Hydrogen Selective Inorganic membranes for Gas Separations under High Pressure Intermediate Temperature Hydrocarbonic Envrionment

Abstract

In this project, we have successfully developed a full scale commercially ready carbon molecular sieve (CMS) based membrane for applications in H{sub 2} recovery from refinery waste and other aggressive gas streams. Field tests at a refinery pilot plant and a coal gasification facility have successfully demonstrated its ability to recovery hydrogen from hydrotreating and raw syngas respectively. High purity H{sub 2} and excellent stability of the membrane permeance and selectivity were obtained in testing conducted over >500 hours at each site. The results from these field tests as well as laboratory testing conclude that the membranes can be operated at high pressures (up to 1,000 psig) and temperatures (up to 300 C) in presence of aggressive contaminants, such as sulfur and nitrogen containing species (H{sub 2}S, CO{sub 2}, NH{sub 3}, etc), condensable hydrocarbons, tar-like species, heavy metals, etc. with no observable effect on membrane performance. By comparison, similar operating conditions and/or environments would rapidly destroy competing membranes, such as polymeric, palladium, zeolitic, etc. Significant cost savings can be achieved through recovering H{sub 2} from refinery waste gas using this newly developed CMS membrane. Annual savings of $2 to 4MM/year (per 20,000 scfd of waste gas) can be realized by recovering the H{sub 2} for reuse (versus fuel). Projecting these values over the entire US market, potential H{sub 2} savings from refinery waste gases on the order of 750 to 1,000MM scfd and $750 to $1,000MM per year are possible. In addition to the cost savings, potential energy savings are projected to be ca. 150 to 220 tBTU/yr and CO{sub 2} gas emission reductions are projected to be ca. 5,000 to 6,500MMtons/year. The full scale membrane bundle developed as part of this project, i.e., 85 x 30 inch ceramic membrane tubes packaged into a full ceramic potting, is an important accomplishment. No comparable commercial scale product exists in the inorganic membrane field. Further, this newly developed full scale bundle concept can be extended to other thin film inorganic membrane technology (Pd, zeolite, etc), providing a potential commercialization pathway for these membrane materials that demonstrate high potential in a variety of separation applications yet remain a laboratory 'novelty' for lack of a full scale support. Overall, the project has been highly successful and all of the project objectives have been met. We have developed the first of its kind commercial scale carbon molecular sieve membrane and demonstrated its performance in field testing under aggressive operating conditions and in the presence of chemical contaminants that would rapidly destroy alternative organic and inorganic membranes. This innovative membrane permits H{sub 2} recovery from gas streams that up until now have not been successfully treated with membrane or conventional technology. Our end user participant is currently pursuing the field demonstration of this membrane for hydrogen recovery at its refinery site.