Progress 09/01/11 to 08/31/16
Outputs
Target Audience:Gasoline station venting is an existing application that is growing significantly in size. Our emission control system should provide savings of 0.14% retail gasoline delivered in the United States. Based on a total of 138 billion gallons of gasoline dispensed in the U.S. per year, 0.14% recovery represents a potential product savings of 200 million gallons per year and equivalent vapor emissions. This technology will be easily retrofittable to existing gasoline stations for retaining significant additional gasoline vapors. Besides this gas station venting application, our technology will also be applicable to similar areas like petrochemical storage facilities. While the initial focus of this program is VOC abatement associated with biofuel storage tanks, we believe there are many other applications as well. A market research study by BCC (Business Communications Company) has identified potential VOC reduction opportunities in the pharmaceutical industry, cement industry, the power industry, surface coating industry, waste water industry, and semiconductor industry. Furthermore, this technology is expected to have a significant global market beyond the U.S.A. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?One junior chemical engineer with an undergraduate degree is working throughout the project under the mentorship of a senior engineer. An undergraduate co-op student from Drexel University and an undergraduate summer trainee from University of Delaware got trained in this program. How have the results been disseminated to communities of interest?CMS worked withVapor Systems Technologies, Inc. (VST) to introduce this technology after the state of California approved the gas station venting process.Because of the low margins due to low crude oil prices, filing stations were reluctant to adopt the venting process.However, ifthe successful technology is developed and applied to all U.S. fuel stations for solving the VOC emissions problem, 200 million gallons per year of E10 or E15 fuel (containing 10 or 15% ethanol) can be recovered. This is both an energy savings and an emissions reduction of equal magnitude. A market research study by BCC (Business Communications Company) has identified potential VOC reduction opportunities in the pharmaceutical industry, cement industry, the power industry, surface coating industry, waste water industry, and semiconductor industry. Furthermore, this technology is expected to have a significant global market beyond the U.S.A. What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
a) Novel polymer manufacturing processes were scaled up successfully. Initial polymer quality problems were resolved successfully. b) Sufficient membrane was manufactured with the novel polymer and the initial lab test data exceeded performance specifications for gas permeation properties. c) The pilot test system was built. The pilot test unit works as per design specifications and gives reproducible data. d) We have optimized the module design and built additional modules that now meet the initial goal performance of E10 gasoline recovery. The problems with module design giving low performance have been resolved. e) We demonstrated the robustness of the CMS membrane module over 30 days of 96 oC exposure under high concentrations of ethanol. There is no degradation of membrane under these severe conditions. f) This analysis shows that the CMS membrane systems have a payback time to the end user of about 29 months assuming gasoline cost of $2.75. This analysis is based exclusively on the ratio of fuel saved to membrane system costs. g) These values are conservative since no credit is given to either: (1) the reduction in emissions, or (2) the reductions in problems (corrosion and phase separation) associated with the water removed. h) Because of the drop in gasoline prices, our partners could not divert time and resources for a field test before the program deadline. Task 1. Scale up fabrication of improved membrane. As planned in Task 1 we have scaled up the fabrication of membranes using the novel polymers CMS 5 and CMS 12. We fabricated 25 sq-ft of membrane coated with CMS 5 polymer and 25 sq-ft of membrane coated with CMS 12 polymer. The membranes were manufactured using the CMS flat sheet coating facility with the novel polymers also synthesized by CMS. The polymer solutions were prepared using FC770 fluorosolvent and coated on polyacrylonitrile (PAN) supports supplied by our commercial development partner Sepro, Inc. Using the above membrane, membrane minimodules were built by CMS for checking the membrane quality through gas testing at CMS. The gas test results showed that the membrane met the performance goal, i.e., N2 permeance is at least 80 GPU and the O2/N2 selectivity is at least 2.5. Therefore this membrane is sufficient and suitable for building larger modules in Task 2. Task 1 was successfully completed. Task 2. Scale up fabrication of modules with improved membrane. In Task 2 we used the membrane made in Task 1 for building 2 spiral-wound membrane modules, each with 1.5 sq-ft of active area. The spiral wound modules were made at the Sepro facilities. These modules were tested at CMS with O2 and N2. The results exceeded the goal performance since the N2 permeance was measured at 105 GPU and the O2/N2 selectivity was measured at 2.8. This task was successfully completed. Task 3. Optimize membrane modules. This task had to be revisited after finding that the first two modules made in Task 2 did not meet the performance goal of Task 5. Three additional modules were built with improved spacers to attain better fluid dynamics inside the modules. Figure 1a shows one of the spiral wound modules that was originally built and did not attain goal performance. Figure 1b shows the optimized module built with hollow fibers and the improved spacer. Performance data from testing in Task 5 show good performance using this improved module. Therefore, this task was successfully completed. Task 4. Fabricate pilot system for volatile organic compounds (VOC) recovery. A pilot test system has been built as per the schematic design shown in Figure 2. The completed pilot unit is shown in Figure 3. This unit will be used in Tasks 5 and 6 for evaluating the modules made in Task 2 and demonstrate that they operate with at least 95% recovery of gasoline vapor components, which include ethanol. In addition, this unit will be used to demonstrate the long term stable performance of the modules. The pilot test data generated will be used in Task 7 for doing an economic evaluation of the VOC recovery process using the CMS novel membrane system. This task was successfully completed. Task 