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At least 19 records

Enhanced alcohol production over binary Mo/Co carbide catalysts in syngas conversion

Recently metal carbide catalysts have attracted attention as alternatives to pure metals for the conversion of syngas to higher oxygenates, a process which could enable the sustainable production of fuels, polymers, and chemicals. Although Mo and Co carbides have both shown promise for higher oxygenate production, they have not achieved the requisite activity and selectivity for practical implementation. In this work we synthesize and characterize a binary Mo and Co carbide catalyst that exhibits improved activity and oxygenate selectivity relative to either pure metal carbide. In this work, we apply a combination of advanced electron microscopy and X-ray diffraction to show that the binary Mo/Co carbide catalyst forms uniformly mixed amorphous nanoparticles. Through in situ X-ray absorption spectroscopy studies, we determine that the structure of the mixed metal carbide catalyst under reaction conditions consists of both carbidic and bimetallic components. By testing the catalytic properties of a series of Mo/Co carbide catalysts prepared by different synthesis methods, we find that the Mo and Co sites must be in close contact to achieve improved syngas conversion to higher alcohols. Through in situ DRIFTS measurements, both Mo and Co atoms at the surface of the catalyst are identified as adsorption sites for reactive species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding Support Effects of ZnO-Promoted Co Catalysts for Syngas Conversion to Alcohols Using Atomic Layer Deposition

Co 2 C, an emerging catalyst for the conversion of syngas to oxygenates, shows support-sensitive behavior that has not yet been fully explained. In this work, we characterize Co catalysts modified with ZnO atomic layer deposition on SiO 2 , carbon, CeO 2 , and Al 2 O 3 supports. We find that under syngas conditions, ZnO-promoted Co transforms into Co 2 C on SiO 2 , carbon, and CeO 2 , but not on Al 2 O 3 . Moreover, the support affects the extent of carburization: while the SiO 2 -supported catalyst carburizes completely, carbon- and CeO 2 -supported catalysts show incomplete conversion of Co to Co 2 C. These three catalysts also exhibit different oxygenate selectivities. In contrast, the modified Al 2 O 3 -supported catalyst retains the Fischer-Tropsch catalytic properties of metallic Co. By depositing increasing amounts of Al 2 O 3 by ALD on the SiO 2 support, decreasing Co 2 C formation and oxygenate selectivity occurs. In-situ XANES reveals that Al 2 O 3 prevents Co 2 C formation by enabling the ZnO to restructure into ZnAl 2 O 4 during reduction. Thus, in addition to modifying the active catalyst phase, the promoter can also strongly interact with the support, significantly impacting catalyst performance.

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Understanding Structure–Property Relationships of MoO 3 -Promoted Rh Catalysts for Syngas Conversion to Alcohols

Rh-based catalysts have shown promise for the direct conversion of syngas to higher oxygenates. Although improvements in higher oxygenate yield have been achieved by combining Rh with metal oxide promoters, details of the structure of the promoted catalyst and the role of the promoter in enhancing catalytic performance are not well understood. In this work, we show that MoO 3 -promoted Rh nanoparticles form a novel catalyst structure in which Mo substitutes into the Rh surface, leading to both a 66-fold increase in turnover frequency and an enhancement in oxygenate yield. By applying a combination of atomically controlled synthesis, in situ characterization, and theoretical calculations, we gain an understanding of the promoter-Rh interactions that govern catalytic performance for MoO 3 -promoted Rh. We use atomic layer deposition to modify Rh nanoparticles with monolayer-precise amounts of MoO 3 , with a high degree of control over the structure of the catalyst. Through in situ X-ray absorption spectroscopy, we find that the atomic structure of the catalytic surface under reaction conditions consists of Mo–OH species substituted into the surface of the Rh nanoparticles. Furthermore, using density functional theory calculations, we identify two roles of MoO 3 : first, the presence of Mo–OH in the catalyst surface enhances CO dissociation and also stabilizes a methanol synthesis pathway not present in the unpromoted catalyst; and second, hydrogen spillover from Mo–OH sites to adsorbed species on the Rh surface enhances hydrogenation rates of reaction intermediates.

