http://www.anl.gov/PCS/acsfuel/preprint%20archive/Files/47_1_Orlando_03-02_0025.pdf
This will be a very lengthy dispatch, with one link above, and two links and three excerpts following; and, two documents attached.
They all concern Penn State University, and the Tri-reforming Process, as described by Dr. Chunsan Song, wherein Carbon Dioxide is reacted with Methane to synthesize organic compounds which can be used, variously, as liquid fuels, or, as the raw materials from which liquid fuels and various plastics, or other organic chemicals of industrial and commercial value, can be manufactured.
We have made earlier reports of Penn State's work in Tri-reforming technology, and have referred to it often in other of our reports about the Carbon Dioxide scam that's being perpetrated on the Coal industry and on all the people resident in US Coal Country. So, some of what we present herein will be redundant relative to information we've already presented; but, hopefully not tediously repetitive.
We felt compelled to make presentation in this fashion since we continue to receive occasional skeptical comment about the true potentials, not just for Coal Liquefaction, but, for the profitable employment of Coal's most misunderstood by-product, Carbon Dioxide.
As a foreword, we remind you that Methane, which is required in the technology explained in this collection of reports for the recycling of Carbon Dioxide, can, itself, as we have many times documented, be synthesized from Carbon Dioxide, via Nobel-winning Sabatier processing as is now being now employed by NASA; or, from Coal, via long-established gasification technologies.
And, note frequent mention of the fact that the processes detailed in these reports are intended to lead to Fischer-Tropsch and Methanol syntheses, wherein liquid fuels are produced.
In any case, from the first link, above, we have:
"Catalytic Tri-reforming of Methane Using Flue Gas from Fossil Fuel-based Power Plants
Wei Pan, Jian Zheng, Chunshan Song
Clean Fuels and Catalysis Program, Energy Institute and Department of Energy & Geo-Environmental Engineering
The Pennsylvania State University, University Park, PA 16802
Introduction
The present work is an exploratory study on a new process for the production of synthesis gas (CO + H2) using CO2 in flue gas from fossil fuel-based electric power plants. The existing processes for synthesis gas production from methane or natural gas include steam reforming, CO2 reforming, auto-thermal reforming, and partial oxidation, of methane or natural gas. The new process is called tri-reforming of methane, referring to simultaneous oxy-CO2-steam reforming.
Tri-reforming is a new process designed for the direct production of synthesis gas with desirable H2/CO ratios by reforming methane or natural gas using flue gas from fossil fuel-based electric power plants without pre-separation of CO2. These flue gases are regarded as major source of CO2 emission in the U.S. Generally the compositions of flue gases depend on the types of fossil fuels used in power plants. Flue gases from natural gas-fired power plants typically contain 8-10% CO2, 18-20% H2O, 2-3% O2, and 67-72% N2; flue gases from coal-fired boilers primarily contain 12-14% CO2, 8-10% H2O, 3-5% O2, 72-77% N2, and trace amount of NOx, SOx, and particulates ... .
(Note, as we have earlier documented: Tri-reforming of CO2 can be accomplished "using flue gas from fossil fuel-based electric power plants without pre-separation of CO2", thus sparing the expense of collecting and concentrating the CO2.)
It is hypothesized that tri-reforming be a synergetic combination of CO2 reforming, steam reforming, and methane oxidation reactions. Therefore, tri-reforming is expected to encompass a number of unique features. One major feature is its ability to convert CO2 in flue gas without CO2 separation while avoiding the use of pure CO2 and the severe problem of carbon deposition encountered in CO2 reforming system. Currently most of pure CO2 is obtained from CO2 separation processes (e.g. absorption, adsorption, and membrane separation) that are often energy-intensive and costly. Some separation processes could lower the power plant energy output as much as 20%.
(According to other of our research and reports, "carbon deposition" is a problem often noted in other CO2 recycling/reuse technologies. This technique avoids that phenomenon.)
Other features of tri-reforming include that there is no need to handle pure oxygen and it directly produces synthesis gas with a desirable H2/CO ratio (e.g. H2/CO = 1.5 ~ 2). Furthermore, oxygen in flue gas may help to ease the reaction energy requirement as encountered in CO2 reforming alone or steam reforming alone. In general, the new tri-reforming process concept is consistent with the goals of DOE Vision 21 for power plants with respect to decreasing greenhouse gas emission, improving power generation efficiency and co-producing fuels and chemicals.
Acknowledgement. The authors are grateful for the financial support from National Energy Technology Laboratory, US DOE (UCR Innovative Concepts Program, DE-FG2600NT40829)... ."
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So, the foregoing concludes with reference to yet another Coal-related, US tax-funded DOE study, that we bet no regular, tax-paying citizen resident in US Coal Country has ever heard anything about.
