Selective Analytical Production of 1-Hydroxy-3,6-dioxabicyclo[3.2.1]octan-2-one from Catalytic Fast Pyrolysis of Cellulose with Zinc-Aluminium Layered Double Oxide Catalyst

Abstract

Zinc-aluminium layered double oxide (Zn-Al-LDO) catalysts derived from layered double hydroxides (LDHs) were prepared and used for the catalytic fast pyrolysis of cellulose to selectively produce 1-hydroxy-3,6-dioxabicyclo[3.2.1]octan-2-one (LAC), which is a valuable anhydrosugar derivative. Analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) experiments were performed to investigate the LAC production under different reaction conditions. The results indicated that the Zn-Al-LDO catalysts were capable of greatly inhibiting the pyrolytic formation of levoglucosan (LG) and capable of promoting the formation of LAC and certain other products. The catalyst with the Zn/Al molar ratio of 2 exhibited the best catalytic capacity for LAC production. Both pyrolysis temperature and the catalyst-to-cellulose ratio affected the pyrolytic product distribution remarkably. The maximal LAC yield was obtained at the pyrolysis temperature of 350 °C and catalyst-to-cellulose ratio of 4 and featured a peak area percentage of 21.9% (calculated by GC/MS), compared with only 3.0% from the non-catalytic process. In addition, the LDO catalyst performed better than the previously reported montmorillonite K-10 catalyst on the enhancement of LAC production.

Vapor-Phase Stabilization of Biomass Pyrolysis Vapors Using Mixed-Metal Oxide Catalysts

“…Similarly, Palinko et al reported higher BET surface area in Mg–Al mixed-metal oxides compared to Zn–Al mixed-metal oxide . An increase in surface area with increasing Al content has been attributed to increased porosity generated by greater CO 2 gas evolution during the calcination of the LDH precursor material caused by decomposition of CO 3 2– . , …”

“…These diffraction patterns are in agreement with those of previously reported Zn−Al and Mg−Al mixed metal oxides which were prepared by calcination in the range of 450−500 °C. 13,28,29 The Mg−Al and Zn−Al materials show broad diffraction peaks indicative of crystalline MgO and ZnO, respectively. We were unable to detect crystalline alumina (Al 2 O 3 ) or spinel-type (MAl 2 O 4 , M = Mg or Zn) phases in any of the materials.…”

Vapor-phase Stabilization of Biomass Pyrolysis Vapors Using Mixed-metal Oxide Catalysts

“…These diffraction patterns are in agreement with those of previously reported Zn-Al and Mg-Al mixed metal oxides which were prepared by calcination in the range of 450-500 °C. 13,[28][29] The Mg-Al and Zn-Al materials show broad diffraction peaks indicative of crystalline MgO and ZnO, respectively. We were unable to detect crystalline alumina (Al2O3) nor spinel-type (MAl2O4, M = Mg or Zn) phases in any of the materials.…”

“…30 An increase in surface area with increasing Al content has been attributed to increased porosity generated by greater CO2 gas evolution during the calcination of the LDH precursor material caused by decomposition of CO3 2-. 16,29 We used CO2-TPD to compare basic site density and strength among the different mixed-metal oxides (Table 1 and Figure S2). Three peaks occurring at low, medium, and high temperatures were resolved from the desorption curves.…”

Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon

“…In recent years, a more attractive technique, catalytic pyrolysis of biomass toward specific compounds through selective control of biomass pyrolysis process (known as selective pyrolysis) has gained extensive attentions, as it offers a promising way to facilitate the application of pyrolytic products (Theodore and Juan, 2013 ; Liu et al, 2014a ; Shen et al, 2015 ; Zhang et al, 2017 ). Such catalytic/selective pyrolysis can be achieved via suitable biomass materials or proper catalysts under specific pyrolysis conditions, so as to obtain different valuable compounds, such as levoglucosenone (Lu et al, 2014 ; Zhang et al, 2015d ; Ye et al, 2017 ), furfural (Lu et al, 2011 ; Zhang et al, 2014 ), 1-hydroxy-3,6-dioxabicyclo[3.2.1]octan-2-one (Fabbri et al, 2007 ; Zhang et al, 2015a ), aromatic hydrocarbons (Vichaphund et al, 2015 ), 4-vinyl phenol (Qu et al, 2013 ), 4-ethyl phenol (Zhang et al, 2015c ; Lu et al, 2016 ), 4-ethyl guaiacol (Lu et al, 2017 ), nicotyrine (Ye et al, 2016 ) and so on.…”