5. Run pilot test. This task had to be repeated with the additional three improved modules built in Task 3. Pilot testing data (Table 1) show that very high E 10 gasoline recoveries are obtained when degassed through the CMS novel membrane module. The stage cut is the % volume of vapor fed to the membrane module that permeates through the membrane and is vented. The data in Table 1 can be used to project that if the module is run at 25% stage cut, 95% recovery of gasoline is attained, which is consistent with our stated goal. Also, the membrane system has been demonstrated to be resistant to ethanol, which is a key component of gasoline. Pilot testing continues to show performance reproducibility. Task 6. Run long term test: This test was an extension of Task 5, and was performed in the pilot system built in Task 4. The objective of this test was to demonstrate the sustained long term performance in a given membrane module. The results of this testing is shown in Figure 4 and demonstrate the robustness of the CMS membrane module over 30 days of 96 oC exposure under high concentrations of ethanol. There is no degradation of membrane under these severe conditions. Milestone: Demonstrated severe condition pervaporation module sustained for at least 3 weeks. Task 7 Engineering and Economic analysis: The preliminary engineering analysis done in Phase I compared the conventional disposal of VOC by catalytic burning vs. the membrane based process. This resulted in large energy and cost savings when using the membrane system instead of the conventional system based on catalytic burning. This analysis was rerun and refined with the additional data collected in Tasks 5 and 6. For the Phase II program, the analysis was expanded to include an examination of the effects of important process variables, including: storage tank size, gasoline consumption rate, and operating conditions. This analysis shows that the CMS membrane systems have a payback time to the end user of about 29 months assuming gasoline cost of $2.75. This analysis is based exclusively on the ratio of fuel saved to membrane system costs. These values are conservative since no credit is given to either: (1) the reduction in emissions, or (2) the reductions in problems (corrosion and phase separation) associated with the water removed. The results show that a CMS membrane system is a very sound investment that pays by itself in about 29 month. Milestone: Demonstrated payback time of system of 2 to 2.4 years. Task 8 Run field test Not Completed. Because of the drop in gasoline prices, our partners could not divert time and resources for a field test before the program deadline. So we are postponing that for a more appropriate time. Problems Encountered • Initially, there were quality problems scaling up the novel polymer manufacture in Task 1. The molecular weight of the polymer was not high enough, which led to membrane instability. This problem was solved by eliminating leaks in the polymerization reactor and by changing the polymerization method from solution to emulsion. Task 1 was successfully completed, but it took longer than anticipated, which delayed the program. • The initial modules built in Task 3 gave VOC recovery of 90% in Task 5. This is below the goal of 95% recovery. Therefore, we had to repeat Tasks 3 and 5, which further delayed this program. Fortunately, the second time through Task 3 we produced additional modules that are meeting goal performance in initial testing done in the second pass through Task 5. • The retirement of the PI, John Bowser, caused additional delays in this program • Because of the drop in gasoline prices, our partners could not divert time and resources for a field test before the program deadline. So we are postponing that for a more appropriate time.
Publications
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Progress 09/01/11 to 08/31/12
Outputs
OUTPUTS: CMS has improved the membrane polymer and scaled up the process in order to fabricate modules for testing. The permeance data is showing excellent results and has exceeded the goals of the program. The program is on schedule to be completed on time and indications are that this will lead to a successful commercialization effort from a technical standpoint. In addition, CMS has completed the commercialization program and there appears to be a viable market in the Navy for use at fuel depots. A novel polymer manufacturing process was scaled up successfully. Successes to date include: the initial polymer quality problem was resolved: Sufficient membranes were manufactured and initial test data exceeded performance specifications; membrane modules have been manufactured and the pilot test system has been fabricated; and, worked with LARTA to develop a commercialization effort to identify and engage partners and customers for the technology. PARTICIPANTS: Not relevant to this project. TARGET AUDIENCES: Not relevant to this project. PROJECT MODIFICATIONS: Not relevant to this project.
Impacts
As planned in task 1 we have scaled up the fabrication of membrane using the novel polymers CMS5 and CMS12. We fabricated 25 sq-ft of membrane coated with CMS5 polymer and 25 sq-ft of membrane coated with CMS12 polymer. The membranes were manufactured using CMS flat sheet coating facility using the novel polymers also manufactured by CMS. The polymer solutions were prepared on FC770 fluorosolvent and coated on polyacrylonitrile (PAN) support supplied by our development partner Sepro, Inc. Membrane minimodules were built by CMS for checking the membrane quality through gas testing at CMS. The gas test results showed that the membrane met the goal performance, i.e., N2 permeance is at least 80 GPU and the O2/N2 selectivity is at least 2.5. We used the membrane for building two modules, each with 1.5 sq-ft of active membrane area. The spiral wound modules were made at Sepro facilities. These modules were tested at CMS with O2 and N2. The results exceeded the goal performance since the N2 permeance was measured at 105 GPU and the O2/N2 selectivity was measured at 2.8. A pilot test system has been built as per the schematic design shown. The completed pilot unit is shown in the picture shown. This unit will be used for evaluating the modules and demonstrating that they operate with at least 95% recovery of gasoline vapors components, which include ethanol. In addition, this unit will be used to demonstrate the long term stable performance of the modules. The pilot test data generated will be used for doing an economic evaluation of the VOC recovery process using the CMS novel membrane systems.
Publications
- No publications reported this period
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