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Catlas: an automated framework for catalyst discovery demonstrated for direct syngas conversion

Catalyst discovery is paramount to support access to energy and key chemical feedstocks in a post fossil fuel era. Exhaustive computational searches of large material design spaces using ab initio methods like density functional theory (DFT) are infeasible. We seek to explore large design spaces at relatively low computational cost by leveraging large, generalized, graph-based machine learning (ML) models, which are pretrained and therefore require no upfront data collection or training. We present Catlas, a framework that distributes and automates the generation of adsorbate-surface configurations and ML inference of DFT energies to achieve this goal. Catlas is open source, making ML assisted catalyst screenings easy and available to all. To demonstrate its efficacy, we use Catlas to explore catalyst candidates for the direct conversion of syngas to multi-carbon oxygenates. For this case study, we explore 947 stable/metastable binary, transition metal intermetallics as possible catalyst candidates. On this subset of materials, we are able to predict the adsorption energy of key descriptors, *CO and *OH, with good accuracy (0.16, 0.14 eV MAE, respectively). Using the projected selectivity towards C 2+ oxygenates from an existing microkinetic model, we identified 144 candidate materials. For 10 promising candidates, DFT calculations reveal a good correlation with our assessment using ML. Finally, among the top elemental combinations were Pt–Ti, Pd–V, Ni–Nb, and Ti–Zn, all of which appear unexplored experimentally.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impurity Control in Catalyst Design: The Role of Sodium in Promoting and Stabilizing Co and Co 2 C for Syngas Conversion

The design of supported heterogeneous catalysts requires a detailed understanding of the structure and chemistry of the active surface. Although the chemical components of the active phase, support material, and process feed are typically considered to be the most important factors governing catalyst structure and performance, many common commercial supports contain trace impurities, which can have profound effects on catalyst properties. In this work, we study silica–supported cobalt–based catalysts, which are widely used in syngas conversion to value–added products. Supported metallic Co is a commercial Fischer–Tropsch catalyst, whereas Co 2 C has shown promise for the direct conversion of syngas to higher oxygenates. This study examines the effects of Na, a commonly detected support impurity and a frequently used promoter, on the structure and reactivity of Co and Co 2 C. We show that trace Na impurities significantly decrease catalyst activity of supported metallic Co, and that high Na concentrations result in Co 2 C formation and a loss in Fischer–Tropsch activity. However, in Co 2 C catalysts, Na plays an important role in stabilizing the Co 2 C phase, but excess Na decreases catalyst activity. We use insitu X–ray absorption spectroscopy to study Co 2 C formation and decomposition in the Na–free catalyst under carburization and reaction conditions. Lastly, the work reveals the importance of carefully controlling alkali metal content, particularly at trace levels, in catalyst design.

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Selective and Stable In-Promoted Fe Catalyst for Syngas Conversion to Light Olefins

A selective and stable alumina-supported In-promoted Fe catalyst (10 mol % In based on Fe) was discovered for converting syngas (2:1 H 2 /CO ratio) to olefins with high selectivity (45% with CO 2 included) and a remarkable stability (72 h run) at a CO conversion of 10% at 400 °C and 5 bar. The X-ray photoelectron spectroscopy results indicated that incorporating In into Fe catalysts changed the chemical bonding state of Fe and Fe/In composition near the surface layers, which affected the catalytic reactivity. Steady-state isotopic transient kinetic analysis showed that more stable CHx fragments are present on the catalyst surface when incorporating In into Fe, which can promote C–C coupling reaction toward olefins. Our study demonstrates that introducing In into Fe catalysts on Al 2 O 3 support can lower CO activation abilities. It has more impacts on lowering hydrogenation activity, which permits more C–C couplings and like of “ene” hydrogenation. Furthermore, weakening CO adsorption both in terms of sites and strength encouraged CO toward hydrocarbons rather than CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Conversion of Syngas and CO2 to Light Olefins using Multi-Functional Catalysts

