 atm H/C ratio 5 0.5 2.5 1 2.0 CO2/CH4 5.5 H2:CO 1:1 2 0.4 H2:CO 2:1 4 3 0. 3.2 0.0 1.0 8 curve.25 atm 1.

5 9 25 atm Carbon formation 2.7 H/C ratio 5 0.0 at 2. the savings are 1.5 1 1 atm 2.5 H2:CO 1:1 Syngas 2 0. 3. At high pressure (25 atm) the duty lines shift right (that is.730. All this confirms the notion that lower pressures favor dry reforming. thus reducing the revenues.0 6 0.75 yield 1.0 O/C ratio Figure 15: Influence of pressure on yield @ 850°C and 1 atm Figure 16 shows the influence of pressure on reactor duty.0 2.4 H2:CO 2:1 4 3 0. The CO2 content at the outlet of the reactor also increases.25 atm 1. the yield reduces by 10 %. 20 .0 8 curve. When operating at higher pressures the importance of this difference can be assessed by the following example: For an industrial size plant processing 4.2 0.0 3.0 1. However.0 0.5 2.000 $/year. 1 atm .5 1.0 CO2/CH4 5.000 lb-mol/hr of methane.0 0 0.5 7 1. bringing higher costs to the separation step.5 3.0 3.0 10 Syngas yield H2O/CH4 3. the duty decrease with increasing pressure).0 at 1.

5 2 H2:CO 1:1 0.071) @ 1 atm H/C ratio 25 atm 0.0 0 0.5 3.071) @25 atm 2.25 atm 1.000 (43.0 1. Increasing temperature increases conversion and 21 .0 2.078) @ 1 atm 7 1. its influence on duty is not straightforward. yield.0 6 0. However.000 (54.75 1.5 2.0 0.0 1.0 5. and CO2 at the outlet stream.000 (43.0 O/C ratio Figure 16: Influence of pressure on duty @ 850°C and 1 atm Effect of Temperature This effect is depicted in Figure 17.0 Carbon formation curve 8 1 atm .0 CO2/CH4 3. meaning that for a feedstock of constant composition.7 90.0 10 H2O/CH4 2.5:1 3 0. at high temperature more water is required to reach that ratio. Figure 18 shows the influence of temperature on CH4 equilibrium conversion.5 1 2. while Figure 19 shows the effect on yield.5 1. 3.5 113.5 9 90.2 0. An increase in temperature shifts the Syngas ratio lines up. The temperature also has a direct influence on the conversion.4 5 H2:CO 2:1 4 H2:CO 1.

4 5 920 °C H2:CO 2:1 4 850 °C 750 °C 3 0.920 °C 1.0 1.5 7 1.8 850°C .5 9 2.0 0.5 2.5 2.0 1. Finally.5 3.0 O/C ratio Figure 17: Influence of temperature on equilibrium Syngas lines @ 1 atm 22 .5 0. No clear tendency on the duty lines (Figure 20) with respect of temperature is observed. however.0 2.0 6 0.0 10 H2O/CH4 2. 3.0 8 carbon form ation line 1. the CO2 content decreases (Figure 21).2 0.0 1 3.0 0 0.0 CO2/CH4 5.5 1.75 A 2 1.35 2.7 H/C ratio 0.yield.

0 10 H2O/CH4 X CH4 2.5 9 carbon 2.0 1.0 0.5 1.2 0. 3.8 % 8 form ation line 850°C at: 850°C .5 7 99.5 2 0.7 H/C ratio 0.0 O/C ratio Figure 18: Influence of temperature on methane conversion @ 1 atm.5 3.5 2.5 2.8 % 920 °C 1.0 1 3.75 A 1.0 99.0 2.920°C 1.0 0 0.0 1.0 CO2/CH4 5.4 5 C 920 C 850 C H2:CO 2:1 4 B 3 0. 23 .0 6 0.

0 2.5 2.5 1.99 850°C .0 0 0.5 7 3.5 3.5 2 0.0 1. 3.99 1.0 1.7 H/C ratio 0.75 A 1.0 920°C 6 0.0 10 H2O/CH4 2.920°C 850°C 1.5 9 carbon Syngas 2.0 1 3.2 0.0 O/C ratio Figure 19: Influence of temperature on yield @ 1 atm.0 CO2/CH4 5.0 8 form ation line Yield at: 3.4 5 C 920 C 850 C H2:CO 2:1 4 B 3 0.5 2.0 0. 24 .

5 7 1.000 (54.556) @ 850°C 1.5 3.920 °C 114.0 0.000 (54.75 A 1.000 (54.2 0.0 1 3.0 1.5 (KJ/kg-m ol CH4) 9 114.0 0 0.5 2.0 2.556) @920°C 114. 3.556) @750°C carbon form ation line at: 2.0 1.0 8 850° C. BTU/m ol CH4 2.4 5 C 920 C H2:CO 2:1 850 C B 4 3 0.7 H/C ratio 0.5 2.0 O/C ratio Figure 20: Influence of temperature on reactor duty @ 1 atm 25 .5 2 0.0 10 H2O/CH4 Duty.5 1.0 CO2/CH4 5.0 6 0.

5 1.0 2.75 A 2 1. 3.0 1.0 0.0 8 form ation line CO2 at: 850°C .0 1 3.5 2.4 5 C 920 C 850 C H2:CO 2:1 4 B 3 0.7 1.5 3.5 mole CH4 7 920°C 0.0 6 0.5 0.0 1.5 9 carbon 2.2 0.0 0 0.920°C mole CO2 0.0 10 H2O/CH4 2.0 O/C ratio Figure 21: Influence of temperature on CO2 content @ 1 atm 26 .7 H/C ratio 0.7 850°C 1.0 CO2/CH4 5.5 2.

