Product Slate Research Articles

Detailed speciation of biomass pyrolysis products with a novel TGA-based methodology: the case-study of cellulose

Pyrolysis of waste biomass represents a key route for the circular economy and a promising solution for the generation of valuable chemicals and liquid biofuels. The complex multi-component and multi-phase nature of the process, however, poses a challenge in acquiring comprehensive experimental data on biomass devolatilization. These data are essential for refining kinetic schemes and optimizing technology. This work presents a novel experimental methodology suitable for the collection of kinetically relevant data on biomass devolatilization combined with a complete characterization of the product slate. This methodology consists of a thermogravimetric analyser employed to carry out pyrolysis experiments, useful for the accurate monitoring of mass loss dependencies at varying heating rate, for the control of reaction temperatures and for the suppression of secondary gas-phase reactions as well as of transfer limitations. Multiple analytical methodologies and sampling protocols were combined for product speciation – downstream online MS for gases and H2O, sorbing traps for integral offline GC–FID/MS measurement of heavy oxygenates, point vapour collection for instant GC–FID/MS analysis of light oxygenates – and allowed to independently determine the integral mass yield of each pyrolysis product, closing mass balances with very high accuracy. Experiments of cellulose pyrolysis at varying heating rate were carried out to tune and validate the methodology. Speciation protocols allowed to identify and individually quantify 31 species among pyrolysis products, including gases, condensable oxygenates, H2O and char. The comparison of experimental findings with predictions from a state-of-art lumped model has highlighted the significance of the present methodology in unravelling the kinetics governing both devolatilization and product distribution.

Three-stage pyrolysis–steam reforming–water gas shift processing of household, commercial and industrial waste plastics for hydrogen production

Five common single plastics and nine different household, commercial and industrial waste plastics were processed using a three-stage (i) pyrolysis, (ii) catalytic steam reforming and (iii) water gas shift reaction system to produce hydrogen. Pyrolysis of plastics produces a range of different hydrocarbon species which are subsequently catalytically steam reformed to produce H2 and CO and then undergo water gas shift reaction to produce further H2. The process mimics the commercial process for hydrogen production from natural gas. Processing of the single polyalkene plastics (high-density polyethylene (HDPE), low-density polyethylene (LDPE), and polypropylene (PP)) produced similar H2 yields between 115 mmol and 120 mmol per gram plastic. Even though PS produced an aromatic product slate from the pyrolysis stage, further stages of reforming and water gas shift reaction produced a gas yield and composition similar to that of the polyalkene plastics (115 mmol H2 per gram plastic). PET gave significantly lower H2 yield (41 mmol per gram plastic) due to the formation of mainly CO, CO2 and organic acids from the pyrolysis stage which were not conducive to further reforming and water gas shift reaction. A mixture of the single plastics typical of that found in municipal solid waste produced a H2 yield of 102 mmol per gram plastic. Knowing the gas yields and composition from the single plastics enabled an estimation of the yields from a simulated waste plastic mixture and a ‘real-world’ waste plastic mixture to be determined. The different household, commercial and industrial waste plastic mixtures produced H2 yields between 70 mmol and 107 mmol per gram plastic. The H2 yield and gas composition from the single waste plastics gave an indication of the type of plastics in the mixed waste plastic samples.Graphical abstract

Conquering the solubility barrier of di-n-octylamine as structure-directing agent in hierarchical silicoaluminophosphate synthesis by using phase-transfer synthesis

Silicoaluminophosphates (SAPOs) are a class of microporous solids employed as solid acid catalysts or adsorbents in petrochemical and coal chemical processes, which are often generated in hydrothermal synthesis using water-soluble organic structure-directing agents (OSDA), resulting in the formation of micron sized, rod-like crystals running along pore-channel direction for unidimensional SAPOs. The use of a low-cost, barely soluble di-n-octylamine (DOA) as OSDA in a water/toluene biphasic media to crystallize SAPO-31 is reported. The product is disclosed to be a hierarchically porous material built up of self-assembled nanocrystals (∼110 nm) with enhanced diffusion property and preserved acidity comparable to that of a standard sample derived using di-n-hexylamine as OSDA. The formation is mediated by the formation of a Pickering emulsion structure that favors crystal nucleation over growth, thus overcoming the solubility barrier of candidate OSDA. The obtained material exhibited higher isomer yield in catalytic hydroisomerization of n-dodecane compared to the control sample. Product distribution analysis discloses that mono-branched isomers are generated mainly inside the micropores, while di-branched isomers are produced via key-lock catalysis on pore-mouth sites. The increase in isomerization selectivity is attributed to the formation of more mono-branched isomers and their lowered cracking probability associated with enhanced diffusion property. This new synthetic protocol expands the toolkit of candidate OSDAs towards hydrophobic molecules and exemplifies porogen-free fabrication of hierarchical SAPOs. The uncovered origin of shape-selectivity offers a guidance towards manipulating hydroisomerization product slates.