Regardless, Dr. Song continues his exposition on the inherent, publicly unrealized and, as yet, unfulfilled value of Carbon Dioxide in:
http://www.anl.gov/PCS/acsfuel/preprint%20archive/Files/45_4_WASHINGTON%20DC_08-00_0772.pdf
"Tri-reforming A New Process Concept for Effective Conversion and Utilization of CO2 in Flue Gas from Electric Power Plants
Chunshan Song
Applied Catalysis in Energy Laboratory, Pennsylvania State University, University Park, PA 16802
CO2 conversion and utilization are a critically important element in chemical research on sustainable development. The prevailing thinking for CO2 conversion and utilization begins with the use of pure CO2, which can be obtained by separation. In general, CO2 can be separated, recovered and purified from concentrated CO2 sources by two or more steps based on either absorption or adsorption or membrane separation. These separation and purification steps can produce pure CO2 from flue gases of power plants but add considerable cost to the CO2 conversion or sequestration system. Even the recovery of C02 from concentrated sources requires substantial energy input. According to US DOE, current CO2 separation processes alone require significant amount of energy which reduces a power plant's net electricity output by as much as 20%. While new technology developments could make this recovery easier to handle and more economical to operate in power plbnts, it is highly desirable to develop novel ways to use CO2 in flue gases without separation.
(So, if CO2 recovery, for sequestration, is going to be mandated, legally required, Tri-reforming raw flue gas automatically spares the loss of "a power plant's net electricity output by as much as 20%", as further detailed, following.)
... flue gases from fossil fuel-based electricity-generating units represent the major concentrated CO2 sources in the US. If CO2 is to be separated, as much as 100 megawatts of a typical 5W megawatt coal-fired power plant would be necessary for today's CO2 capture processes based on the alkanolamines. Therefore, it would be highly desirable if the flue gas mixture can be used for CO, conversion but without pre-separation of CO2. Based on our research. there appears lo be a unique advantage of directly using flue gases, rather than pre-separated and purified CO2 ftom flue gases, for the proposed tri-reforming process.
In the proposed tri-reforming process, CO2 in the flue gas does not need to be separated. In fact. H2O and O2 along with CO2 in the waste flue gas from fossil-fuel-based power plants will be utilized for tri-reforming of natural gas for the production of synthesis gas.
(In other words, it is advantageous to use raw flue gas for Tri-reforming.)
PROPOSED TRI-REFORMING PROCESS
The tri-reforming refers to simultaneous oxy-C02-steam reforming of natural gas ... and ... is a synergetic combination of endothermic CO2 reforming and steam reforming and exothermic partial oxidation of methane.
(As we've elsewhere documented, a part of the Tri-reforming reaction is "exothermic", generating heat which might be recovered to help drive other segments of the process.)
The tri-reforming is an innovative approach to CO2 conversion using flue gases for syngas production. Coupling CO2 reforming and steam reforming can give syngas with desired (gas) ratios for methanol (MeOH) and Fischer-Tropsch (F-T) synthesis. Steam reforming is widely used in industry for making ... syngas... . When CO-. rich syngas for oxo synthesis and syngas with H2/CO ratio of 2 are needed for F-T synthesis and ... Steam reforming (of Methane alone - JtM) gives too high a H to CO ratio and thus (there is a) need to import CO2 for making synges with H/CO (of appropriate ratios).
(So, additional CO2 is actually needed.)
CO2 reforming (dry reforming) of CH4 has attracted considerable attention worldwide ... and the research up to 1998 has been reviewed ... . A simple estimate of energetics indicates that CO2 reforming is more endothermic than steam reforming ... and so it does cost more energy. However. it can be done and is indeed necessary for adjusting H2/CO ratio for making MeOH or F-T synthesis gas. There are two industrial processes that utilizes this reaction ... . CO2 reforming of methane suffers fiom a major problem of carbon formation, particularly at elevated pressures ... . When CO2 reforming is coupled to steam reforming, this problem can be effectively mitigated.
(Again, deposition of Carbon in CO2 reforming processes "can be effectively mitigated".)
The combination of dry reforming with steam reforming can accomplish two important missions: to produce syngas with desired H to CO ratios and to mitigate the carbon formation problem that is significant for dry reforming. Integrating steam reforming and partial oxidation with CO2 reforming could
dramatically minimize or eliminate carbon formation on reforming catalyst thus increase catalyst life and process efficiency. Therefore, the proposed tri-reforming can solve two important problems that are encountered in individual processing. The incorporation of O2 in the reaction generates heat in situ that can be used to increase energy efficiency and O2 also reduces or eliminates the carbon formation on the reforming catalyst. The tri-reforming can thus be achieved with natural gas and flue gas, using the ’waste heat’ in the power plant and the heat generated in situ from oxidation with the O2 that is already present in flue gas.
... the tri-reforming is the key step in the recently proposed CO2-based Tri-generation of fuels, chemicals, and electricity ... . In principle, once the syngas with desired H2/CO ratio is produced from tri-reforming, the syngas can be used to produce liquid fuels by established routes such as Fischer-Tropsch synthesis, and to manufacture industrial chemicals by methanol and oxo synthesis. Syngas can also be used for generating electricity either by IGCC type generators or by using fuel cells.
(There you have it: "liquid fuels", "industrial chemicals", and "electricity" - all from recycling CO2.)