This report describes our effort in developing a novel zeolite encapsulated metal nanoparticle catalyst for the conversion of syngas to light olefins. We have adopted a ligand assisted synthesis protocol in which first metal-amine was prepared using metal salts and suitable amine ligands. The stable metal-amine complex thus prepared was then used as the seed for the growth of zeolite in alkaline solution. We have optimized the synthesis condition as well as different amine ligand to identify the condition to obtain stable metal-amine complex. Upon synthesis of zeolite, metal particles are encapsulated inside the zeolite in a confined space. We have synthesized both Fe and Co catalyst inside silicalite and chabazite zeolite. Catalytic activity of these catalysts were evaluated for syngas conversion reaction and compared with a baseline catalyst. The activity trend of zeolite encapsulated catalyst show very different activity trend compared to the baseline catalyst. While a distribution of products with different carbon number was obtained with baseline catalyst, zeolite encapsulated catalyst show ethylene as the major product. While ~73% selectivity to C 2 -C 6 products were obtained with cahabazite encapsulated Fe catalyst, only 53% selectivity was obtained for the corresponding products with silica-alumina supported Fe catalyst. Not only higher selectivity, Fe-chabazite also produces only C 2 products (ethylene/ethane) while a distribution of products was obtained with Fe-SiAl catalyst. The significantly different reactivity associated with the chabazite encapsulated Fe catalyst was attributed to the confinement effect. We hypothesized that due to the small size of the pore, only ethylene was obtained as the product.

10 SYNTHETIC FUELS↗

Identifying higher oxygenate synthesis sites in Cu catalysts promoted and stabilized by atomic layer deposited Fe 2 O 3

The conversion of syngas to higher oxygenates is an important step in the pathway towards the long-term sustainable production of fuels and chemicals. Mixed Cu/Fe catalysts combine metals with different CO activation characteristics, a property that makes them promising candidates for higher oxygenate production. However, Cu/Fe catalysts suffer from instability due to sintering and phase separation, and the active sites for higher oxygenate formation on these materials are not well understood. In this work, we use atomic layer deposition (ALD) to modify silica-supported Cu nanoparticles with monolayer precise amounts of Fe 2 O 3 and study the effects on catalyst structure, reactivity, and stability. We demonstrate that the Fe 2 O 3 ALD process is inherently selective towards deposition on the SiO 2 surface versus the Cu nanoparticles. As a result, a sufficiently thick Fe 2 O 3 layer surrounding the Cu nanoparticles acts as a barrier against Cu migration, preventing catalyst deactivation through sintering without covering the Cu. In syngas conversion reactions, we find that higher oxygenate selectivity increases with Fe 2 O 3 loading at low and intermediate ALD cycle numbers. Furthermore, using in situ X-ray absorption spectroscopy, we demonstrate that the Fe near the Cu nanoparticles is reduced to a metallic state under reaction conditions. From these measurements, we identify these metallic Cu/Fe interfaces as the active sites for higher oxygenate formation, which are most abundant at intermediate Fe 2 O 3 ALD cycle numbers. As the Fe 2 O 3 loading increases, higher oxygenate selectivity falls, resulting from encapsulation of the Cu nanoparticles by thick Fe 2 O 3 layers. Overall, the results demonstrate how thickness-controlled ALD Fe 2 O 3 can be used as both a promoter and stabilizer of Cu-based higher oxygenate synthesis catalysts.

