2a. Identification and Significance of the Problem, and Technical Approach
There are increased concerns by the natural gas industry over economically upgrading of natural gas containing high levels of contaminants, mostly CO2. This affects 17% of US reserves. The goal is to lower the CO2 content below 2%, a typical pipeline specification. CO2 removal from methane is also of concern where 1) CO2 flooding of oil wells is used for secondary recovery and 2) the upgrade of landfill gas from solid waste-disposal sites.
Presently, carbon dioxide is commercially separated from methane with a non-porous polymer membrane system using bundles of hollow cellulose acetate fibers. These bundles are placed in modules known as permeators. The permeator vessel is provided with an inlet and outlet for the mixed gases (the feed) and the outlets for the product or permeate stream. Gases permeate through the membrane by a solution-diffusion mechanism where the rate of CO2 permeation is much faster than methane Improvements in the economics and performance have been sought and much effort has been focussed on polyimide and polyamide polymeric membranes but commercialization has not occurred with these newer systems.
It is surprising that carbon has rarely been tried as a membrane material since large differences in the rate of adsorption and permeation between CO2 and methane occur with active carbon. Some of the difficulty in making hollow fibers of active carbon with sufficient strength to withstand the pressures of natural gas at the well-head. It is also difficult to fabricate a successful membrane from material in powder form. However some laboratory studies with membranes of carbon molecular sieves have indicated significantly higher permeabilities and selectivities of many of the common gases including CO2 compared with polymer membranes. In the case of carbon molecular sieve membranes, the mechanism for transport is one of adsorption and pore diffusion.
Mega-Carbon Company believes it has the capability to solve the present technical problem of making carbon membranes with the necessary properties for removing CO2 from natural gas and in an economic way. Mega-Carbon has much expertise in the making and molding active carbon systems with different carbons and with different porosities. These are the properties that are going to determine the selectivity and the permeability of any resulting membrane. In terms of different carbons Mega-Carbon approach will include identifying carbons with varied structure, particularly with combination of macropore (diameter > 1000A> feeder pores in combination with smaller mesopores (20A<diameter< 1000A) and modification of existing activated carbons via additional activation. The carbons will then be formulated in the same manner as Mega-Carbon has developed adsorbent carbon blocks to control gasoline vapor emissions with a major automotive company.
The basis of this technology are two patents that will be granted to Mega-Carbon in a few months on a novel bonding technology. This bonding process called Mega-Cast has been developed to bond carbon powders and adsorbent blocks. What makes Mega-Cast bonding unique is that very little of the adsorption capacity is lost due to pore plugging. The illustration of the bonded carbon in Figure is one way to view the process with the carbon particles bonded at various points by a polymer binder.
Carbon particles are shown darker and are bonded by the polymer droplets shown in the lighter shade. Every carbon is different and adjustments are always necessary in the formulation. Blocks can be cast routinely but extrusion is a special challenge and requires additives to impart desired rheological properties and stabilization of the slip.
To prepare a carbon adsorbent block, a carbon slip is first prepared with a polymer binder. There are two types of binders, one suitable for temperatures in the range of 200 C and the other a higher temperature version which retains its strength at temperatures as high as 350 C. The carbon slip can be prepared from either powder or granules and is then extruded, slip-cast, or compression molded to a variety of shapes( blocks, cubes, etc. ). The binder cures at modest temperatures, eliminating the need for high temperature calcination and most of the adsorption capacity is preserved. The use of compression during the forming process translates into higher bulk densities and will frequently lead to higher adsorption capacity per unit volume. Dynamic performance of the carbon blocks depends directly on how the block is formed, flow channels, and type/size of starting material. Most importantly, there are cases where the bonded carbon is noticeably better than a granular bed. Pressure drop of the carbon block depends on the form of the starting carbon and the incorporation of flow channels.
Mega-Carbon Company believes it has the capability to solve the present technical problem by successful application of this new approach for the following reasons:
Mega-Carbon plans to produce a high flux, high selectivity active carbon membrane. Active carbon has a high adsorption selectivity over methane and should make an excellent material for this separation. (See Figure 2 below).