20%.95%. the yield is almost 4. the Syngas yields to 3. The negative effect on costs is caused by the increase on the amount of water needed or the more favorable conditions for carbide formation.It is clear that increasing temperature can increase conversion and yield and lower the CO2 content at the outlet reactor stream. for a typical size of plant (methane feed = 1. which has to be compared to the reduction in revenues caused by a lower Syngas yield and the higher costs of the CO2 separation step caused by the increase in CO2 content at the outlet stream. Therefore. while the amount of CO2 to be removed is equivalent to 36. when analyzing a single reactor scheme. This is performed in the next section. the influence of a CO2 recycle can be analyzed on the equilibrium chart and determine whether recycling is beneficial in terms of methane conversion. while point C gives 0. Methane conversion is 99. Regarding the effect of pressure.2:1). This feedstock is located at the point A in Figure 22. The change in duty is less than 1.461 KJ/kg-mol CH4. although it decreases. the amount is negligible. the main point is the reduction of duty obtained when operating at high pressure (25% when increasing pressure from 1 to 25 atm). This is studied later.992 Kg-mol/Kg-mol CH4.131 KJ/kg-mol CH4. Use of a Single Reactor The first gas feedstock to investigate is Terrell natural gas. The addition of water prevents carbon deposition.85 kg-mol of CO2/Kg-mol CH4 in the feed.500 kg/hr. which contains high proportion of CO2/CH4 (1.7/1 (point B). If the production of a Syngas ratio of 2/1 is desired. especially the one related to the reduction in steam consumption.52/1 represented by point C by introducing a CO2 separation step and moving the CH4/CO2 ratio to point A2.2%.700 kg/hr. The point is inside the region favorable for carbon formation (to the left of the carbon formation line). Regarding the CO2 content at the outlet stream. The methane conversion lowers to 99. water needs to be added until the ratio H2O/CH4 is about 2.0 Kg-mol of Syngas/Kg-mol CH4. Regarding the duty. and reactor duty. That amount of water can be reduced to a H2O/CH4 ratio of 1. For example. and the duty is 55. 27 .8%. and the duty to 54. point B gives a value of 0.814 kg/hr) the steam reduction is of 37. and the change in Syngas yield is less than 0.39 kg-mol of CO2/kg-mol CH4. In an economy of scale these savings are significant. Syngas yield.

8% 8 Kg.035 2.0 0.509 KJ/kg-mol CH4). It is observed that a process to obtain a lower syngas H2/CO ratio of 1.5 1.5/1 needs less water.5 :1 3 0.0 CO2/CH 4 5. If a different temperature is analyzed on the equilibrium chart.993 Kg-mol/Kg-mol CH4).5/1 (point B1 in Figure 22).99 1.0 99.5 2.75 1. when compared with a process to obtain the Syngas H2/CO ratio of 2/1.58 Kg-mol/Kg-mol CH4) at the outlet stream. has a slightly lower syngas yield (3.5 3.0 1.0 2.5 1 2. 3.556 7 99.0 10 H 2O/CH 4 Constant duty Constant 55. making in this particular case 28 . and has a lower CO2 content (0.4 H 2 :C O 2 .078 6 H 2 :C O 3 :1 0. single reactor configuration (1atm. has a lower reactor duty (54. lower methane conversion (99. the required water addition corresponds to a H2O/CH4 ratio of 1.95% 1.2 B1 0.85%).7 H/C ratio 0.48/1 (at the same pressure and temperature conditions as above).0 0 0.0 A 1.5 54.5 :1 5 4 H 2 :C O 2 :1 B C H 2 :C O 1. the whole equilibrium diagram has to be built for the new temperature conditions.mol CH4 3.0 O/C ratio Figure 22: Terrell gas.999 Kg-mol 2.5 methane KJ/Kg-mol CH4 9 Constant Yield conversion 3.0 54.0 3.5 A1 H 2 :C O 1:1 2 0. 850 °C) If the desired Syngas ratio using Terrell gas is 1.

one obtains point D.642 KJ/Kg-mol CH4. increasing conversion and yield.95 Kg-mol/Kg-mol CH4. and on the availability of CO2. Syngas yield (0. and the favored carbon formation are the price to pay. The best option is based on the constraints imposed on the particular case (high methane conversion. Thus. However. to move to the right side of the carbon formation line. making this option not worthwhile. one can add CO2 and H2O to read for example point D1. We now turn to analyze the processing of California gas in a single reactor (Figure 23). Such gas is represented by point C. a Syngas yield of 3. and a duty of 52. desired H2/CO ratio. However. H2O and CO2 have to be added to go from point D to its right. which contains a very low CO2/CH4 ratio (typical for most natural gas feedstock).16 %). an addition of water of 0. 29 .0%.9/1 H2O/CH4 and 0. From here. Depending on the desired yield. Two options are available to get Syngas H2/CO ratios of 2/1.the process simulator more useful. a qualitative analysis is still valid. By adding a little amount of water. since it is known how temperature affects the equilibrium. the values for methane conversion (2.13 Kg-mol Syngas per Kg-mol of CH4). high yield) and the economics of each alternative.45 CO2/CH4 renders a methane conversion of almost 99.

5 3.5 3.556 6 3.mol Syngas 1.0 CO2/CH 4 5.5 :1 0.0 1.99 Constant Yield Kg. 30 . Through that equilibrium point.0 Constant duty H 2O/CH 4 KJ/Kg-mol CH4 2.500 5 30% D D1 H 2 :C O 2 :1 4 C H 2 :C O 1.7 43.0 0 0.0 1.5 :1 3 0. 10 3.0 33. For a given composition of natural gas represented by point A.0 3.2 0.0 99% H 2 :C O 3 :1 52.5 2.078 0.642 54.4 2.999 8 conversion 3. a desired Syngas ratio of 2/1 is reached by adding water to get point B.0 0.071 H/C ratio H 2 :C O 2 . the line of constant CO2 corresponding to 0.5 1 2.035 9 Constant methane 2.0 3.8 54.5 1.95 1.98 7 Kg-mol CH4 3.0 2.0 O/C ratio Figure 23: California gas on a single reactor configuration Recycle of CO2 The recycle of CO2 can also be studied using a procedure illustrated in Figure 24 for a final desired syngas ratio of 2:1.75 1.5 H 2 :C O 1:1 2 0.55 Kg-mol of CO2/Kg-mol of CH4 intersects.5 55.