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Efficient conversion of syngas to linear α-olefins by phase-pure χ-Fe5C2

Abstract Oil has long been the dominant feedstock for producing fuels and chemicals, but coal, natural gas and biomass are increasingly explored alternatives 1–3 . Their conversion first generates syngas, a mixture of CO and H 2 , which is then processed further using Fischer–Tropsch (FT) chemistry. However, although commercial FT technology for fuel production is established, using it to access valuable chemicals remains challenging. A case in point is linear α-olefins (LAOs), which are important chemical intermediates obtained by ethylene oligomerization at present 4–8 . The commercial high-temperature FT process and the FT-to-olefin process under development at present both convert syngas directly to LAOs, but also generate much CO 2 waste that leads to a low carbon utilization efficiency 9–14 . The efficiency is further compromised by substantially fewer of the converted carbon atoms ending up as valuable C 5 –C 10 LAOs than are found in the C 2 –C 4 olefins that dominate the product mixtures 9–14 . Here we show that the use of the original phase-pure χ-iron carbide can minimize these syngas conversion problems: tailored and optimized for the process of FT to LAOs, this catalyst exhibits an activity at 290 °C that is 1–2 orders higher than dedicated FT-to-olefin catalysts can achieve above 320 °C (refs. 12–15 ), is stable for 200 h, and produces desired C 2 –C 10 LAOs and unwanted CO 2 with carbon-based selectivities of 51% and 9% under industrially relevant conditions. This higher catalytic performance, persisting over a wide temperature range (250–320 °C), demonstrates the potential of the system for developing a practically relevant technology.

Science & Technology - Other Topics↗

Conversion of Syngas to Light Olefins and Oxygenates using Multi-Functional Catalysts

This report describes our effort in developing catalysts for the conversion of syngas to light olefins and oxygenates. We have developed a series of metal/zeolite catalysts and tested their activity towards the conversion of syngas to light olefins. Light olefins produced in our case mostly comprised of C 2 /C 3 . A series of multimetallic catalyst also synthesized and their performance was evaluated for the conversion of syngas to the production of oxygenates. In case of oxygenates, our specific focus was to maximize the selectivity of C 2+ oxygenates which is a precursor for fuel or can be used as high value chemicals. In this direction, we have identified several Rh based catalysts that are specifically shows superior activity towards oxygenates formation.

10 SYNTHETIC FUELS↗

Direct conversion of syngas to lower olefins precursors of jet fuel and chemicals

This study investigates the direct conversion of syngas to olefins as a pathway to produce sustainable aviation fuels. This approach combines methanol/ dimethyl ether synthesis with methanol-to-olefins into one unit operation to avoid the equilibrium limitation of methanol synthesis and the Anderson–Schulz–Flory distribution limitations from the Fischer Tropsch process. The ability to combine reactor functionalities into a single step are also projected to significantly lower capital costs over current synthesis approaches for the syngas to olefins process.

10 SYNTHETIC FUELS↗

Conversion of syngas into light olefins in one step for process-intensified production of sustainable aviation fuels

Here, we report on a preliminary investigation for direct conversion of syngas into olefins. This technology combines alcohol(s) production and olefin(s) production into a single unit operation to improve process efficiencies due to the overcoming of equilibrium limitations and also to offer capital savings relative to current synthesis approaches including Fischer-Tropsch synthesis, methanol-to-olefins followed by olefins to gasoline/distillate process and alcohol-to-jet process.

10 SYNTHETIC FUELS↗

A separations and purification process for improving yields and meeting fuel contaminant specifications for high-octane gasoline produced from dimethyl-ether over a Cu/BEA catalyst

