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Researchers propose CO2 recycling to improve Fischer-Tropsch GTL efficiency and reduce total CO2 emissions

21 June 2014

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Overview of the CUGP processes. Credit: ACS, Zhang et al. Click to enlarge.

Researchers in South Korea are suggesting two new carbon-dioxide-utilized Gas-to-Liquids processes (CUGP) to increase the overall efficiency of conventional Fischer-Tropsch GTL. In a paper in the ACS journal Environmental Science & Technology, they report that the two CUGP options increase carbon efficiency by 21.1−41.3% and thermal efficiency by 15.7−40.7%, with total CO2 emissions reduced by 82.0−88.4%, compared to different conventional F-T processes.

This results in a decrease in total CO2 emissions to less than 5g CO2/MJ F-T product, compared to a range of 27.0 to 36.2g CO2/MJ F-T product for the conventional processes.

Thanks to the improved exploring, boring, and retrieving skills, the extremely abundant nontraditional natural gas resources such as shale gas and coal-bed methane are recently being discovered and utilized. This abundance in natural gas makes the energy paradigm promptly shift from petroleum to natural gas in some regions including US and China, and the shift will be worldwide. At this moment, it is very important to render the GTL technology more efficient because we do not need to disturb ourselves to change the energy-related infrastructure and the transportation vehicles already fitted to petroleum if we can effectively convert natural gas to the clean liquid fuels and useful basic chemicals.

—Zhang et al.

Broadly, GTL processing using natural gas as feedstock entails three stages: reforming of methane to produce syngas (a mixture of H2 and CO); conversion of the syngas using F-T synthesis to produce a broad range of hydrocarbons; and upgrading of the F-T products to naphtha, diesel, liquefied petroleum gas, etc., through catalytic hydrocracking.

Typically, iron (Fe) or cobalt (Co) catalysts are used in the F-T reactors. Although Co-based catalysts have higher activity and selectivity to long chain hydrocarbons compared to Fe-based catalysts, Fe-based catalysts are much less expensive than Co-based catalysts and active for the reverse water gas shift (RWGS) reaction. Thus, note the researchers, Fe-based F−T synthesis catalysts are beneficial for CO2 conversion.

Unfortunately, in conventional low temperature F−T process using Fe-based catalysts, the optimum H2/CO molar ratio is around 1.7. In this case, about 30% CO is converted to CO2 due to WGS reaction. Consequently, carbon loss resulting from CO2 formation cannot be avoided and large amounts of CO2 are emitted back from the process. If syngas with high concentration of CO2 is provided in the F−T synthesis unit using Fe-based catalyst, then not CO2 formation, but CO2 consumption can occur…

Therefore, on the basis of our previous work based on Co catalysts for F−T synthesis, we are now suggesting two new processes using Fe-based F−T catalysts, which can convert CO2 to CO by not only dry reforming but also RWGS. It was found that increased process efficiency and significantly reduced CO2 emission could be realized by recycling some unreacted syngas to reforming and F−T synthesis units.

—Zhang et al.

The team developed two process models for CUGP mainly producing light olefins and Fischer–Tropsch (F–T) synthetic oils with Aspen Plus software. Both models are mainly composed of a reforming unit, an F–T synthesis unit and a recycle unit;the main difference is the feeding point of fresh CO2.

  • In option 1, fresh CO2 is fed to the reforming unit combined with natural gas and steam to produce CO by CO2/steam-mixed reforming first and then to the F−T synthesis unit to produce targeted hydrocarbons through RWGS and F−T synthesis reactions;

  • For option 2, fresh CO2 is directly fed to the F−T synthesis unit to produce targeted hydrocarbons through RWGS and F−T synthesis reactions without entering into the reforming unit.

After F–T synthesis, the unreacted syngas is recycled to F–T synthesis and reforming units to enhance process efficiency. From the simulation results, the researchers found that the carbon efficiencies of both CUGP options successfully improved, and total CO2 emissions were significantly reduced, compared with the conventional GTL processes.

While both CUGP options performed well, Option 2 delivered better results reducing total CO2 emissions to 4.03g CO2/MJ F-T product, with carbon efficiency of 86.9% and thermal efficiency of 69.5%.

Process efficiency was sensitive to recycle ratio; more recycle seemed to be beneficial for improving process efficiency and reducing CO2 emissions.

Resources

  • Chundong Zhang, Ki-Won Jun, Kyoung-Su Ha, Yun-Jo Lee, and Seok Chang Kang (2014) “Efficient Utilization of Greenhouse Gases in a Gas-to-Liquids Process Combined with CO2/Steam-Mixed Reforming and Fe-Based Fischer–Tropsch Synthesis,” Environmental Science & Technology doi: 10.1021/es501021u

June 21, 2014 in Carbon Capture and Conversion (CCC), Emissions, Fuels, Gas-to-Liquids (GTL), Lifecycle analysis, Natural Gas | Permalink | Comments (7) | TrackBack (0)

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Comments

carbon efficiency of 86.9% and thermal efficiency of 69.5%.

F/T may be the way to go for large volumes where you want other products, but if you want moderate volumes of synthetic fuels I would go with the Methanol To Gasoline process. Mobil showed in the 1980s you could turn natural gas into gasoline, diesel or jet fuel without F/T.

70% thermal efficiency... hmmm...

I keep coming back to the use of SOFCs as thermal fuel reformers.  If you can turn the entropy increase in the reforming process into electricity, the overall efficiency could be considerably higher.

Sounds good - turning methane into gasoline or diesel would be very useful.

better start to build some of theses ASAP, presumably starting with a smaller model.

My understanding is that these (GTL) tend to be huge undertakings, so scale is important.

Here F/T

Pushed the wrong button...here F/T is almost 70%, MTG using waste heat might be 70% with a smaller capital investment, that would allow fuel making closer to the point of use.

We have several ways of making coal, natural gas and biomass into fuels for transportation, it is a matter of capital. After 100 years of Standard Oil becoming Exxon and Chevron, they have a HUGE head start and a reason to protect their positions.

This is very congruent with a process known as direct chemical looping, which by now has probably advanced most with iron based catalysts. The oxidation of methane or coal is accomplished via an oxygen holding catalyst. Entropy is so low but emitted heat is so high that CO2 or H2O are rebroken into their constituents. The concentration of CO2 eventually can be very high and of great purity, which allows better reaction management of a controlled reactant. You get the proportions of CO, H2O and CO2 you want.

Yes you can utilize methanol for gasoline synthesis, but there is the intermediate step of creating dimethyl ether, and then utilize the DME down to allow polymerization. That makes for some elaborate reaction kinetics and high catalytic demands. If you could just stick an oxygen onto a methane (proposed at MIT via bromine), well, that would be better.

TOTAL, Haldor and others have a process that goes from synthesis gas to DME at 70% to gasoline at about 65%. Using waste heat from a power plant would bring the efficiency up, considering what it takes to turn tar sands into gasoline, that could be a bargain.

I favor the synthesis gas to DME to gasoline process because it does not take billions of dollars in capital expense like F/T. You can start with natural gas and work in more coal and biomass as time goes on, producing fuel closer to the city centers where lots of it is used.

It is not meant to be a complete replacement, but blended with refined product. E10 reduced the amount of imported oil, now make E10 with cellulose and 10% synthetic with another 10% bio synthetic over time. That coupled with vehicle efficiency like hybrids and we might be able to eliminate OPEC oil imports.

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