Mega-Carbon plans to develop improved activated carbons which have a pore size distribution that will facilitate diffusion from the external surface to the inside of the carbon membrane.
Mega-Carbon will take advantage of previously investigations on the mass transport of gases across different active carbon blocks with and without channels. These studies were made in order to minimize pressure drop and maximize adsorption of gasoline vapors on carbon contained in automobile canisters
Mega-Carbon has made tubes of active carbon both supported and unsupported that can be used as membrane units for the investigation of the gaseous separation of methane and carbon dioxide.
In summary, Mega-Carbon has a unique mix of technologies and materials that will allow us to develop a commercial membrane of active carbon, a material ideally suited for the separation of carbon dioxide and methane. A solution to a problem affecting at least 17% of US natural gas supply.
2b. Anticipated Benefits
The successful completion of the Phase I program will mean that base technology is available for a carbon membrane system that can meet certain criteria. These criteria are the following:
A high flux rate of CO2. At least 0.1cc STP/cm3/min of CO2. This is an order of magnitude higher than that reported for polyamide membranes, the most investigated material studied for this purpose .We believe that this is not an unrealistic goal considering the reported values of permeabilities reported by Koresh and Sofer
A high selectivity of CO2 over methane of the order of 40.
Physical and mechanical properties that can withstand separation conditions over a long period. Our present intent is to concentrate on supporting the carbon membranes on ceramic or metal porous tubes. By usging a robust substrate, this should eliminate any problem in withstanding the high pressures of well-head natural gases, especially if the inlet gas is placed on the outside of the membrane tubes.
Geometric forms that can be economically fabricated for commercial operation, preferably tubular. Final configuration of a membrane separation module will only be decided upon on completion of Phase I, but other forms may be needed to maximize performance.
Phase II can then proceed to examine and construct a larger scale membrane unit to handle larger through puts of natural gas. To examine certain parameters not previously considered. These will include the presence of other contaminant gases such as H2S and N2.
In Phase II, Mega-Carbon expects that scaling problems will be identified for the eventual construction of a semi-commercial plant.
3. The Phase I Project
3a. Technical Objectives-Phase I
Phase I is critical in establishing the technical feasibility of fabricating a high flux, high selectivity membrane of active carbon with the desired physical properties. We will approach these problems by addressing the following questions:
Can the high adsorption uptake and high adsorption rate of CO2 relative to methane be utilized as a membrane separation medium?
What are the characteristics of the active carbon needed to maximize this separation and maintain a high selectivity?
How can a solid continuous membrane be made out of active carbon that comes in a powder or granular form?
Can the resulting form withstand the conditions of separation?
The following objectives for Phase I will address the questions listed above:
Select best active carbon for separation of CO2 and methane
Fabricate carbon membrane
Construct a membrane separation unit and test different candidate carbons for maximum performance
Correlate carbon properties to performance
Use Mega-Carbons' bonding technique to cast or extrude tubes of the appropriate dimensions (wall thickness etc)
Conduct long duration tests at the maximum conditions for separation
3b. Phase I Work Plan
Research Approach and Work to Be Performed
The work to be performed consists of the following tasks and subtasks:
Task 1. Fabrication of an active carbon membrane
Subtask 1.1 Characterize the Carbons. Identify best carbons that give the highest ratio of CO2 to methane adsorption uptakes. A number of active carbons, both commercial and developmental, will be studied as potential sorbents for membranes. It is our intention to obtain their surface area and pore size distribution via BET nitrogen sorption. Furthermore, we will extend the adsorption studies using CO2 and methane as adsorbates Some of the samples that we plan to analyze include those shown in the Table. Depending on results mixtures will also be tested.
Carbon Samples for Surface Analysis
|Sample||BET area||Pore distribution||CH4 and CO2 Adsorption|
Most of these analyses will be subcontracted to Argonne National Laboratory, since they have extensive analytical capabilities.
Subtask 1.2 Formulate a workable carbon slip. A carbon slip (stable slurry of binder, additives and the chosen carbon) to cast or extrude suitable membrane tubes. Alternatively dipping process may be used to coat a carbon thin film on a porous ceramic tubular base as a support. The carbon slip needs the right rheological properties either to coat the porous support or to be cast in tubular form. Our experience with rheological aids will aid our selection.
