Combined Chemical Looping Combustion and Calcium Looping for Enhanced Hydrogen Production from Biomass Gasification

Abstract

Production of hydrogen from biomass steam gasification can be enhanced by using calcium oxide sorbents for CO2 capture in the gasifier. Calcium looping suffers from two main drawbacks: the need for high-purity oxygen in order to regenerate the sorbent under oxy-fuel combustion conditions and the loss of sorbent reactivity over several cycles due to sintering of pores upon calcination at high temperatures. One method of addressing the issue of oxygen supply for calcination in calcium looping is to combine the calcium looping and chemical looping processes, where the heat produced by the reduction of an oxygen-carrier by a fuel such as natural gas or gasification syngas, drives the calcination reaction. The technologies can be integrated by combining an oxygen carrier such as CuO with limestone within a composite pellet, or by cycling CuO and limestone within distinct particles. The goal of this project is thus to investigate the different sequences of solids circulation and the cyclic performance of composite limestone-CuO sorbents under varied operating conditions for this novel process configuration. Using a thermogravimetric analyzer (TGA), it was found that using composite CaO/CuO/alumina-containing cement pellets for gasification purposes required oxidation of Cu to be preceded by carbonation (Sequence 2) as opposed to the post-combustion case where the pellets are oxidized prior to carbonation (Sequence 1). Composite pellets were tested using Sequence 2 using varying carbonation conditions over multiple cycles. While the pellets exhibited relatively high carbonation conversion, the oxidation conversion underwent a decrease for all tested conditions, with the reduction in oxygen uptake particularly drastic when the pellets were pre-carbonated in the presence of steam. It appears that the production of a layer of CaCO3 fills up the pellets pores, obstructing the passage of O2 molecules to the more remote Cu sites. Limestone-based pellets and Cu-based pellets were subsequently tested in separate CaL and CLC loops respectively to assess their performance in a dual-loop process (Sequence 3). A maximum Cu content of 50% could be accommodated in a pellet with calcium aluminate cement as support with no loss in oxidation conversion and no observable agglomeration.