DOE OSTI2011
Due to the very small relative volatility difference between propane and propylene, current propane/propylene separation by distillation requires very tall distillation towers (150-250 theoretical plates) and large reflux ratios (up to 15), which is considered to be the most energy consuming large-scale separation process. Adsorptive separation processes are widely considered to be more energy-efficient alternatives to distillation. However, slow diffusion kinetics/mass transport rate through the adsorbent bed often limits the performance of such processes, so further improvements are possible if intra-particle mass transfer rates can be improved. Rive Technology, Inc. is developing and commercializing its proprietary mesoporous zeolite technology for catalysis and separation. With well-controlled intracrystalline mesoporosity, diffusion kinetics through such mesoporous zeolite based catalysts is much improved relative to conventional zeolites, leading to significantly better product selectivity. This 'proof-of-principle' project (DE-EE0003470) is intended to demonstrate that Rive mesoporous zeolite technology can be extended and applied in adsorptive propane/propylene separation and lead to significant energy saving compared to the current distillation process. In this project, the mesoporous zeolite Y synthesis technology was successfully extended to X and A zeolites that are more relevant to adsorbent applications. Mesoporosity was introduced to zeolite X and A for the first time while maintaining adequate adsorption capacity. Zeolite adsorbents were tested for liquid phase separation performance using a pulse flow test unit and the test results show that the separation selectivity of the mesoporous zeolite adsorbent is much closer to optimal for a Simulated Moving Bed (SMB) separation process and the enhanced mesoporosity lead to >100% increase of overall mass transport rate for propane and propylene. These improvements will significantly improve the performance of an adsorptive separation unit for propane/propylene separation compared with traditional zeolite adsorbents. The enhanced transport will allow for more efficient utilization of a given adsorbent inventory by reducing process cycle time, allowing a faster production rate with a fixed amount of adsorbent or smaller adsorbent inventory at a fixed production rate. Smaller adsorbent inventory would also lead to significant savings in the capital cost due to smaller footprint of the equipment. Energy consumption calculation, based on the pulse test results for rived NaX zeolite adsorbent, of a hypothetical moderate-scale SMB propane/propylene separation plant that processes 6000 BPSD refinery grade propylene (70% propylene) will consume about 60-80% less energy (both re-boiler and condenser duties) compared to a C3 splitter that process the same amount of feed. This energy saving also translates to a reduction of 30,000-35,000 tons of CO 2 emission per year at this moderate processing rate. The enhancement of mass transport achievable by introduction of controlled mesoporosity to the zeolite also opens the door for the technology to be applied to several other adsorption separation processes such as the separation of xylene isomers by SMB, small- and large scale production of O 2 /N 2 from air by pressure swing adsorption, the separation of CO 2 from natural gas at natural gas wellheads, and the purification of ultra-high purity H 2 from the off gas produced by steam-methane-reforming.