Subtask 1.3 Fabricate Membrane. Determine the best fabrication process ( slip casting, compression casting, extrusion etc ) Our first priority will be to concentrate on active carbon coating of porous supports. Adequate adhesion of the carbon to the support will be of main consideration. A schematic is shown for carbon membrane in a typical processing scheme.
Task 2. Construction of a separation unit housing the membrane tube
Subtask 2.1 Produce Seals. Find suitable seals between carbon membrane tube and the inlet and outlet lines. This not an insignificant task as many membrane systems have failed on this issue. Our knowledge of polymeric glues for carbon should be of assistance here.
Subtask 2.2 Construct Module. Design and construct the desired gas flow system for both shell and tube sides of the membrane. A typical schematic is shown below of membrane module that will be constructed. This design minimizes the seal problem.
Subtask 2.3 Set-up Analyzers. Set-up gas chromatographic analyzers for measuring shell and tube exit gas flows Analysis of gases are an essential item and proper calibration will be needed.
Task 3. Evaluation of the membrane tubes for separation performance
Subtask 3.1 Study Parameters.
The process parameters of temperature, pressure, flow rate, composition of the gases will be examined. Parameters of the membrane will include, besides those previously discussed, thickness, length of the membrane and external surface area.
Subtask 3.2 Data Analysis
Evaluation of membranes will be made on the basis of two main parameters namely, flux and selectivity. The product of the two parameters will produce a hypothetical yield that can be a single value for rating and comparing each membrane
Task 4. Final Report Preparation
A final report will be prepared summarizing and analyzing the data for the carbon forming and natural gas adsorption tests. We plan to keep the analysis and monthly reporting very current so that this task will not involve excessive time.
3b. Phase I Performance Schedule
Task 1 to be completed 2 ½ months after start of work.
Task 2 to be completed 4 ½ months after start of work.
Task 3 to be completed 5 ½ months after start of work.
Task 4 to be completed six months after start of work.
1 2 3 4 5 6
Task 1:Fabrication of Carbon membrane
Subtask 1.1 Charactize Carbons >
Subtask 1.2 Formulate Carbon Slip >
Subtask 1.3 Process Fabrication >
Task 2: Module Construction
Subtask 2.1Produce seals >
Subtask 2.2 Construct module >
Subtask 2.3 Set-up Analyzers >
Task 3: Membrane Evaluation
Subtask 3.1 Study parameters >
Subtask 3.2 Analyze Data >
Task 4: Final Report Preparation >
3c. Related Research and Development
To the best of our knowledge no work is being conduted in this novel area. The pertinent refences have already been discussed in section 2a.
3d. Principal Investigator and other Key Personnel
Dr. Rodney L. Mieville (Principal Investigator)
Ph.D. Physical Chemistry, 1964, University of Western Ontario, Canada, Thesis: Photo-Addition of Methyl Mercaptan to Olefins
ARIC Chemistry, 1953, Northern Polytechnic London University, England
1993 to present: Vice President of Mega-Carbon Company
1964-1992: Amoco Oil Research and Development
Associate Research Scientist
1954-1961 British Petroleum Research and Development
Worked on a variety of projects including combustion kinetics, oil additives and catalysis, petroleum processes, adsorption, and inorganic membranes. The catalytic work involved all aspects of catalysis including reaction kinetics, coke and poisoning deactivation, synthesis and characterization and assessment of adsorbent and catalytic materials.
Member of the ACS, RSC (Royal Society of Chemistry), NATAS (Thermal Society), and the Catalysis Society of North America. Chairman of Surface Acidity Task Group of D.32 Committee ASTM
10 Patents, 35 Publications
Some of the more recent publications:
1. R. L. Mieville "Measurement of Microporosity in the Presence of Mesopores," JOURNAL OF COLLOID & INTERFACE SCIENCE, Vol. 41, No. 2, November 1972.
2. R. L. Mieville "Measuring Acidity by Temperature-Programmed Desorption," JOURNAL OF CATALYSIS 74, 196-198 (1982).
3. R. L. Mieville "Studies on the Chemical State of Cu during Methanol Synthesis," JOURNAL OF CATALYSIS 90, 165-172 (1984).