556) Syngas Yield Duty.8 2. more water is needed to keep the same Syngas ratio of 2/1 and the duty increases.99 0.2 1. Since the yield at point B is already close to the maximum theoretical of 4.0 1.6 1.8 1.4 (KJ/kg-m ol CH4) line 1. In addition. which renders point B2 through which a constant CO2 line intersects with a value that is equal to the increment of CO2 in the feed. duty.2 2. syngas yield. 4 O/C ratio Figure 24: Partial and total recycle on the equilibrium chart The operation using partial recycle is obtained by adding to the feed a constant CO2 value (a fraction or all the value from the outlet stream.3 114.7 5 H/C ratio 0.0 2. It is clear that an increase of CO2 recycle increases methane conversion.5 carbon BTU/m ol CH4 7 form ation 0.999 8 H2O/CH4 Constant CO2 3. 1.6 0. the new equilibrium syngas over the 2/1 lines is point B2.5 1 0. The total recycle operation is obtained when the increment in CO2 to the feed reaches point A2. 2.000 (54.5 6 0.0 2 A A1 1.000 (55.0 3. represented by point A1).6 0. the cost of compression is higher and the increasing amount 31 . Finally.0 0.0 2.9 B B1 B2 H2:CO 2:1 4 3 115. no clear gain is obtained.5 A2 CO2/CH4 2.7 0.035) 0.4 1. the amount of water needed and the CO2 content of the outlet stream. This new feed renders a Syngas represented by point B1. Since the production goal is a 2/1 H2/CO ratio.75 1.

5 1.5 A1 2.1 7 0.3 H2O/CH4 BTU/m ol CH4 Kg-m ol CO2/Kg-m ol CH4 (KJ/kg-m ol CH4) 2.6 114.0 0 0.99 0.5 0.9 6 0.5 3.075 0.75 1. In other words.02 0.0 H 2 :C O 3 :1 0.5 :1 0.556) form ation line 0.5 9 115.999 yield 0.7 0.4 5 H 2 :C O 2 :1 4 B B1 C C1 H 2 :C O 1.0 CO2/CH4 5.55 Kg-mol/Kg-mol of CH4.5 H 2 :C O 1:1 2 0.5/1) is desired.5 2.000 (54.0 2.01 0.5 :1 3 0.4 3. there is no incentive to recycle CO2 in this case.005 0.0 8 3.0 A 1.7 H/C ratio H 2 :C O 2 .05 1.2 2.of CO2 at the outlet stream increases the cost of the CO2 separation stage.0 1 3.0 1.5 carbon 1.031) Syngas 0. 32 .000 (55.0 O/C ratio Figure 25: Recycling CO2 with Terrell gas For the case in which a lower Syngas ratio (1.0 0. The amount of CO2 in the outlet stream is 0. 3. The values of Syngas yield and methane conversion obtained on the diagram are still high not justifying the recycle either.2 0. Terrell gas represented by point A (Figure 25) needs the addition of water to reach point C.0 10 Duty Constant CO2 at outlet stream 0.

0.000 (43. As in the previous case. when recycling all the CO2.02 0.75 H2:CO 1:1 2 1.2 3 H2:CO 1.005 H2:CO 3:1 Kg-m ol CO2/Kg-m ol CH4 110.642) 5.0 0. increasing the CO2 recycle increases the syngas yield and methane conversion. the total recycle gives a new feed composition represented by point C1.000 (52.05 6 0.000 (33.071) H/C ratio D E D1 4 H2:CO 2:1 C C1 3.5:1 0.500) 5 0.5 90.8 1. its flowrate at the outlet stream is too low making it impossible to reach the H2/CO ratio of 2/1 with a high syngas yield and methane conversion and away from the carbon formation region.0 1. Point D1.0 0. any point at the right of the carbon formation curve cannot be obtained just by recycling. as desired.01 H2O/CH4 Constant CO2 at outlet stream 0. As a consequence.5 CO2/CH4 0.5:1 70. Indeed. Therefore. Therefore. 33 .6 0.5 0.7 carbon form ation line H2:CO 2. however.2 1.4 O/C ratio Figure 26: Recycling CO2 with California gas When processing California gas without CO2 recycling in a single reactor (point C in Figure 26). any desired ratio of H2/CO (for example 2/1) can be reached at point D with very low conversions and yield. it is still located inside of the region favorable for carbon formation.5 2.4 0.1 1.0 0.2 0. addition of external CO2 and H2O to the reactor has to be considered.5 0. to reach point E (outside of the carbon formation region).4 4.

0 2.5 1 2.0 0 CO2/CH4 0.0 1.0 113.4 Syngas 3.5 2. more addition of both CO2 and H2O has to be considered.6 % max.2 2.0 1.5 :1 3 0.0 5.7 H2O/CH4) to reach point D1.071) C H 2 :C O 1.75 1.0 3.0 Constant CO2 at outlet 0.3 H2O/CH4 stream Kg-m ol/Kg-m ol CH4 2.0 8 3.2 C1 C2 H 2 :C O 1:1 0.5 1.556) 1.0 0. because the recycling option is not enough to move the equilibrium away from the carbon formation region.4 5 H 2 :C O 2 :1 D2 D D1 4 90. The new feedstock also needs the addition of water (0. the effect of recycling CO2 on the duty of the reactor for the case of California gas with external CO2 addition results in an increase of duty increases.02 6 0.000 (54. Finally.7 H 2 :C O 2 .5 carbon 114. but at a very low rate (0.000 (52.35 CO2/CH4 (Point C1).01 110.1 7 0. Since the operation on the safe side of the carbon formation line is desired. 10 3.5 3.5 :1 H/C ratio 0.).642) 0.000 (43.99 0.05 H 2 :C O 3 :1 1.5 2 0.0 O/C ratio Figure 27: CO2 recycle on Single reactor.Consider the addition of external CO2 (Figure 27) to obtain a syngas ratio of 2/1 with high methane conversion (95%) and high syngas yield. which is located on the borderline of the carbon formation line.5 form ation line 0.078) 0. California gas 34 . This is reached by adding CO2 to the feed to get 0.5 9 Duty 0.4% to 0.000 (54.999 yield 0.