Economic analysis of the benefits to petroleum refiners for low carbon boosted spark ignition biofuels

A refinery modeling framework is developed to estimate the benefits of blending high-quality biofuels directly with refinery gasoline components to produce premium grade fuels. The results offer a change in paradigm - instead of biofuels being competitors to fossil fuels, biofuels can add value to refineries’ product slates, because of their favorable properties. This potential value can be characterized by calculating the breakeven value (BEV), as defined below. The proposed modeling framework incorporates extensive data from (1) projected product demands over the next few decades, (2) crude oil and refinery products pricing, and (3) fuel specifications. The complete refinery models serve as a basis for assessing the value of biofuels, assuming profitability remains the same for representative petroleum refinery configurations. Resulting valuations varied widely with BEVs observed between $10-$120/bbl given the considered blending levels and crude prices. Further, BEV was correlated with the fuel octane ratings such as octane numbers (research, RON and motor octane numbers, MON) and both antiknock index (AKI, average of RON and MON) and sensitivity (S, difference between RON and MON), with a slightly higher correlation with the sensitivity. However, the expected decrease in gasoline demand for the upcoming years could negatively impact biofuels demand and value, in a business-as-usual scenario. The analysis also showed high valuations in smaller refineries since they can enhance the capabilities for producing specialty, high-value fuels/products, and introduce high octane-barrels into otherwise constrained blending operations. Additional implications towards refiners include opportunities to rebalance operations, access to high-value fuel markets, and synchronization with broader transportation industry trends. Furthermore, results indicate the value of Co-Optima boosted spark ignition (BSI) efficiency gains can extend to refiners to incentivize decarbonization and diversified feedstock production.

A low carbon route to ethylene: Ethane oxidative dehydrogenation with CO2 on embryonic zeolite supported Mo-carbide catalyst

The study reports a novel catalyst based on supported molybdenum-carbide (Mo2C) phase for oxidative dehydrogenation of ethane with CO2 (ODH-CO2). The optimal result is obtained with MoS2-precursor as the intermediate supported on a non-acidic embryonic zeolite, which is transformed in situ to Mo2C (Mo2C@EZ). The ultimate catalyst and its intermediates are characterized. 66% conversion of ethane, 58% of ethylene yield, and 56% conversion of CO2 to CO with the in situ co-produced hydrogen obtained from ethane to ethylene transformation are the achievements of utilizing Mo2C@EZ. The performed techno-economic study on Mo2C@EZ results in a potentially CO2 negative route for ethylene production with 109% of CO2 reduction per ton of produced ethylene in comparison with a conventional ethane cracker. The process is expected to be cheaper in capital expenditure (CAPEX) and operating expenses (OPEX) thanks to a simpler product slate, lower energy demand, and no requirement for steam dilution.

A Materials Science Perspective of Midstream Challenges in the Utilization of Heavy Crude Oil.