4. R. L. Mieville "Platinum-Rhenium Interaction: A Temperature-Programmed Reduction Study," JOURNAL OF CATALYSIS 87, 437-442 (1984).
5. R. L. Mieville, "Coking Characteristics of Reforming Catalysts," JOURNAL OF CATALYSIS 100, 482-488 (1986).
6. R. L. Mieville, "The Chemical State of Copper during Methanol Synthesis," JOURNAL OF CATALYSIS 97, 284-286 (1986).
7. R. L. Mieville, "N2 Adsorption Method for Measuring Certain Acid-Base Sites on Alumina," JOURNAL OF CATALYSIS 105, 536-539 (1987).
8. R. L. Mieville and M. G. Reichmann, "Temperature-Programmed Desorption Study of CO on Pt-Reforming Catalysts," AMERICAN CHEMICAL SOCIETY (1989).
9. R. L. Mieville, "Coking Kinetics of Reforming," CATALYST DEACTIVATION (1991).
10. B. L. Meyers, R. S. Kurek, and R. L. Mieville, "Microchemisorrption," JOURNAL OF CATALYSIS, Volume 127, No. 2, (February 1991).
11. R. L. Mieville, presentation at the Symposium on Effect of Pore Size on Catalytic Behavior Presented before the Division of Petroleum Chemistry, Inc., American Chemical Society in Miami Beach on September 10-15, 1976, entitled "Temperature-Programmed Desorption Studies of Cracking Catalysts. Relationship with Microporosity and Activity."
12. R. L. Mieville, presentation at the Symposium on Zeolite and Shape Selective Catalysis Presented at the AIChE Annual Meeting in Houston on March 29-April 2, 1987, entitled "Interacrystalline Zeolite Diffusion."
13. R. L. Mieville, D. M. Trauth, and K. K. Robinson, presentation at the Symposium on Convection and Diffusion in Porous Catalysts at the AIChE Annual Meeting in San Francisco on November 5-10, 1989, entitled "Asphaltene Characterization and Diffusion Measurements."
14. U. Balachandran, J. J. Picciolo, J. T. Dusek, R. A. Russell, R. B. Poeppel (Argonne National Laboratory) and R. L. Mieville, presentation at the 1992 International Gas Research Conference (IGRC 92), Orlando, Florida on November 16-19, 1992, entitled "Fabrication of Ceramic Membrane Tubes for Direct Electrochemical Conversion of Natural Gas," July 1991.
15. P. S. Maiya, U. Balachandran, J. T. Dusek, R. L. Mieville, M. S. Kleefisch and C. D. Udovich.,"Oxygen Transport by Oxygen Potential Gradient in Dense Ceramic Membranes", Solid State Ionics, 99, 1, 1997.
16. R. L. Mieville et al., "Failure Mechanisms of Ceramic Membranes Reactors in Partial Oxidation of Methane to Synthesis Gas", Catalysis Letters 30, 201, 1995.
17. R. L. Mieville, et al., "Methane to Syngas via Ceramic Membranes", Am. Ceramic Bul.,74, 71 1995.
18. R. L. Mieville et al., "Dense Ceramic Membranes for Partial Oxidation of Methane to Syngas", Appl., Catalysis A. 133, 19, 1995.