and a marginal increase in Syngas yield). (Kg-mol/Kg-mol CH4) 3.9 % Syngas Yield.85 3. 1 atm Terrell gas processing – optimal conditions from equilibrium chart H2 XCH4 H2O CO2 outlet. The addition of external CO2 is considered for the case of Syngas ratio 1/1 to meet our set of constraints regarding Syngas yield as it was seen from previous equilibrium chart analysis.99 CO2 outlet (Kg-mol/Kg-mol CH4) The minimum possible Water addition (Kg-mol/Kg-mol CH4) The minimum possible Duty The minimum possible Reactor pressure.85 1. In such case. recycling can be of value.42 0. atm 1. it is desired to establish a set of optimum operating conditions for the processing of both Terrell and California gas.509 2/1 99. Table 7: Optimal conditions Terrell gas from Equilibrium chart at 850°C. when recycling CO2 the separation and compression step has to be considered.5/1 99. °F 650°C-930°C From the equilibrium chart at a fixed temperature of 850°C. especially if the generation of CO2 proves to be more costly than its generation. minimum flowrate of water. the CO2 recycling option does not help to obtain good syngas yield or a high methane conversion. Reactor Temperature.Concluding.599 1. for Terrell gases processing the use of CO2 recycle does not have an advantage over the no-recycling option (more addition of water. For California gas processing. more duty required. higher conversion. Optimal conditions for Single Reactors After analyzing the single reactor configuration on the equilibrium chart. higher yield possible.55 3. and minimum duty.70 0. Table 6: Set of constraints for single reactor configuration Constraint Value Methane conversion 99. On the other hand. To obtain the optimum temperature.96 Addition/recycle 53. These values are depicted for the case of Terrell gas processing in Table 7.95 2. the simulator Pro II TM (Simulation Sciences) has been used.999 No recycle 55.0 0. and the addition of CO2 has to be considered. these optimum values can be obtained.15 3. The fixed range for the constraints of the problem is shown in Table 6.993 No recycle 54.22 0. Syngas yield Recycle Duty CO % CH4 Kg-mol CO2 Kg-mol /Addition (KJ/Kgmol CH4) ratio Ratio Kg-mol CH4 Kg-mol CH4 1/1 99.274 35 .

there is convergence for all the set of data.99 Both 54. the methane conversion has been fixed at 99. the conditions chosen have fulfilled the constraints of methane conversion and syngas yield.95 1.509 829-862 2/1 99.999 Recycle 55.95% and a fixed ratio of H2/CO has been set as constraint. when a constant high CH4 conversion is desired under the same scheme of Terrell gas processing. to reach the constraints it is required an increase in the reactor temperature for the other ratios.5/1 Infeasible 2/1 Infeasible 3/1 1078 99.999 Recycle 54. Duty ratio Temp.42-2.95 3.7-3. Therefore. H2+CO.561 898 1.Only for the case of required 2/1 ratios.48 0.999 53.95 1. When the syngas ratio increases to values of 3/1 and higher.999 56. ratio Kg-mol CH4 Kg-mol CH4 Addition CH4) °C 1/1 99.659 5/1 860 99. California gas-No recycle California gas. a reasonable syngas yield cannot be obtained unless external CO2 addition is considered. To find the optimal temperature required to meet the constraints. XCH4 CH4 Kg-mol Kg-mol KJ °C Kg-mol CH4 Kg-mol CH4 Kg-mol CH4 1/1 Infeasible 1. In addition.22-0. for H2/CO ratios from 5/1 and above.1 0. Table 8: Optimal conditions Terrell gas and recycling CO2 H2 XCH4 H2O CO2 out.55-0. The amount of water added to the feed and the temperature of the reactor were adjusted to achieve this goal. Since this effect is not easily visualized using the equilibrium chart.15-0. its processing is convenient.715 36 . However. under the set of constraints imposed. This is shown in Table 9.42 3.01 3.9 3. adding water to the feed to meet H2/CO ratio H2/CO Rx.85-1.95 2.5/1 99. a process simulator is used. Table 9: Temperature to get constant XCH4.6 0. Syngas Recycle Duty Temp CO % CH4 Kg-mol Kg-mol Or (KJ/Kgmol Rx. as one can infer from the equilibrium chart. The results are given in Table 8. the system evaluated turns out to be infeasible for the cases when the goal was a syngas ratio from 1/1 to less than 3/1. % H2O CO2 outlet.57 3.95 0.6 0.76 0. Since conversion and H2/CO syngas ratio are set only one temperature satisfies this goal.274 814-850 When processing California gas at H2/CO ratios ranging from 1/1 to 2/1.35 3.

For example for the case with an H2/CO ratio of 2/1.95 3.882 1/1 60 917 99.89 1.999 56.95 0.097 1.999 56.999 58.470 2/1 100 767 99.95 2.39 0.146 1.999 57.5/1 40 846 99.99 54.22 1. Duty ratio Recycle Temp. external CO2 is needed.95 0. recycling CO2 from simulator H2/CO % Rx.95 2. 37 . However.047 2/1 60 790 99.98 3. H2+CO.30 1.93 0.23 3. etc.43 2.57 3.95 3.95 5.999 56. shows similar calculations for Terrell gas processing. recycling CO2 is not enough to get high yields and conversion.829 1/1 40 930 99.5/1 100 806 99.999 56.49 0. recycling CO2 increases the yield.43 1.5/1 20 862 99.999 57. The cost of CO2 separation and recycling needs to be considered.61 1. Table 10.935 1/1 100 898 99. the duty of the reactor increases in approximately 5 % when going from 0% to 100% CO2 recycle.). • For California gas processing.It is observed that the temperature required to get fixed methane conversion decreases as the recycle of CO2 increases but the duty goes up. The H2O/CH4 ratio also increases significantly.25 3.625 2/1 40 806 99.61 3.95 4.95 0.99 55. when recycling all the CO2 the temperature can be reduced from 850°C to 767°C.41 3. the following conclusions are made: • When using Terrell gas. the water required. and working at low desired Syngas H2/CO ratios. Thus. XCH4 CH4 Kg-mol Kg-mol KJ °C Kg-mol CH4 Kg-mol CH4 Kg-mol CH4 1/1 20 946 99. carbon deposition.58 0.421 Conclusions for Single reactor configurations Assuming that a catalyst able to work under the predicted conditions exists (high temperature.74 3.780 1.999 55.99 54.95 3.76 0. the duty. allowing the catalyst to work under less severe conditions.99 54. Table 10: Terrell gas and recycling CO2 Terrell gas. presence of water.33 3.942 2/1 20 824 99.30 1.87 3.95 0.84 3.414 1. This effect plays a very important role in deciding to recycle CO2.95 1. and the methane conversion at constant desired H2/CO ratios.5/1 60 829 99. % H2O CO2 out.36 3.09 3.