In this work, we have been developing a three-step conversion of biomass-derived syngas to methanol to dimethyl-ether (DME) to non-aromatic hydrocarbons for use as high-octane gasoline and sustainable aviation fuel. This process produces branched alkanes from DME using a Cu/BEA catalyst and is a promising alternative to other syngas conversion processes such as Fischer-Tropsch to linear alkanes and traditional ZSM-5 catalyzed methanol to aromatic gasoline. In this short article we describe some advances in our understanding related to separations and purification via the use of more detailed experimental speciation in an updated process model involving multiple phase equilibrium-based separation steps. Primary modeled reactor outlet constituents (and weight %) are: C3 and lighter hydrocarbon gases (11.1%), C4s (54.5%), H 2 (1.2%), CO 2 (2.9%), water (5.0%), unreacted DME (16.5%), methanol (2.3%), and C5+ hydrocarbons (6.4%). DME (the primary reactant) and H 2 recycle and reuse are important for the overall process efficiency, and the recycle of C4s is important to increase the C5+ yield via reactivation and homologation. Thus H 2 , C4s, and DME are targeted for recycle, while methanol and water need to be removed from the product to conform with fuel specifications. Model predictions from Aspen Plus using the NRTL-RK property method indicate a fuel composition with C5+ content of 97.1 wt%, with minor constituents: 2.4 wt% C4s, 0.3 wt% methanol, 0.1 wt% DME, 0.03 wt% water, and 0.01 wt% C3s. These ranges of minor components conform with fuel quality requirements, and the modeled product is amenable for unconstrained blending to boost gasoline octane ratings.

09 BIOMASS FUELS↗

CO 2 conversion to syngas via electrification of endothermal reactors: Process design and environmental impact analysis

CO 2 utilization via reverse water gas shift (rWGS) reaction has been proposed as a path to the sustainable utilization. Here this work presents a detailed process modelling study where steam methane reforming (SMR) generated hydrogen was combined with rWGS to produce syngas (CO + H 2 ) with various hydrogen-to-carbon oxide ratios. To further decrease CO 2 emissions that may offset the benefits of CO 2 converted in rWGS, electrification of endothermal reactors, both SMR and rWGS was considered where CO 2 emitting fuel burning in the furnace was replaced by the emerging ohmic (resistive) heating. Material and energy inventory obtained from process design calculations was used to perform Life Cycle Analysis (LCA) to calculate environmental impacts of CO 2 consumption and reactor electrification. The results showed that greenhouse gas emissions, in CO 2 kg equivalent, were the lowest when both SMR and rWGS were heated using wind-generated electricity, decreasing from 25 to 10 kg CO 2 equivalent for H 2 :CO = 2:1 while the conventional electricity mix used for furnace electrical heating across the board of scenarios generated highest environmental impacts, much higher than those that used natural gas as fuel. Process economics calculations suggested that, when both SMR and rWGS were electrically heated, the process only showed product syngas cost parity with the conventional fuel heated design when electricity cost was ~$0.008/kWh. This suggests that CO 2 utilization scenarios involving process electrification need to be carefully considered from the total design perspective so they do not produce more greenhouse gases than in conventional non-electrified scenarios.

42 ENGINEERING↗

Phosphate-passivated mordenite for tandem-catalytic conversion of syngas to ethanol or acetic acid

Selective and stable production of C 2 oxygenates from syngas is enabled by a phosphate-passivated mordenite catalyst used in tandem with a commercial Cu/ZnO/AlMgO x catalyst. Unmodified mordenite used in this arrangement is accompanied by substantial hydrocarbon formation and carbon deposition. Therefore, phosphate groups are used to remove or significantly reduce Brønsted acidity in mordenite by capping aluminum sites. Such groups are stable to calcination and catalyst regeneration. Here, trimethylphosphite is used as a phosphate precursor because it is able to enter the 12 membered-ring pores of mordenite where hydrocarbon formation occurs, but not enter the 8 membered-ring sidepockets, where methanol carbonylation occurs selectively. The catalyst was characterized using X-ray fluorescence, X-ray diffraction, and thermal gravimetric analysis. Optionally, a third bed of Cu/ZnO/AlMgO x catalyst is able to hydrodeoxygenate acetic acid to ethanol. The C 2 oxygenate selectivity is over 96% and among the best reported in a single reactor with a syngas feed.

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