An increasing global population and a sharply upward trajectory of per capita energy consumption continue to drive the demand for fossil fuels, which remain integral to energy grids and the global transportation infrastructure. The oil and gas industry is increasingly reliant on unconventional deposits such as heavy crude oil and bitumen for reasons of accessibility, scale, and geopolitics. Unconventional deposits such as the Canadian Oil Sands in Northern Alberta contain more than one-third of the world’s viscous oil reserves and are vital linchpins to meet the energy needs of rapidly industrializing populations. Heavy oil is typically recovered from subsurface deposits using thermal recovery approaches such as steam-assisted gravity drainage (SAGD). In this perspective article, we discuss several aspects of materials science challenges in the utilization of heavy crude oil with an emphasis on the needs of the Canadian Oil Sands. In particular, we discuss surface modification and materials’ design approaches essential to operations under extreme environments of high temperatures and pressures and the presence of corrosive species. The demanding conditions for materials and surfaces are directly traceable to the high viscosity, low surface tension, and substantial sulfur content of heavy crude oil, which necessitates extensive energy-intensive thermal processes, warrants dilution/emulsification to ease the flow of rheologically challenging fluids, and engenders the need to protect corrodible components. Geopolitical reasons have further led to a considerable geographic separation between extraction sites and advanced refineries capable of processing heavy oils to a diverse slate of products, thus necessitating a massive midstream infrastructure for transportation of these rheologically challenging fluids. Innovations in fluid handling, bitumen processing, and midstream transportation are critical to the economic viability of heavy oil. Here, we discuss foundational principles, recent technological advancements, and unmet needs emphasizing candidate solutions for thermal insulation, membrane-assisted separations, corrosion protection, and midstream bitumen transportation. This perspective seeks to highlight illustrative materials’ technology developments spanning the range from nanocomposite coatings and cement sheaths for thermal insulation to the utilization of orthogonal wettability to engender separation of water–oil emulsions stabilized by endogenous surfactants extracted during SAGD, size-exclusion membranes for fractionation of bitumen, omniphobic coatings for drag reduction in pipelines and to ease oil handling in containers, solid prills obtained from partial bitumen solidification to enable solid-state transport with reduced risk of damage from spills, and nanocomposite coatings incorporating multiple modes of corrosion inhibition. Future outlooks for onsite partial upgradation are also described, which could potentially bypass the use of refineries for some fractions, enable access to a broader cross-section of refineries, and enable a new distributed chemical manufacturing paradigm.

CAI Performance Additives announces two pelletized light stabilizing agents

Massachusetts based CAI Performance Additives has announced a slate of new products, including ST-LST5350 and ST-LST0850, two proprietary light stabilizing agents. They are said to be extremely low VOC-additives, so compounders can deliver light stabilization for their customers without worrying about inducing smell or surface bloom of VOCs.

How Many Molecules Can Fit in a Zeolite Pore? Implications for the Hydrocarbon Pool Mechanism of the Methanol-to-Hydrocarbons Process

The methanol-to-hydrocarbons (MTH) process is a very advantageous way to upgrade methanol to more valuable commodity chemicals such as light alkenes and gasoline. There is general agreement that, at steady state, the process operates via a dual cycle “hydrocarbon pool” mechanism. This mechanism defines a minimum number of reactants, intermediates, and products that must be present for the reaction to occur. In this paper, we calculate (by three independent methods) the volume required for a range of compounds that must be present in a working catalyst. These are compared to the available volume in a range of zeolites that have been used, or tested, for MTH. We show that this straightforward comparison provides a means to rationalize the product slate and the deactivation pathways in zeotype materials used for the MTH reaction.

Combinatorial Assortment Optimization

Assortment optimization refers to the problem of designing a slate of products to offer potential customers, such as stocking the shelves in a convenience store. The price of each product is fixed in advance, and a probabilistic choice function describes which product a customer will choose from any given subset. We introduce the combinatorial assortment problem, where each customer may select a bundle of products. We consider a choice model in which each consumer selects a utility-maximizing bundle subject to a private valuation function, and study the complexity of the resulting optimization problem. Our main result is an exact algorithm for additive k -demand valuations, under a model of vertical differentiation in which customers agree on the relative value of each pair of items but differ in their absolute willingness to pay. For valuations that are vertically differentiated but not necessarily additive k -demand, we show how to obtain constant approximations under a “well-priced” condition, where each product’s price is sufficiently high. We further show that even for a single customer with known valuation, any sub-polynomial approximation to the problem requires exponentially many demand queries when the valuation function is XOS and that no FPTAS exists even when the valuation is succinctly representable.

Virgin Heavy Gas Oil from Oil Sands Bitumen as FCC Feed

This study deals with a systematic investigation of the fluid catalytic cracking (FCC) performance of a bitumen-derived virgin heavy gas oil (HGO) in the presence of its counterpart from bitumen-derived synthetic crude oil (SCO). The objective is to determine the amelioration effect on yield and product slate by the addition of the premium SCO HGO. The 343–525 °C cut virgin bitumen HGO was obtained from distillation of a raw Athabasca oil sands bitumen. It was then blended with different amounts of the 343 °C+ fraction of commercial SCO. Four HGO blends were prepared containing 75, 64, 61, and 48 v% of SCO HGO. Each HGO blend, as well as 100% SCO HGO, were catalytically cracked at 500 and 520 °C using a bench-scale Advanced Cracking Evaluation (ACE) unit. The results show acceptable FCC performance of bitumen virgin HGO when an adequate amount of SCO HGO is added. However, the resulting liquid product may need some quality improvement before use. Several observations, including catalyst poisoning by feed nitrogen and the refractory nature of virgin HGO, are evident and help to explain some observed cracking phenomena.