19 99.5/1 829-862 1. one reactor configuration 1/1 898 1.163 Terrell gas. 38 .22-0.95 2.999 54. while in the second one the objective ratio of H2/CO of 2/1 is reached. The goal is to find a reactor scheme that might competitively produce syngas (high conversion. H 2O California/ Terrell H2 CO H 2 O /CO 2 H 2O CO2 CH4 C 2H 6 Rx-1 Rx-2 H 2 O /CO 2 N2 Figure 28: Generalized series reactor scheme Several arrangements of two series reactors were evaluated.95 1.19 99.87 50.19 99.6 0. Both reactors working at the same temperature. a.42-2. CH4 Total.6 0.57 3.66 0. high yield.999 55.85-1. the first one to get an intermediate Syngas ratio H2/CO.55-0.004 3.95 0.990 54.7-3. addition of CO2 and H2O to the feed California gas. one reactor with fixed temperature. and with better economics) when compared to the single reactor scheme. % CH4 Kg-mol CO2 Kg-Mol KJ °C Kg-mol CH4 Kg-Mol CH4 Kgmol CH4 2/1 927 0. low CO2 at the outlet stream. Removal of H2O and/or CO2 after the first reactor and an eventual addition of water to the second reactor to meet the desired H2/CO ratio at the outlet syngas (Figure 28) are considered.42 3. There is no CO2 or water removal after the first reactor.509 2/1 814-850 1. H2/CO Rx 1 CO2 X CH4 H2O CO2 out Syngas Duty Ratio Temp. Table 11: One reactor-California gas.32 99. some for simple illustration of the way the equilibrium chart can be used.15-0.76 0.95 0.561 1.9 3.274 Reactors in Series We first consider the case of reactors in a series configuration. • The best conditions for Single reactor configuration are given in Table 11.

the equilibrium chart can 39 . and addition of water to the second reactor. whereas in the second reactor the final H2/CO ratio of 2/1 is obtained. using the temperature and feedstock conditions the second reactor. This scheme is advantageous for a gas like Terrell gas. the performance of two reactors in series can easily be reached with just one step (single reactor scheme). b. for example. in the first reactor an intermediate syngas H2/CO ratio is obtained adding water to the feed to operate outside of the region favorable for carbon formation. Addition of water to the first reactor. These cases are summarized in Figure 29. c. This scheme is not good for a Terrell gas. As it will be shown later case a can be optimized using different reactor temperatures. In case b. Addition of CO2 and water to the first reactor. which in turn needs additional water to reach the desired final syngas H2/CO ratio of 2/1 (point B). one can. Same as case b but recycling the CO2 from the separation stage. there is an intermediate step of CO2 removal before the second reaction step. and addition of water to meet the desired H2/CO ratio. Using Terrell gas represented by point A (Figure 30). As long as the temperatures in both reactors are the same. H2O H2O California/Terrell California/Terrell H2O H2O H2/CO=2 CO2 Rx-1 Rx-2 Rx-1 Rx-2 CASE A CASE B H2O H 2O California/Terrell California/Terrell H2O H2O H2/CO=2 H2/CO=2 CO2 CO2 CO2 CO2 Rx-1 Rx-2 Rx-1 Rx-2 CASE D CASE C Figure 29: Layout of cases study with series reactors For case a. removal of CO2 from the outlet stream. removal of CO2 from the outlet stream. This point represents the feed to the second reactor. Clearly.25/1 by adding water to move to point A1. obtain a syngas ratio of 1. so it is used for a California type gas. d.

3. The final yield and methane conversion is lower than in a single reactor configuration (point B).0 10 Constant duty H2O/CH4 BTU / mole CH4 2.000 (54. 850 °C.5 1 2.5 3.071) 0.5 3.078) 6 0.5 115.0 0 0.2 0.0 2. point A2 is obtained.0 1.still accurately represent the behavior of this reactors scheme (Figure 30).500) B1 H 2 :C O 2 :1 4 B A2 H 2 :C O 1.556) 1.0 A 1.Terrell gas.75 1.000 (43.5 A1 H 2 :C O 1:1 2 0.0 3.98 7 3. From here. When performing the CO2 removal of the mixture of composition of point A1. since water has to be added to get the final ratio.000 (33.99 114.22 Kg-mol H2O/Kg-mol CH4.0 113.5 1.70 H2O/CH4).5 2.5 :1 3 0.95 H 2 :C O 3 :1 1.0 CO2/CH4 5.7 110.0 O/C ratio Figure 30: Series reactors cases a and b .0 0. This point lies directly on a constant water line.000 (54. 1 atm 40 .5 :1 H/C ratio 90.000 (55035) 9 (KJ/Kg-mol CH4) 2.999 Constant Yield 8 Kg-mol/Kg-mol CH4 3. but the total amount of water used is lowered by 0.4 5 70.000 (52. the point is moved following the non-rectangular equilibrium coordinates until it reaches the 2/1 Syngas ratio line represented by point B1 (the total water required per mol of methane fed to the set of reactors is 1.0 3.642) H 2 :C O 2 .

Table 12 shows a comparison between a single reactor and two reactors in series using Terrell gas as feedstock and the configuration of case b.63 Reactor duty. °C 850 850 Reactor Pressure.65 2.0 2. Table 12: Comparison of reactors in series (case b) with single reactor at 850 °C Single Reactors in series Reactor Case b Reactor Temperature. Figure 31 shows California gas represented by point A. The only advantage of the series reactors scheme is therefore the reduction in steam usage.95 99. total H2O/CH4 ratio 2. % 99. which with addition of CO2 and H2O in the first reactor reaches the point A1 (0. 41 . unless syngas ratios lower than 1:1 are desired. atm. 1 1 Methane conversion. However.65 H2O/CH4. and 0.82 0. it was concluded that this gas needs the addition of both CO2 and H2O as well as a recycle of CO2 in order to obtain a mixture outside of the region favorable for carbon formation with relevant conversions or yields. which is followed by water addition to reach the final 2/1 Syngas ratio (Point B1).82 Syngas yield. Kg-mol CO2/Kg-mol CH4 0. total KJ/Kg-mol CH4 56.0 Water added.993 CO2 outlet. a CO2 separation step is performed reaching point A2.088 57.3 H2O/CH4.777 Reactors involved 1 2 CO2 separation Final Intermediate and final. adding CO2 to a Terrell gas does not make sense.999 3. The total amount of water is 1. After the first reactor. It is clear that. In the single reactor configuration analysis. Kg-mol /Kg-mol CH4 3.44 Final H2/CO ratio 2. there is an increase in duty (3%).75 CO2/CH4). We illustrate case c using California gas because it is the appropriate option for this gas.