1. R. L. Mieville, "Improvements in or Relating to the Production of Oxygenated Organic Compounds," US 882,863.
2. R. L. Mieville, "Middle Distillate Fuel Oil Compositions Having Improved Pumpability," US 3,807,975.
3. R. L. Mieville, "Middle Distillate Fuel Oil Compositions Having Improved Pumpability," US 3,807,990.
4. R. L. Mieville, "Catalyst for Selective Hydrocracking of Alkylbenzenes," US 4,171,290.
5. R. L. Mieville, "Reforming with a Catalyst Comprising Iridium, Zirconia, and Alumina," US 4,297,205.
6. R. L. Mieville, "Methods to be Used in Reforming Processes Employing Multi-Metallic Catalysts," US 4,048,058
7. R. L. Mieville, "Emmissions control System and Method", US 5660800
8. R. L. Mieville, "Emmissions control System and Method", US 5609832
9. R. L. Mieville, "Emmissions control System and Method", US 5303547
10. R. L. Mieville, "Membrane and use thereof in oxidative conversion", US 5276237
Dr. Ken Robinson
D.Sc. Ch.E. 1970, Washington University-St. Louis
M.S. Ch.E. 1964, University of Michigan
B.S. Ch.E. 1963, University of Michigan
4/93-present: Mega-Carbon Company, President
11/89 to 4/93: Amoco Corporation Manager, Technical University Relations
11/84-01/89: Amoco Oil Company, Research and Development Research Associate
01/80-11/84: Standard Oil (Indiana) Director, Coal Utilization
01/73-01/80: Amoco Oil Company, Research and Development Project Manager
1/65-1/73: Monsanto Company Senior Development Engineer
Member of AIChE, ACS, Chicago Catalysis Society
Professional Engineer in Illinois
5 Patents, 14 Publications
1. K. K. Robinson, and D. E. Briggs, "Isothermal Pressure Drop Across Banks of Finned Tubes," Heat Transfer-Los Angeles, Chemical Engineering Progress Symposium Series, Vol. 62, No. 64, 177 (1966).
2. K. K. Robinson, A. Hershman, F. E. Paulik, and J. F. Roth, "Catalytic Vapor Phase Hydroformylation of Propylene Over Supported Rhodium Complexes," JOURNAL OF CATALYSIS, Volume. 15, No. 3, 245 (1969).
3. A. Hershman, K. K. Robinson, J. H. Craddock, and J. F. Roth, "Continuous Propylene Hydroformylation in a Gas Sparged Reactor," INDUSTRIAL AND ENGINEERING CHEMISTRY, PRODUCT R&D, Vol. 8, No. 4, 372 (1969).
4. K. K. Robinson, and E. Weger, "High Temperature Pyrolysis of Propylene-Propane Mixtures," INDUSTRIAL AND ENGINEERING CHEMISTRY FUNDAMENTALS, Vol. 10, No. 2, 198 (1971).
5. K. K. Robinson, A. Hershman, J. H. Craddock, J. F. Roth, "Kinetics of the Catalytic Vapor Phase Carbonylation of Methanol to Acetic Acid," JOURNAL OF CATALYSIS, Vol. 27, No. 3, 389 (1972).
6. E. C. Meyers, and K. K. Robinson, "Multiphase Kinetic Studies with a Spinning Basket Reactor," ACS Symposium Series No. 65, Chemical Reaction Engineering 37 (1978).
7. J. A. Mahoney, K. K. Robinson, and E. C. Myers, "Catalyst Evaluation with the Gradientless Reactor," CHEMTECH, 758 (December 1978).
8. R. J. Bertolacini, L. C. Gutberlet, D. K. Kim and K. K. Robinson, "Catalyst Development for Coal Liquefaction," EPRI, AF-574 (1977).
9. R. J. Bertolacini, L. C. Gutberlet, D. K. Kim, and K. K. Robinson, "Catalyst Development for Coal Liquefaction," EPRI AF-1084 (1979).
10. D. K. Kim, R. J. Bertolacini, J. M. Forgac, R. J. Pellet, and K. K. Robinson, "Catalyst Development for Coal Liquefaction," EPRI AF-1233 (1979).
11. D. F. Tatterson, K. K. Robinson, T. L. Marker, and R. Guercio, "Coal Flash Pyrolysis in a Free-Jet Reactor," I&EC RESEARCH, 27 1606 (1988).
12. K. K. Robinson "Molecular Structure of Heavy Coal Liquids," EPRI ER-6099-SR (1988).
13. R. J. Bertolacini, J. M. Forgac, D. K. Kim, R. J. Pellet, and K. K. Robinson "Catalytic Functionality for Cool Hydroliquefaction," Third International Conference--The Chemistry and Uses of Molybdenum (1979).
14. D. F. Tatterson, K. K. Robinson, R. Guercio, and T. L. Marker, "Feedstock Effects in Coal Flash Pyrolysis," Communication, I&EC, to be published (1990).