Correlation of combustor lean blowout performance to supercritical pyrolysis products

Studies to assess correlations between fuel pyrolysis products and fuel-to-air equivalence ratio at combustor lean blowout (LBO) were conducted. Eighteen fuels, including conventional and alternative fuel formulations and blends, single compounds and binary surrogates of hydrocarbon compounds, were studied. The pyrolysis tests consisted of thermally cracking the fuels in a flow reactor at supercritical conditions of 4.14 MPa and up to 625 °C, at varying residence times. The liquid and gaseous pyrolysis products were analyzed via gas chromatography to correlate yields to the fuel LBO data acquired in a previous study on a single-nozzle swirl-stabilized combustor. Focus was given to correlate LBO with primary decomposition products, since it is hypothesized that fuel combustion characteristics, particularly ignition and flame extinction, are related to the rate and type of products formed upon initial thermal decomposition of the parent fuel. Therefore, only the range of conversions for which low molecular weight products had a near-constant formation rate was considered. Results show that the highly branched fuels primarily decomposed to branched C4 and methane, while fuels with high concentration of linear alkanes show greater yields of C2-C4 alkanes and 1-alkenes. Regression analyses of the pyrolysis gas and LBO data show very strong correlations (R2 > 0.90) for several pyrolysis products for the conventional and alternative fuels, with ethane, ethylene and iso-butylene yields providing the best correlations to LBO. The calculated LBOs based on regression parameters and concentrations of the pyrolysis gases were within 2% of the measured LBO for most fuels tested. These initial results suggest that despite the vast differences in fuel reaction timescales in the flow reactor (∼0.2–11 s) and combustor environments (<0.5 ms), fuel pyrolysis species in a flow reactor environment are relevant and may be used to predict fuel combustion behavior. If further validated, this method provides a capability to identify fuel components that can improve combustion performance via their primary pyrolytic product slates, potentially providing a more cost-effective alternative to combustion testing for determination of fuel combustion performance metrics. Results of the pyrolysis tests of all fuels, and future efforts are discussed.

Activated Niobium and Tantalum Imido Complexes: From Tuneable Polymerization to Selective Ethylene Dimerization Systems

AbstractThe niobium and tantalum imido complexes [CpMCl2(NDipp)], [MCl3(NR)(dme)] (R=tBu, Ph, 2,6‐iPr2C6H3 (Dipp), and Mes), and [TaCl3(NDipp)(tmeda)] were tested in combination with EtAlCl2 for the dimerization of ethylene. The niobium systems afforded dimers or polymers, depending on the nature of the imido ligand, with overall productivities in the range 720 to 13,720 (mol C2H4)(mol Nb)−1. The nature of the polyethylene produced (LDPE or HDPE) depended on the imido ligand and the niobium concentration at which catalysis was run. In contrast, the tantalum/dme systems all mediated ethylene dimerization with productivities of up to 4,503 (mol C2H4)(mol Ta)−1, with overall selectivities to butenes of between 73–81 wt %; selectivity within the dimer fraction to 1‐butene was in the range 72 to 100 %. The productivity of [TaCl3(NDipp)(tmeda)] was six times higher than that of its dme‐bearing counterpart, but at the cost of selectivity to 1‐butene. For the tantalum imido‐mediated ethylene dimerization the composition of the product slate formed is indicative of a metallacyclic mechanism being operative.