078) 110.98 7 3.99 114.0 O/C ratio Figure 31: Series reactors with California gas-case c Case d.0 1.5 3. if no recycle exists.5 3.5/1.0 113.5 H 2 :C O 1:1 2 0.2 0.500) B1 H 2 :C O 2 :1 4 A H 2 :C O 1.0 3.556) 1.0 2.0 0 0.000 (54. can also be represented on the equilibrium chart (Figure 32).000 (43. where recycling of CO2 is performed after the first reactor.5 115.5 1.999 Constant Yield 8 Kg-mol/Kg-mol CH4 3.642) 6 0.0 1.5 2.5 1 2.071) H/C ratio 0. the reactor requires water to go from A to A1 to reach a desired partial ratio of 1.035) 9 (KJ/Kg-mol CH4) 2.000 (54.0 0.0 CO2/CH4 5.0 10 H2O/CH4 Constant duty BTU / mole CH4 2.5 :1 90.75 1. there is an intersection line of constant CO2 (0.000 (55.0 3.5 :1 A2 A1 3 0.000 (33. At that point.000 (52. Starting with Terrell gas as feedstock.4 5 70. The segment A2 to B represents the partial recycling operation 42 .7 H 2 :C O 2 .95 H 2 :C O 3 :1 1.6 moles/mol CH4). 3.

simulations using ProII 43 .000 (55.500) B1 H 2 :C O 2 :1 4 B H 2 :C O 1.642) H/C ratio H 2 :C O 2 .75 1.5 Constant duty 9 BTU /mole CH4 Kg-mol KG-/mol CH4 2. showing a H2O/CH4 ratio increase from 2.078) 3.2 0.0 3.999 (KJ/Kg-mol CH4 ) 8 3. the usage of water and the duty increases. the requirements of water increases when increasing temperature. water has to be added to the second reactor to reach point B1 and as a consequence a higher reactor duty is needed.5 H 2 :C O 1:1 2 0.000 (33.556) 7 3. 3. thus identifying savings on steam when working at lower temperatures.4 5 70.5 :1 0.95 1.0 H 2 :C O 3 :1 113. However.9 6 0.0 CO2/CH4 5.mol/Kg.67 to 3.000 (52.000 (54. as in the previous case d.5 2.01 (12.5 110.5 A2 1 2. to accurately predict the behavior of series reactors arrangement.5 1.0 O/C ratio Figure 32: Series reactor with CO2 recycle-Terrell gas It is very important to point out that to reach the final H2/CO ratio. however.98 114.0 3.0 0. In the single reactor analysis it is shown that there is no monotone dependence of duty with temperature.5 3.0 0 0. Therefore.0 2.0 10 H2O/CH4 Constant CO2 115.mol CH4 3.0 1.035) 2.5 0. Another option to consider is the separation and recycling of CO2 at each step of reaction.6 Kg.5 :1 A1 3 0.7 3.000 (54.4%).0 A 1.8 0.99 Constant Yield 1.

conversion. This is done just to assess the differences. the system converges to a solution using only one reactor. one reactor with fixed temperature. the use of CO2 recycle increases the duty at higher levels and also involves the cost of separation and compression. the use of Terrell gas in series reactors configuration is not worthwhile because of the higher duty required when compared to single reactor operation. When comparing with data for single reactor (Table 12) one can realize that higher duty is required for this case (an additional 2.25. Reactor 2= 2.0 • Variables: Temperature reactor 1 (593-927°C) Temperature reactor 2 (760-927°C) Flowrate of water to reactor 1 and 2 When there is no specification for the syngas ratio at the outlet of reactor 1.(Simulation Sciences) have to be performed to obtain the values of temperatures and corresponding duties. 44 . and CO2 content at the outlet stream. conversions. Optimal conditions for two reactors in series Case a is now optimized varying the temperature of both reactors.95% • Specifications: H2/CO ratio Reactor 1= 1.95% 2. Therefore a syngas ratio specification for reactor 1 was introduced to force the system to choose one non-optimal alternative.84 3.63 0. % CH4 Kg-mol CH4 Kg-mol CH4 Kg-mol CH4 2/1 701 850 99.999 58. Table 13: Series reactors at two temperatures-Terrell gases Terrell gas.8%.222 Therefore. yield. and total flowrate of water are almost the same when comparing to single reactor performance.134 KJ/Kg-mol CH4). which represents an increase of 3. The Syngas yield. variables and constraints have been set up in the simulator: • Objective Function: Minimization of the total duty (KJ/Kg-mol CH4) • Constraint: Total methane conversion = 99. The following objective function. X CH4 H2O Kg-mol CO2 Kg-mol KJ Ratio °C °C Total. In addition the effect of recycling CO2 needs to be analyzed. Table 13 shows the results for Terrell gas. Temp. In addition. Rx1 Rx2 CO2 out Syngas Duty H2/CO Temp.

