ConocoPhillips GTL Technology: The COPox Process as the SynGas Generator

H. A. Wright, J. D. Allison, D. S. Jack, G. H. Lewis; S. R. Landis Ponca City Technology Center, ConocoPhillips, PO Box 1267, Ponca City, OK 74602 Abstract This paper discusses the development of ConocoPhillips GTL technology specially the development of our proprietary COPox SynGas technology. This paper discusses what the COPox process is; how ConocoPhillips has developed the technology; and where ConocoPhillips is in the development of the technology. This paper will also discuss general syngas chemistry and where the COPox process fits into the spectrum of syngas technologies. A comparison with the leading SynGas technology shows that for an integrated GTL plant, COPox technology can improve the overall carbon efficiency of the GTL plant. Introduction ConocoPhillips has developed proprietary Gas-to-Liquids (GTL) technology to use to convert stranded natural gas to easily transportable fuels. This Gas-to-Liquids technology actually consists of at least three separate technologies that are integrated together to produce a highly efficient GTL process. 1. 2. 3. 4. ConocoPhillips has developed a syngas process, catalyst, and reactor system for syngas generation called the COPox process. ConocoPhillips has also developed a proprietary FischerTropsch catalyst and reactor. ConocoPhillips has also developed a proprietary Product Upgrading technology to convert the long chain hydrocarbons to useful fuel range materials. ConocoPhillips has integrated these processes to enable high carbon efficiency; which results in a lower gas consumption per barrel of product produced.

In 1998, we started the development of the COPox process after a process economics review indicated that it could result in a lower cost, more efficient GTL process than other available technologies. Since 1998, we have initiated a technology program for the COPox process as part of an overall GTL effort. Over 40 full time individuals work in the continuing development of COPox technology. This includes work in all areas of the technology commercialization including catalyst development, reactor process and mechanical design, reactor modeling including computational fluid dynamics; and process design engineering for scale up of our technology to the demonstration scale. Another 60 individuals work in the operations and maintenance of our new 400 BPD Demonstration Plant. We currently have reactors of many different sizes in operation in Ponca City, OK. We learned early on in the development of the COPox technology, that most experiments needed to be done in high-pressure pilot reactors instead of the quartz atmospheric reactors often used in academia. We have two demonstration scale reactors that will be started up this summer that are each capable of processing enough natural gas to produce 400 BPD of liquid product out the back end of the plant. Table 1 shows the number and type of COPox reactors in operation in Ponca City. Table 1. COPox High Pressure Reactors in Operation in Ponca City Reactor Type Number FT Liquid Production Demonstration Scale 2 400 BPD Pilot Scale 2 >2 BPD Catalyst Testing 12 0.2 0.5 BPD Scale SynGas Chemistry In addition to the partial oxidation reaction already mentioned, there are several other reactions that need to be accounted for in understanding the various means for syngas generation. The first is the steam methane reforming reaction CH4+ H2O 3H2 + CO. The next is full combustion: CH4 +2 O2 2 H2O + CO2. The last key reaction is the water gas shift reaction CO + H2O CO2 + H2 The combination of these reactions can aid in our understanding of why ConocoPhillips COPox technology can result in a very highly efficient GTL process. Each of the other syngas technologies use these reactions and approach thermodynamic equilibrium. Lets compare several possible syngas generators to COPox process for GTL plants. 1. 2. 3. 4. Steam Methane Reformer (SMR) Autothermal Reformer (ATR) COPox Process Non-Catalytic POX reactor (POX)

What is the COPox Process This paper concentrates on the COPox technology at ConocoPhillips. The COPox process is a synthesis gas generation technology. It is based on the catalytic partial oxidation of natural gas: CH4 + O2 2 H2 + CO This reaction is exothermic and with preheat can be run autothermally so that no additional external heat source is needed to aid in the generation of synthesis gas. We have found that successful catalytic partial oxidation should be operated with millisecond contact times with Gas Hourly Space Velocities around 500,000 hr-1 . The high space velocity of the COPox process relative to other systems means that the reactor volumes are considerably smaller leading to lower reactor and catalyst costs. We started the development of ConocoPhillips GTL technology in 1997. We initially started working on Fischer Tropsch technology but quickly realized that if we were to get a breakthrough in this overall area we would have to tackle the syngas generation costs as well. Some studies were showing that upwards of 60% of the cost of a GTL plant could be in the syngas and related areas of the plant.[1] It was clear, that even a breakthrough in Fischer Tropsch would not make GTL economically viable without more.

An important understanding of a natural gas feed, Cobalt FT catalyst based GTL Process is that H2 is consumed with CO in an overall ratio of 2.0 to 2.2. The closer this ratio is achieved in the syngas manufacturing step coupled with maximizing CO production, the more efficient the GTL Process will be. There are several competitor syngas technologies used in a GTL process. Some potentially use a SMR to generate syngas. This uses the steam methane reforming reaction to make syngas with a H2/CO ratio of about 3. An ATR makes syngas from the combustion, reforming, and water gas shift reaction. Oxygen is fed to the reactor so that the

Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2003, 48(2), 791

system is autothermal. The H2/CO ratio of the syngas is dependent upon the steam to carbon ratio. Typically the steam to carbon ratio ranges from 0.6 to 1.0 or even more. This S/C ratio results in a syngas with a H2/CO ratio of 2.3 2.5 or so. As the amount of steam declines the H2/CO ratio of the product syngas moves closer to the desired 2.0. The COPox process will result in a syngas slightly below 2.0 in practice. The higher-pressure operation reduces the ratio from the ideal H2/CO ratio of 2 [2]. A non-catalytic POX reactor will result in a syngas H2/CO ratio in the 1.7-1.8 range. Figure 1 shows the H2/CO ratios of syngas produced by these various means.
3.2 H2/CO Ratio of Syngas 3 2.8 2.6 2.4 2.2 2 1.8 1.6 SMR ATR COPox POX

Conclusions In conclusion, the COPox process provides the means to have a high efficiency and lower cost GTL facility. ConocoPhillips has spent the last 5 years developing the technology through the demonstration scale. The Demonstration Plant is in the commissioning stage and includes 2 reactors capable of producing syngas for a 400 BPD Fischer Tropsch plant. References:
(1) (2) Choi, G.; Kramer, S.; Tam, S.; and Fox, J; Prepr. Pap. - Am. Chem. Soc., Div. Fuel Chem., 1997, 42 (2), 667-671. Allison, J. D.; Swinney L. D.; Niu, T; Ricketson, K; Wang, D; Ramani, S.; Straguzzi, G. I.; Minahan, D. M.; Wright, H. A.; Hu, B.; U.S. Patent Application 20020115730; 2002.

Figure 1. The Hydrogen to CO ratio of the syngas from various syngas generators determines the ultimate efficiency of the GTL process. Clearly the farther from the Fischer Tropsch ideal ratio slightly greater than 2, then the more inefficient the overall GTL process probably is. Another way to look at syngas generators is to look at the CO yield of the various means of producing syngas. If you pay for carbon from some natural gas source, it is clear that you want as much of it as possible to end up as CO not carbon dioxide. Figure 2 shows the single pass CO yield of the COPox process versus an ATR with a S/C (steam to carbon) ratio of 1.0 and 1.5 (assuming no CO2 or heavy hydrocarbon recycling). You can now see why there will be a continuing drive to lower the steam to carbon ratios in ATRs even further.
95 90 85 80 75 70 65 60 55 50 ATR S/C = 1.5 ATR S/C = 1.0 CoPOX

Figure 2. Carbon Monoxide yields for several ATR cases versus a COPox process. Assumes no recycle.

Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2003, 48(2), 792