Technologies and Measures for Increasing Gasoline Production

As an important fuel energy source, gasoline plays a very important role in the national economy development of our country. Gasoline production increasing is a primary mission for petrochemical enterprises at present and even over a long period in the future to optimize production operation plan, adjust product slate, meet market demand and improve economic performance. This paper deeply analyzes and identifies gasoline production increasing potential of enterprises based on the practical production operation of C Company, considering the development progress and industrialized application of alkylation technology, isomerization technology, etherification technology, MTBE technology, residue hydrogenation technology, catalytic cracking and LCO hydro-upgrading-catalytic cracking combination technology at home and abroad. Additionally, this paper proposes constructive solutions for enterprises to further increase the production of gasoline, reduce diesel-gasoline ratio, optimize product slate, tap potentiality and increase efficiency and provides a reference for petroleum and petrochemical enterprises to establish slate adjustment development plan, on the basis of the long-term development plan of enterprises, aiming at “comprehensive utilization of resources by refining-chemical integration, increase gasoline blending components, increase the production of automobile gasoline and optimize product slate”, in the aspects of “plant operation scheme, catalyst grading scheme, production and processing scheme, plant slate adjustment and plant general process design”, etc.

Hydrothermal Treatment of E-Waste Plastics for Tertiary Recycling: Product Slate and Decomposition Mechanisms

Amounts of e-waste plastics have been one of the fast growing global waste streams and threaten to grow into an unmanageable problem. This phenomenon needs to be solved urgently by efficient and cost-effective ways. In this study, a novel hydrothermal treatment technology was implemented to convert the e-waste plastics into organic products which can be used as monomers of plastic production or chemical feedstock. We systematically investigated the recovery efficiencies of organic products, the product slate, the possible hydrothermal degradation mechanisms, and the microstructure of solid residues. The results showed that the yields of organic products derived from four kinds of e-waste plastics ranged from 81.4 to 97.6 wt % at 350 °C. The recovered products contained styrene monomers, styrene derivatives, bisphenol A (BPA), caprolactam (CPL), and other valuable commodity chemicals. On the basis of the systematic analysis of hydrothermal organic products, the possible degradation mechanisms were proposed...

Photosensitization of electro-active microbes for solar assisted carbon dioxide transformation

Tandem bio-inorganic platform by combining efficient light harvesting properties of nano-inorganic semiconductor cadmium sulfide (CdS) with biocatalytic ability of electro-active bacteria (EAB) towards carbon dioxide (CO2) conversion is reported. Sulfur was obtained from either cysteine (EAB-Cys-CdS) or hydrogen sulfide (EAB-H2S-CdS) and experiments were carried out under similar conditions. Anchoring of the nano CdS cluster on the microbe surface was confirmed using electronic microscope. Bio-inorganic hybrid system was able to produce single and multi-carbon compounds from CO2 in visible spectrum (λ > 400 nm). Though, acetic acid was dominant (EAB-Cys-CdS, 1.46 g/l and EAB-H2S-CdS, 1.55 g/l) in both the microbe-CdS hybrids, its concentration as well as product slate varied significantly. EAB-H2S-CdS produced hexanoic acid and less methanol fraction, while the EAB-Cys-CdS produced no hexanoic acid along with almost double the concentration of methanol. Due to easy harvesting process, this bio-inorganic hybrid represents unique sustainable approach for solar-to-chemical production via CO2 transformation.

Influence of catalyst bed temperature and properties of zeolite catalysts on pyrolysis-catalysis of a simulated mixed plastics sample for the production of upgraded fuels and chemicals

The pyrolysis-catalysis of a simulated mixture of plastics representing the plastic mixture found in municipal solid waste has been carried out to determine the influence of process conditions on the production of upgraded fuel oils and chemicals and gases. The catalysts used were spent zeolite from a fluid catalytic cracker (FCC), Y-zeolite and ZSM-5 zeolite. The addition of a catalyst to the process produced a marked increase in gas yield, with more gas (mainly C1–C4 hydrocarbons) being produced as the temperature of the catalyst was raised from 500 °C to 600 °C. The Si/Al ratio of the catalysts influenced the composition of other gases with the more basic catalysts producing more CO and the strongly acidic catalyst producing more H2. The yield of product oil decreased with the addition of the catalysts, but the oil was of significantly lower molecular weight range, containing a product slate of premium fuel range C5–C15 hydrocarbons. In addition, the content of aromatic compounds in the product oil was increased; for example, benzene and toluene accounted for more than 90% of the aromatic content of the oil from the strongly acidic Y-zeolite catalysts. A reaction scheme is proposed for the production of single-ring aromatic compounds via pyrolysis-catalysis of plastics.