1. F. E. Paulik, K. K. Robinson, and J. F. Roth.
"Vapor Phase Hydroformylation Process," US 3,487,112--British Patent 1,228,201.
2. D. K. Kim, R. J. Bertolacini, L. C. Gutberlet, and K. K. Robinson, "Process for Coal Liquefaction and Catalyst," US 4,257,922.
3. D. K. Kim, R. J. Bertolacini, L. C. Gutberlet, and K. K. Robinson, "Process for Coal Liquefaction and Catalyst," US 4,294,685.
4. J. S. Meyer, K. K. Robinson, J. M. Forgac, and D. F. Tatterson, "Rapid Hydropyrolysis of Carbonaceous Solids," US 4,326,944.
5. K. K. Robinson, "Granulated Activated Carbon for Water Treatment," US 4,954,469.
Mega-Carbon has their laboratory and corporate offices in St. Charles, IL. The research facilities provide a full service organization in which all resources are under one roof: chemical engineering, computer technology, process assembly, and maintenance. Additionally Mega-Carbon has a full complement of chemical research equipment including UV spectrometers, gas chromatographs, analytical balances, temperature controllers, furnaces, and test rigs. Presently Mega-Carbon is conducting research on an improved evaporative loss control device to capture gasoline vapors in automobiles. Additionally Mega-Carbon is located near both Northwestern University, in Evanston IL and Argonne National Laboratory in Argonne, IL where it is possible to have analyses run on the adsorbents to determine surface area, examine its microstructure via scanning microscopy, and measure its adsorption capacity.
3f. Consultants and Subcontractors
C. David Livengood (Argonne Subcontractor)
EDUCATION: Ph.D., Nuclear Engineering, Purdue University, 1970
M.S., Nuclear Engineering, Purdue University, 1967
B.A., Physics (Cum Laude), Wabash College, 1964
Since 1979 Environmental Systems Engineer, Argonne National Laboratory
Leads research activities focused on flue-gas cleanup technologies for SO2, NOx, and air toxics, site-remediation technologies for soils and groundwater, development of advanced sensors, reduction of greenhouse-gas emissions, and energy systems studies.
1984 - 1993 Section Manager, Environmental Technology Section, Argonne National Laboratory.
1981 - 1984 Deputy Section Manager, Environmental Control Technology Section, Argonne National Laboratory
1975 - 1979 Assistant Nuclear Engineer, Argonne National Laboratory
1975 - 1976 Visiting Professor, Nuclear Engineering Program, Northwestern University
1970 - 1975 Assistant Professor, Nuclear Engineering Program, Northwestern University.
PROFESSIONAL: Air and Waste Management Association
Vice-Chairman of the Particulate and Associated Acid Gases Committee
American Association for the Advancement of Science
PUBLICATIONS: Author/coauthor of 1 book, 10 journal articles, 20 topical reports, 87 conference papers, and numerous presentations.
Dr. David Livingood has met with Mega-Carbon and agreed to serve as a consultant for the work performed at Argonne, as well as work in Mega-Carbon's laboratories. His letter confirming this understanding is shown on page 24 of this proposal.
Dr. John B. Butt (Consultant)
D.Eng. Ch.E. 1960, Yale University
M.Eng. Ch.E. 1958, Yale University
B.S. Ch.E. 1963, Clemson University
1969 to Present: Northwestern University, Department of Chemical Engineering, Professor. Walter P. Murphy Professor
1964-1969: Yale University, Department of Engineering and Applied Science, Associate Professor
1963-1964: Yale University, Department of Engineering and Applied Science, Assistant Professor
1961: University of Texas, Visiting Professor of Chemical Engineering
Member of AIChE, ACS, Chicago Catalysis Society
New York Academy of Sciences
American Association for the Advancement of Science
Associate Editor, "Catalysis Reviews-Science and Engineering"
168 technical publications, 1 patent and 2 textbooks
John Butt has met with Mega-Carbon and agreed to serve as a consultant on the Phase I proposal described, herein. He has agreed to the salary indicated in the budget sheet and also the number of hours listed. A letter confirming his involvement is included as page 23.
4. Similar Grant Applications, Proposals, or Awards
No prior, current, or pending support for proposed work.