0 0. Since a high conversion is set as constraint.0 %). California gas without CO2 addition is not an option to be considered to produce Syngas with a ratio lower than 3/1. X CH4 H2O Kg-mol CO2 Kg-mol Ratio °C °C Total.79 0.01 0. Rx 1 Rx 2 CO2 out Syngas Duty H2/CO Temp.029 0 0. Table 15: Simulation results for series reactors – California gas CALIFORNIA NATURAL GAS – no CO2 addition to the feed CO2 out Syngas H2/CO Rx 1 temp. However. 45 . in this case the amount of water used is considerably lower when comparing to the single reactor configuration. it is possible to produce the syngas ratio of 2/1 but the yield of Syngas as well as the conversion are too low. The same values for the temperature range in reactor 1 were chosen. We now turn to the case of processing California gas without any addition of CO2 to the feed (using case b).001 3/1 650 760-816 86.84 3. Clearly. % CH4 Kg-mol CH4 Kg-mol CH4 Kg-mol CH4 2/1 747 899 99.93 0. in addition the temperature range in reactor 2 is allowed to vary between 760°C to 930°C. % CH4 Kg-mol CH4 Kg-mol CH4 1/1 650 816 1. The duty is still higher (an additional 1665. The results of the simulation studies when there is no addition of CO2 to the feed are shown in Table 15.4 KJ/Kg-mol CH4. As it was confirmed using the equilibrium chart. Temp.5 0. Table 14: Series Reactors with CO2 removal – Terrell gas case b Terrell Gas. CO2 removal after first reactor.026-0.753 The CO2 recycling option is not analyzed in the simulator since it is already known that an increase in recycle increases the duty and the water required to reach the fixed Syngas H2/CO ratios. X CH4 H2O Kg-mol CO2 Kg-mol KJ Ratio °C °C Total.999 57. Rx 2 temp. and. both conversion and Syngas yield are at its maximum value. or 3.03 When comparing these results with a single reactor configuration for California gas shown in Table 7 it is seen that there is no advantage in this alternative scheme.95% 1.00 2/1 650 760-816 2.9 0 0 0. Results for the optimization of case b are shown in Table 14 (also using Terrell gas as feedstock).73-0.

% Kg-mol CH4 Kg-mol CH4 Kg-mol CH4 2/1 809 927 99.983 Conclusions for two reactors in series • Using Terrell gas the series reactors scheme has no advantage over the single reactor configuration because the duties obtained with series reactors are in all cases higher. constraints and variables are as follows: Objective Function: Minimizing Cost Constraint: Methane conversion: 99. Table 16: Simulation results for series reactors: California gas with CO2 addition California gas and addition of CO2 = 0. When minimizing the duty.999 55. The amount of CO2 at the outlet stream also increases. For this case the objective function. However. at the same time the usage of water in both reactors. and.0 to 3. With the addition of CO2 and H2O in the feed. the maximum yield obtained is close to the stoichiometric value of 4.95% Specifications: H2/CO reactor 1: 1.25/1 H2/CO reactor 2: 2/1 Variables: Temperature reactor 1: 593°C-927°C Temperature reactor 2: 593°C-927°C Water to reactor 1 Water to reactor 2 CO2 to reactor 1 The cost is based on duty and water usage.6 CO2/CH4 Rx 1 Rx 2 H2O CO2 out Syngas Duty H2/CO Temp. the duty is still high in the order of 3.5 %. However.28 3. • The alternative of recycling CO2 when using Terrell gas as feed. 46 .0 moles Syngas/lb-mol CH4. X CH4 CH4 Kg-mol CO2 Kg-Mol KJ Ratio °C °C Total. methane conversion as well as the Syngas yield increase for a fixed H2/CO ratio.95% 1.49 0. which can be obtained using just a single reactor. Temp. The results of using case c for California gas are shown in Table 16. is not a good option for any configuration because the duty and the water requirements increases with increasing recycle. the system gives a solution with lower steam consumption.

Therefore water addition is needed to move the feed composition to point B1. The duty also follows the lever rule and is equal to 54. while keeping at a minimum the amount of water added and the CO2 flowrate at the outlet stream. (Mixtures follow the lever rule). For producing lower Syngas ratios. Water is separated from the outlet streams. Now the point M represents mixture of A and B1 reactors. it needs CO2 addition. In Figure 33. No configuration of reactors in series is advantageous. over the line joining B and A. Point B is obtained by adding CO2 to the feed and performing dry reforming. Both extreme feedstock are evaluated using this arrangement. a methane conversion of 99. which are mixed to form the final outlet Syngas stream. It is important to point out that the operation of point B is inside the region favorable for carbon formation. CO2 recycling from the CO2 reforming reactor has also been explored. one under steam reforming conditions and the other under CO2 reforming conditions. Both reactors operate using California gas feedstock.556 KJ/Kg-mol CH4. The goal is to find the best set of operating conditions (maximum yield and methane conversion) under which CO2 reforming of CH4 is a good production scheme for several fixed H2/CO ratios. and a CO2 content in the outlet stream of 0.19 Kg-mol CO2/Kg-mol CH4 is obtained. this alternative can be used effectively. 47 . Only when the cost of external CO2 is zero or very low.6 %. Analysis of Parallel Reactors using the equilibrium chart Consider a parallel arrangement of reactors. • California gas is better suited for hydrogen processing through the Steam reforming process. Any mixture of both reactors is located at point M.994 Kg-mol /Kg-mol CH4. and the other working only under CO2 reforming conditions (B). a Syngas yield of 3. two options have been represented: the first consists of a reactor working under steam reforming (A).

2 0.8 6 3. the operation of the CO2 reforming reactor falls inside of the carbon formation region (Point A).5 B1 H 2 :C O 1:1 2 0.000 (52.5 1 2.5 :1 0. Mixtures of B and C follow the lever rule.5 3. the point should be moved to point C.0 CO2/CH4 5.5 2.078) 3.75 1.0 B 1.95 H 2 :C O 3 :1 1.4 5 2 M H 2 :C O 2 :1 4 C H 2 :C O 1.98 7 3.5 0.5 3.999 2.5 1. Point B corresponds to steam reforming operation.0 8 3.7 110.035) 9 Constant Yield mole Syngas/mole CH4 3.556) 2.0 O/C ratio Figure 33: Parallel reactors California gas When processing Terrell gas (Figure 34).5 :1 3 0.0 113.000 (55. with addition of water.000 (54.642) 3 114.000 (54. 3.5 115.0 0. 48 .0 2.0 10 Constant Duty.0 1.99 A 1. BTU/mole CH4 H2O/CH4 (KJ/Kmol CH4) 2. Therefore.0 3.0 0 0.5 H/C ratio H 2 :C O 2 .

5 2.0 0.642) 3 B 2.0 0 0.0 CO2/CH4 3.078) 6 0.7 3.5 C H 2 :C O 1:1 2 0.0 1.556) 3.5 1.2 M 0.5 H2O/CH4 115.0 10 Constant Duty.0 2.5 H/C ratio 0. variables and constraints: 49 .0 H 2 :C O 3 :1 114.5 3.000 (52.0 5.0 3.000 (54.75 1. Terrell gas Optimal conditions for parallel reactors configuration To accurately predict the behavior of parallel reactors a simulator is used with the following objective function. BTU/mole CH4 (KJ/Kg-mol CH4) 2.000 (54.98 7 3.5 :1 3 0.5 1 2.4 2 H 2 :C O 2 .5 3.035) 9 Constant Yield mole Syngas/mole CH4 2.5 :1 5 H 2 :C O 2 :1 4 H 2 :C O 1.0 O/C ratio Figure 34: Parallel reactors.99 8 1.95 1.999 3.5 110.000 (55.8 113. 3.0 A 1.