Products derived from waste plastics (PC, HIPS, ABS, PP and PA6) via hydrothermal treatment: Characterization and potential applications

In this study, hydrothermal method was applied for the treatment of five typical waste plastics (PC, HIPS, ABS, PP and PA6). The hydrothermal products of oils and solid residues were analyzed for the product slate and combustion behaviors. Some predominant chemical feedstock were detected in the oils, such as phenolic compounds and bisphenol A (BPA) in PC oils, single-ringed aromatic compounds and diphenyl-sketetons compounds in HIPS and ABS oils, alkanes in PP oils, and caprolactam (CPL) in PA6 oils. The hydrothermal solid residues were subjected to DSC analysis. Except the solid residues of PA6, all the solid residues had enormous improvement on the enthalpy of combustion. The solid residues of PC had the maximum promotion up to 576.03% compared to the raw material. The hydrothermal treatment significantly improved the energy density and facilitated effective combustion. Meanwhile, the glass fiber was recovered from the PA6 plastics. In addition, the combustion behaviors of the uplifting residues were investigated to provide the theoretical foundation for further study of combustion optimization. All the results indicated that the oils of waste plastics after hydrothermal treatment could be used as chemical feedstock; the solid residues of waste plastics after hydrothermal treatment could be used as potentially clean and efficient solid fuels. The hydrothermal treatment for various waste plastics was verified as a novel waste-to-energy technique.

Fast Pyrolysis of Opuntia ficus-indica (Prickly Pear) and Grindelia squarrosa (Gumweed)

Opuntia ficus-indica (prickly pear) and Grindelia squarrosa (gumweed) are two exceptionally drought tolerant plant species capable of growing in arid and semiarid environments. Additionally, they have unique cell wall structures. Prickly pear contains pectin and high levels of ash (16.1%) that is predominantly Ca and K. Gumweed has high levels of extractives that contain grindelic acid and monoterpenoids. The objective of this paper was to evaluate how these unique cell wall components alter the pyrolysis performance of prickly pear and gumweed. Using a tandem micropyrolyzer with GC-MS/FID/TCD, a detailed account of the product slate is given for products generated between 450 and 650 °C. Pyrolysis of prickly pear showed that the high levels of ash increase the amount of organics volatilized and shifted product pools, making it possible to generate up to 7.3% carbonyls vs 3.8% for Pinus taeda (loblolly pine) and 10.5% hydrocarbons vs 1.8% for pine depending on reaction conditions. Pyrolysis of gumweed sho...

Long-term operation of electro-biocatalytic reactor for carbon dioxide transformation into organic molecules

Electro-biocatalytic reactor was operated using selectively enriched mixed culture biofilm for about 320 days with CO2/bicarbonate as C-source. Biocathode consumed higher current (−16.2 ± 0.3 A/m2) for bicarbonate transformation yielding high product synthesis (0.74 g/l/day) compared to CO2 (−9.5 ± 2.8 A/m2; 0.41 g/l/day). Product slate includes butanol and butyric acid when CO2 gets transformed but propionic acid replaced both when bicarbonate gets transformed. Based on electroanalysis, the electron transfer might be H2 mediated along with direct transfer under bicarbonate turnover conditions, while it was restricted to direct under CO2. Efficiency and stability of biofilm was tested by removing the planktonic cells, and also confirmed in terms of Coulombic (85–97%) and carbon conversion efficiencies (42–48%) along with production rate (1.2–1.7 kg/m2 electrode) using bicarbonate as substrate. Selective enrichment of microbes and their growth as biofilm along with soluble CO2 have helped in efficient transformation of CO2 up to C4 organic molecules.

Scalable and Tunable Carbide–Phosphide Composite Catalyst System for the Thermochemical Conversion of Biomass

We have prepared composite materials of hexagonal nickel phosphide and molybdenum carbide (Mo2C) utilizing a simple and scalable two-stage synthesis method composed of carbothermic reduction followed by hydrothermal incubation. We observe the monophasic hexagonal phosphide Ni2P in the composite at low phosphide-to-carbide (P:C) ratios. Upon an increase in the proportion of P:C, the carbide surface becomes saturated, and we detect the emergence of a second hexagonal nickel phosphide phase (Ni5P4) upon annealing. We demonstrate that vapor-phase upgrading (VPU) of whole biomass via catalytic fast pyrolysis is achievable using the composite material as a catalyst, and we monitor the resulting product slates using pyrolysis-gas chromatography/mass spectrometry. Our analysis of the product vapors indicates that variation of the P:C molar ratio in the composite material affords product slates of varying complexity and composition, which is indicated by the number of products and their relative proportions in the...