Bifunctional fixed-bed catalysts improve CFP performance.

In situ and ex situ catalytic pyrolysis were compared in a system with two 2-in. bubbling fluidized bed reactors. Pine was pyrolyzed in the system with a catalyst, HZSM-5 with a silica-to-alumina ratio of 30, placed either in the first (pyrolysis) reactor or the second (upgrading) reactor. Both the pyrolysis and upgrading temperatures were 500 °C, and the weight hourly space velocity was 1.1 h −1 . Five catalytic cycles were completed in each experiment. The catalytic cycles were continued until oxygenates in the vapors became dominant. The catalyst was then oxidized, after which a new catalytic cycle was begun. The in situ configuration gave slightly higher oil yield but also higher oxygen content than the ex situ configuration, which indicates that the catalyst deactivated faster in the in situ configuration than the ex situ configuration. Analysis of the spent catalysts confirmed higher accumulation of metals in the in situ experiment. In all experiments, the organic oil mass yields varied between 14 and 17% and the carbon efficiencies between 20 and 25%. The organic oxygen concentrations in the oils were 16−18%, which represented a 45% reduction compared to corresponding noncatalytic pyrolysis oils prepared in the same fluidized bed reactor system. GC/MS analysis showed the oils to contain one-to four-ring aromatic hydrocarbons and a variety of oxygenates (phenols, furans, benzofurans, methoxyphenols, naphthalenols, indenols). High fractions of oxygen were rejected as water, CO, and CO 2 , which indicates the importance of dehydration, decarbonylation, and decarboxylation reactions. Light gases were the major sources of carbon losses, followed by char and coke.

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Three HZSM-5 catalysts with different binders (alumina, silica, and clay) were evaluated for upgrading of pine pyrolysis vapors. All catalysts were based on the same HZSM-5 with silica to alumina molar ratio of 30. Experiments in micro-scale analytical Py-GCMS/FID showed that fresh catalysts with silica and clay produced predominantly aromatic hydrocarbons at similar carbon yields. The catalyst with alumina gave lower vapor yields and produced both hydrocarbons and partially deoxygenated products, in particular furans. The catalyst with alumina also gave higher coke yields and exhibited faster deactivation than the catalysts with clay and silica binders. The low hydrocarbon yields and coke formation were attributed to the acidic sites provided by alumina and blocking of the zeolite sites. The catalysts with silica and clay as binders were further tested in a 2-inch fluidized bed system for ex situ catalytic pyrolysis of pine. Similar oils were produced over both catalysts with carbon yields of approximately 23 % and oxygen contents of 20-21 %.

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Metal-impregnated (Ni or Ga) ZSM-5 catalysts were studied for biomass pyrolysis vapor upgrading to produce hydrocarbons using three reactors constituting a 100 000× change in the amount of catalyst used in experiments. Catalysts were screened for pyrolysis vapor phase upgrading activity in two small-scale reactors: (i) a Pyroprobe with a 10 mg catalyst in a fixed bed and (ii) a fixed-bed reactor with 500 mg of catalyst. The best performing catalysts were then validated with a larger scale fluidized-bed reactor (using ∼1 kg of catalyst) that produced measurable quantities of bio-oil for analysis and evaluation of mass balances. Despite some inherent differences across the reactor systems (such as residence time, reactor type, analytical techniques, mode of catalyst and biomass feed) there was good agreement of reaction results for production of aromatic hydrocarbons, light gases, and coke deposition. Relative to ZSM-5, Ni or Ga addition to ZSM-5 increased production of fully deoxygenated aromatic hydrocarbons and light gases. In the fluidized bed reactor, Ga/ZSM-5 slightly enhanced carbon efficiency to condensed oil, which includes oxygenates in addition to aromatic hydrocarbons, and reduced oil oxygen content compared to ZSM-5. Ni/ZSM-5, while giving the highest yield of fully deoxygenated aromatic hydrocarbons, gave lower overall carbon efficiency to oil but with the lowest oxygen content. Reaction product analysis coupled with fresh and spent catalyst characterization indicated that the improved performance of Ni/ZSM-5 is related to decreasing deactivation by coking, which keeps the active acid sites accessible for the deoxygenation and aromatization reactions that produce fully deoxygenated aromatic hydrocarbons. The addition of Ga enhances the dehydrogenation activity of the catalyst, which leads to enhanced olefin formation and higher fully deoxygenated aromatic hydrocarbon yields compared to unmodified ZSM-5. Catalyst characterization by ammonia temperature programmed desorption, surface area measurements, and postreaction temperature-programmed oxidation (TPO) also showed that the metal-modified zeolites retained a greater percentage of their initial acidity and surface area, which was consistent between the reactor scales. These results demonstrate that the trends observed with smaller (milligram to gram) catalyst reactors are applicable to larger, more industrially relevant (kg) scales to help guide catalyst research toward application.

Catalytic fast pyrolysis (CFP) has been identified as a promising pathway for the production of renewable fuels and co-products. However, continued technology development is needed to increase process efficiency and reduce process costs. This report builds upon previous research in which a bifunctional metal–acid Pt/TiO2 catalyst was utilized in a fixed-bed reactor operated with co-fed H2 to improve product yield and reduce coke generation compared to conventional CFP methods. Here, we report further process optimization, in which we achieved similar CFP oil carbon efficiency (>35%) and CFP oil oxygen content (<20 wt %) to our previous report while reducing catalyst and equipment costs by increasing time-on-stream between regenerations by 40–95% and decreasing required regeneration time by more than a factor of 2. These process improvements were achieved by conducting parameter sweeps to determine optimum conditions for CFP and regeneration with key variables including pyrolysis temperature, catalytic upgrading temperature, hydrogen partial pressure, and regeneration oxygen concentration. Coupled with comprehensive oil analyses, these data provide foundational insight into the deoxygenation and coking chemistries for CFP under realistic process conditions while also advancing the technology through applied engineering.

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