Carbon dioxide-selective membranes and their applications in hydrogen processing

Fuel cells, which are regarded as a promising energy conversion approach in the 21st century, are now receiving increasing attention worldwide. In most cases, hydrogen is the preferred fuel for fuel cells, especially for proton-exchange membrane fuel cells (PEMFCs). One key issue in the development of PEMFC is how to generate hydrogen from the available hydrocarbon fuels. Most feasible strategies consist of a reforming step followed by the water gas shift (WGS) reaction. The resulting synthesis gas (syngas) still consists of 0.5--1.0% CO, which needs to be reduced to less than 10 ppm to meet the requirement of PEMFCs. Therefore, a further CO clean-up step is usually used to decrease CO concentration.In the present work, new CO2-selective membranes were synthesized and their applications for fuel cell fuel processing and synthesis gas purification were investigated. In order to enhance CO2 transport across membranes, the synthesized membranes contained both mobile and fixed site carriers in crosslinked poly(vinyl alcohol). The effects of crosslinking, membrane composition, feed pressure, water content, and temperature on transport properties were investigated. The membranes have shown a high permeability and a good CO 2/H2 selectivity and maintained their separation performance up to 170°C. One type of these membranes showed a permeability of 8000 Barrers (1 Barrer = 10-10 cm3 (STP).cm/(cm 2.s.cm.Hg)) and a CO2/H2 selectivity of 290 at 110°C. This membrane had a permeability of 1200 Barrers and a CO 2/H2 selectivity of 33 even at 170°C. The applications of the synthesized membranes were demonstrated in a CO2-removal experiment, in which the CO2 concentration in retentate was decreased from 17% to less than 10 ppm.With such membranes, there are several options to reduce the CO concentration of syngas. One option is to develop a WGS membrane reactor, in which both the low temperature WGS reaction and the CO2-removal take place. Another option is to use a proposed process consisting of a CO2-removal membrane module followed by a conventional low-temperature WGS reactor. A third option is to use methanation after the CO2-removal, one of the most widely used processes for the CO clean-up step. Experimental results showed that CO concentration was reduced to below 10 ppm with all three approaches. In the membrane reactor, a CO concentration of less than 10 ppm and a H 2 concentration of greater than 50% (on the dry basis) were achieved at various flow rates of a simulated autothermal reformate. In the proposed CO2-removal/WGS process, with more than 99.5 % CO2 removed from the synthesis gas, the reversible WGS was shifted forward so that the CO concentration was decreased from 1.2% to less than 10 ppm (dry), which is the requirement for PEMFC. The WGS reactor had a gas hourly space velocity of 7650 h-1 at 150°C and the H2 concentration in the outlet was more than 54.7% (dry).The applications of the synthesized CO2-selective membranes for high-pressure synthesis gas purification were also studied. Synthesis gas is the primary source for hydrogen as well as an intermediate for a broad range of chemicals. The separation of CO2 from synthesis gas is a critical step to obtain high purity hydrogen in many industrial plants, especially refinery plants. We studied the synthesized polymeric CO2 -selective membranes for synthesis gas purification at feed pressures higher than 200 psia and temperatures ranging from 100 to 150°C. The effects of feed pressure, microporous support, temperature, and permeate pressure were investigated using a simulated synthesis gas containing 20% carbon dioxide and 80% hydrogen. The membranes synthesized showed best CO2 permeability and CO2/H2 selectivity at 110°C. At a feed pressure of 220 psia, the CO2 permeability and CO2/H2 selectivity reached 756 Barrers and 42, respectively, whereas at a feed pressure of 440 psia, the CO2 permeability was 391 Barrers and the CO 2/H2 selectivity was about 25.