The first approach to perform the simulations is to work under same temperature conditions and fixing the flow of CH4 to the CO2 reforming reactor. Objective function: Minimize cost (duty + water usage) Constraints: H2/CO syngas ratio = 2/1 Total XCH4= 0.98. When the duty is minimized by varying reactor temperatures and by keeping the flowrate to each reactor fixed and adding water only to the second reactor. 0. the results shown in Table 17 are obtained.99.9995 Gas flow to both reactors = 45. or to both reactors. 50 .3 Kg-mol/hr (100 lb-mol/hr) Variables: Water to Reactor 1 Temperature of reactor 1 Temperature of reactor 2 Flowrate of gas to reactor 1 Flowrate of gas to reactor 2 Terrell gas processing For the parallel reactors case studies. 0. For this case point M represents the mixture corresponding to 95% of reactor 2 and 5% of reactor 1. This is necessary because otherwise. 0. OUT-STEAM-RX TERRELL-1 S3 INLET-RX1 WATER-RX1 E1 COOLER-1 M1 REACTOR-1 S9 SYNGAS S1 M3 OUT-CO2RX S13 TERRELL-2 S10 INLET-RX2 WATER-RX2 COOLER-2 E3 M2 REACTOR-2 S2 Figure 35: Parallel reactors optimization flowsheet – Pro II This simulation has been plotted on Figure 36.995. both gas feedstock have been evaluated using the flowsheet from Figure 35. the optimization chooses one reactor.

556) H 2 :C O 3 :1 1.643 56.5 1 2.5 110.0 Reactor 2 1.078) 6 3.538 59.8 57.0 1. the duty of the parallel reactors arrangement is always higher than the case of one reactor operation (for any combination of flows).99 per mole CH4 1.0 8 mole Syngas 3.642) H/C ratio H 2 :C O 2 .572 57.844 51 .5 3.5 9 (KJ/Kg-mol CH4) 3.000 (52.610 56.0/36.000 (55.999 Constant Yield 2.0 56.3/43.035) 2.5/40.5 3.5 2.0 3.4 5 Reactor 1 H 2 :C O 2 :1 4 M H 2 :C O 1.007 4.624 57. 10 3.95 114.75 1.8 0.0 O/C ratio Figure 36: Parallel reactors – Terrell gas For a fixed flowrate.605 59. Table 18 provides additional results.533 55.7 3.5 H 2 :C O 1:1 2 0. Table 17: Duties calculated for the different approaches of Parallel reactors Flow reactor 1/2 Fixed Water to Water to both Single reactor Kg-mol/hr reactor 1 only reactors configuration 2.000 (54.0 0.3 59.0 113.000 (54.5 1.5 :1 3 0.0 2.0 0 0.0 CO2/CH4 5.2 0.614 56.98 7 3.452 55.5 :1 0.944 9.0 Constant duty H2O/CH4 BTU / mole CH4 115.

17 0. kg-mol/hr 2. it has been shown.9965 0.288 H2/CO ratio 2. that the CO2 reforming reactor requires additional CO2 to increase the Syngas yield and make the process profitable. Both Reactors changing 59. Both reactors changing 56.536 9. kg-mol/hr 43. C 841 828 811 Reactor 2 temperature.9990 X CH4 Figure 37: Reactor duty as a function of methane conversion at fixed H2/CO ratios Table 18: Parallel reactor simulation data-Terrell gas Reactor 2.9970 0.9979 0.500 KJ/kg-mol CH4 Temp.500 and addition of water to Reactor 2 56.9987 0.999 3.77 2.9985 0.15 California gas processing When processing California gas with the parallel arrangement.072 Reactor 1. using the equilibrium chart.000 59.500 Temp.15 0.824 36. C 824 829 831 (H2O/CH4) reactor 2 ratio 0. Both Reactors Constant 58.91 3.9980 0.268 4.000 Temp.5/1 and below.999 (H2O/CH4) reactor 1 ratio 2.092 40.452 Total X CH4 0. kg-mol/kg-mol CH4 3.9975 0. The table clearly shows that California gas is not suitable for Syngas ratios in the range of 2.0 2.0 Duty.000 58. 52 .0 2.000 57. The results are shown in table 19. KJ/kg-mol CH4 56.999 3.9966 Yield.37 Reactor 1 temperature.533 59.500 minimizing duty 57. 60.610 57.000 0.

Acknowledgements This work was supported by the DoE/EPSCOR program of the Department of Energy (DE-FG02-99ER45759).8 760.3 760.0000 5. A previously developed equilibrium chart was expanded to include constant conversion and yield. The use of this chart proves to be useful to pick the right processing conditions.Parallel Reactors -No CO2 addition to the CO2 Reforming Reactor Flow to reactors.0 788. CO2 ref 1.0037 117.02 0. °C X CH4 H2O/CH4 CO2 outlet H2+CO Kg-mol/hr Ratio Reactor 1 Reactor 2 In feed Mole frac.0250 0.0 0. as well as constant duty and constant outlet CO2 lines.5 3/1 812.5 Conclusions for parallel reactors • The parallel scheme of processing the two feedstocks (Terrell and California gas) does not offer advantages over the single reactor configuration.3 0. Lower duty.6 0. The recycling option was not included in the simulations because the recycling increases the usage of steam and also the duty of the reactor.9 29.5/1 760.2 15.9 12. a thermodynamic analysis of the steam and dry reforming of methane is performed.70 0. Kg-mol/hr Steam Ref. H2/CO Temp.4 0. Table 19: California gas processing California gas . Single and multiple reactor configurations are investigated to conclude that single reactor configurations are the optimum.0 2/1 808. and the same level of yield are obtained using a single reactor for both cases.3 32.6460 0.0000 3. Conclusions In this paper.0081 0.01 0. 53 .1 45.

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