Faculty Advisor or Committee Member

Jennifer L. Wilcox, Advisor

Faculty Advisor or Committee Member

Jennifer L. Wilcox, Committee Member

Faculty Advisor or Committee Member

Nikolaos K. Kazantzis, Committee Member

Faculty Advisor or Committee Member

Michael T. Timko, Committee Member

Faculty Advisor or Committee Member

John A. Bergendahl, Committee Member

Faculty Advisor or Committee Member

Fereshteh Rashidi, Committee Member

Identifier

etd-3756

Abstract

The industrial sector is one of the largest emitters of CO2 and a great potential for retrofitting with carbon capture systems. In this work the performance of a palladium-based membrane reactor at 400°C and operating pressures between 100-400 kPa have been studied in terms of methane conversion, hydrogen recovery, hydrogen purity, and CO2 emission. It is found that the MR has the potential to produce high purity hydrogen while the methane conversion values could be as high as 40% at very moderate operating conditions and without using any sweep gases. The H2 permeation and separation properties of two Pd-based composite membranes were evaluated and compared at 400 °C and at a pressure range of 150 kPa to 600 kPa. One membrane was characterized by an approximately 8 μm-thick palladium (Pd)-gold (Au) layer deposited on an asymmetric microporous Al2O3 substrate; the other membrane consisted of an approximately 11 μm-thick pure palladium layer deposited on a yttria-stabilized zirconia (YSZ) support. At 400 °C and with a trans-membrane pressure of 50 kPa, the membranes showed a H2 permeance of 8.42 × 10−4 mol/m2·s·Pa0.5 and 2.54 × 10−5 mol/m2·s·Pa0.7 for Pd-Au and Pd membranes, respectively. Pd-Au membrane showed infinite ideal selectivity to H2 with respect to He and Ar at 400 °C and a trans-membrane pressure of 50 kPa, while the ideal selectivities for the Pd membrane under the same operating conditions were much lower. Furthermore, the permeation tests for ternary and quaternary mixtures of H2, CO, CO2, CH4, and H2O were conducted on the Pd/YSZ membrane. The H2 permeating flux decreased at the conclusion of the permeation tests for all mixtures. This decline however, was not permanent, i.e., H2 permeation was restored to its initial value after treating the membrane with H2 for a maximum of 7 h. The effects of gas hourly space velocity (GHSV) and the steam-to-carbon (S/C) ratio on H2 permeation were also investigated using simulated steam methane reforming mixtures. It was found that H2 permeation is highest at the greatest GHSV, due to a decline in the concentration polarization effect. Variations in S/C ratio however, showed no significant effect on the H2 permeation. The permeation characteristics for the Pd/YSZ membrane were also investigated at temperatures ranging from 350 to 400 °C. The pre-exponential factor and apparent activation energy were found to be 5.66 × 10−4 mol/m2·s·Pa0.7 and 12.8 kJ/mol, respectively. Scanning Electron Microscope (SEM) and X-ray diffraction (XRD) analyses were performed on both pristine and used membranes, and no strong evidence of the formation of Pd-O or any other undesirable phases was observed. The permeation tests with pure hydrogen and inert gases indicate that the MR is highly selective toward hydrogen and the produced hydrogen is an ultrahigh purity grade. The carbon capture experiments in the work consists of dehydrating the retentate stream and redirecting it to a 13X packed bed before analyzing the stream via mass spectrometry. The carbon capture studies reveal that approximately 5.96 mmole CO2 (or 262.25 mg of CO2)can be captured per g of 13X. In this study, SEM-EDS, and XRD technics have been used to characterize the crystallography and morphology of the membrane surface. These material characterization techniques reveal that the surface of the membrane has gone through significant oxidation during the steam methane reforming reaction, although this oxidation is only limited to the few nanometers of depth through the surface of the palladium membrane.

Publisher

Worcester Polytechnic Institute

Degree Name

PhD

Department

Chemical Engineering

Project Type

Dissertation

Date Accepted

2020-05-11

Accessibility

Unrestricted

Subjects

Hydrogen, Carbon capture, Palladium, Steam methane reforming, Zeolite 13X, Techno economic analysis

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