The proposed tri-reforming concept is consistent, in general, with the goals of Vision 21 EnergyPlex concept ... being developed by the U.S. DOE. The goals of Vision 21EnergyPlex (plants) include greater efficiency of power generation (>60% with coal. >75% with natural gas), greater overall thermal efficiency (85-90%), near zero-emissions of traditional pollutants, reduction of greenhouse gas (40-50% reduction in CO2 emission), and coproduction of fuels.
The challenges and feasibility issues and related literature information have been discussed recently ... . Current flue gases contain inert N2 gas in high concentrations. and thus the conversion process design requires the considerations on how to dispose inert gas. It is possible that oxygen-enriched air or oxygen will be used in power plants in the future. If that becomes a reality, then the proposed tri-reforming process will be even more attractive because of much lower inert gas concentration and thus higher system efficiency.
... some recent laboratory studies ... have shown that the addition of oxygen to CO2 reforming ... or the addition of oxygen lo steam reforming of CH4 ... can have some beneficial effects in terms of improved energy efficiency or synergetic effects in processing and in mitigation of coking. ... the proposed tri-reforming of flue gas from power plants appears to be feasible and safe.
A new process concept, tri-reforming. is proposed for effective conversion and utilization of CO2 in the waste flue gases from fossil fuel-based power plants ... . The CO2,. H2O and O2 in the gas need not be pre-separated because they will be used as co-reactants for the tri-reforming of natural gas. ... the flue gas and natural gas are used as chemical feedstock for production of synthesis gas ... .
The tri-reforming process solves some of the major problems in CO2 reforming, in steam reforming, and in partial oxidation. It also makes use of the waste heat in the power plant and heat generated in situ from oxidation with the O2 that is already present in flue gas. This tri-reforming process could be applied, in principle, for natural gas-based or coal-based power plants and IGCC power plants.
Another important feature of the proposed tri-reforming is that this is the first innovative approach to conversion and utilization of CO2 in flue gases from power plants without CO2 separation."
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Again, it was repeated: "utilization of CO2 in flue gases from power plants without CO2 separation." It is an important point.
Finally, we submit, following, yet another explication of the Tri-reforming process, as in:
Tri-reforming of methane: a novel concept for catalytic production of industrially useful synthesis gas with desired H2/CO ra.
"Title: Tri-reforming of methane: a novel concept for catalytic production of industrially useful synthesis gas with desired H2/CO ratios
Authors: Chunsan Song; Wei Pan
Affiliations: Clean Fuels and Catalysis Program; Pennsylvania State University
Abstract: A novel process concept called tri-reforming of methane has been proposed in our laboratory using CO2 in the flue gases from fossil fuel-based power plants without CO2 separation... . The proposed tri-reforming process is a synergetic combination of CO2 reforming, steam reforming, and partial oxidation of methane in a single reactor for effective production of industrially useful synthesis gas (syngas). Both experimental testing and computational analysis show that tri-reforming can not only produce synthesis gas (CO + H2) with desired H2/CO ratios ... , but also could eliminate carbon formation which is usually a serious problem in the CO2 reforming of methane. These two advantages have been demonstrated by tri-reforming of CH4 in a fixed-bed flow reactor ... . Over 95% CH4 conversion and about 80% CO2 conversion can be achieved in tri-reforming over Ni catalysts supported on an oxide substrate. The type and nature of catalysts have a significant impact on CO2 conversion in the presence of H2O and O2 in tri-reforming ... Among all the catalysts tested for tri-reforming, their ability to enhance the conversion of CO2 follows the order of Ni/MgO > Ni/MgO/CeZrO > Ni/CeO2 Ni/ZrO2 Ni/Al2O3 > Ni/CeZrO. The higher CO2 conversion over Ni/MgO and Ni/MgO/CeZrO in tri-reforming may be related to the interaction of CO2 with MgO and more interface between Ni and MgO resulting from the formation of NiO/MgO solid solution. Results of catalytic performance tests over Ni/MgO/CeZrO catalysts at 850 C and 1 atm with different feed compositions confirm the predicted equilibrium conversions based on the thermodynamic analysis for tri-reforming of methane. Kinetics of tri-reforming were also examined.
Journal: Catalysis Today. Source: Symposium on Utilization of Greenhouse Gases, Anaheim, CA 2004"
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Well, there you have it. A technology exists which would enable us to efficiently transform the Carbon Dioxide byproduct of our Coal use into "fuels, chemicals, and electricity".
Methane is needed for the process, and it, too, can be manufactured from CO2, via the Sabatier process; or, from Coal, via well-known gasification techniques.
Sounds a lot better, doesn't it, than taxing our Coal-use industries out of existence through Cap & Trade shell games; or, forcing them, at gunpoint, as it were, to subsidize the petroleum industry through enforced Geologic Sequestration in fading oil fields to scrounge the dregs?
Through the technologies of Coal Liquefaction and Carbon Dioxide Recycling, we have all we need to establish domestic liquid fuel self-sufficiency and to improve the environment.