Industrial Off-gas Research Articles

Biocatalytic conversion of carbon dioxide to formate using a robust metal-independent Thiobacillus formate dehydrogenase

The capture and utilization of CO2 from industrial off-gases to produce commodity chemicals has the potential to make an important contribution to the transition to a circular economy. Formate, and its conjugate formic acid, is a potential sustainable platform chemical that can be produced from CO2. Electrochemical reduction of CO2 to formate is a promising route, but biocatalysis with formate dehydrogenase (FDH) as biocatalyst may offer advantages for industrial implementation such as mild conditions, high product selectivity, and less expensive down-stream processing. Here, we investigated the potential of a metal-independent Thiobacillus FDH (TsFDH) as a biocatalyst for the production of formate from CO2-rich industrial offgases. An excellent stability was demonstrated, also in the presence of potential off-gas impurities. A formate titer of 14 mM could be achieved at pH 6.5 and 37 °C, with an initial specific productivity of 0.37 mmol g−1 FDH h−1. TsFDH compares favorably to metal-dependent FDHs with respect to stability, O2-sensitivity and activity at low pH values, but unfavorably in terms of CO2 reduction activity, hampering its potential as industrial biocatalyst. Specific rates could be significantly improved by further reaction engineering, and possibly also by enzyme engineering.

Fine-Tuning Microporosity of Crystalline Vanadomolybdate Frameworks for Selective Adsorptive Separation of Kr from Xe.

Selective adsorptive capture and separation of chemically inert krypton (Kr) and xenon (Xe) noble gases with very low ppmv concentrations in air and industrial off-gases constitute an important technological challenge. Here, using a synergistic combination of experiment and theory, the microporous crystalline vanadomolybdates (MoVOx) as highly selective Kr sorbents are studied in detail. By varying the Mo/V ratios, we show for the first time that their one-dimensional (1D) pores can be fine-tuned for the size-selective adsorption of Kr over the larger Xe with selectivities reaching >100. Using extensive electronic structure calculations and grand canonical Monte Carlo simulations, the competition between Kr uptake with CO2 and N2 was also investigated. As most materials reported so far are selective toward the larger, more polarizable Xe than Kr, this work constitutes an important step toward robust Kr-selective sorbent materials. This work highlights the potential use of porous crystalline transition metal oxides as energy-efficient and selective noble gas capture sorbents for industrial applications.

Pros and cons of airlift and bubble column bioreactors: How internals improve performance

Gas fermentation is a promising technology of high commercial interest, particularly for capturing CO2 and CO from industrial off-gases to reduce greenhouse gas emissions and replace fossil fuels for bulk chemical production. Therefore, evaluating promising bioreactor settings ab initio is a crucial step. Whereas alternate configurations may be tested in laborious scale up studies, the procedure may be accelerated by in silico studies that accompany or even partially replace wet-lab work once the models are validated. In this context, the current study compares various pneumatically agitated reactor types – bubble column reactor (BCR), annulus- and center-rising internal-loop airlift reactor (AR-IL-ALR and CR-IL-ALR), and external-loop airlift reactor (EL-ALR) – to identify advantages and disadvantages for the given application based on computational fluid dynamics (CFD) models. Process performance is optimized by introducing internal structures to guide the flow. Despite a significant increase in the mass transfer coefficient (kLa) through internal modifications, the CR-IL-ALR still exhibited the poorest performance. The optimized AR-IL-ALR demonstrated good mixing and, after introducing an open-cone shaped internal in the head part and a conical bottom, superior mass transfer, achieving an enhancement over 10 % in the mass transfer coefficient to 315 1/h. This study thereby outlines the potential of internal structures for process improvement, as well as the value of a priori in silico design of reactor configurations.

Tailored Cu-Fe-based oxygen carrier for moderate-temperature chemical looping hydrogen generation from blast furnace gas

Chemical looping hydrogen generation (CLHG) offers a promising solution for producing H2 from industrial off-gas, such as blast furnace gas. However, increasing H2 production capacity of the oxygen carrier (OC) at moderate temperature remains a significant challenge. In this study, a novel Cu-Fe-based OC is tailored for moderate-temperature CLHG from blast furnace gas. The results demonstrates that the tailored OC exhibits a superior H2 production capacity of 12.99 mmol·g−1 at 550 °C, which is 6.5 times higher than that of Fe2O3 at the same temperature. The addition of Cu leads to the formation of oxygen defects, which facilitate the migration of lattice oxygen, thereby the activity of the OC is enhanced. Furthermore, cyclical experiments demonstrates that O2-assisted regeneration strategy can effectively suppress the segregation of Cu during the cycling process, and the tailored OC shows good stability during 10 redox cycles. No additional separation process was required and the purity of the hydrogen was higher than 99%. The findings here open a new avenue for efficient CLHG from industrial off-gas at moderate operation temperature.

Demonstrating Pilot-Scale Gas Fermentation for Acetate Production from Biomass-Derived Syngas Streams

Gas fermentation is gaining attention as a crucial technology for converting gaseous feedstocks into value-added chemicals. Despite numerous efforts over the past decade to investigate these innovative processes at a lab scale, to date, the evaluation of the technologies in relevant industrial environments is scarce. This study examines the fermentative production of acetate from biomass-derived syngas using Moorella thermoacetica. A mobile gas fermentation pilot plant was coupled to a bubbling fluidized-bed gasifier with syngas purification to convert crushed bark-derived syngas. The syngas purification steps included hot filtration, catalytic reforming, and final syngas cleaning. Different latter configurations were evaluated to enable a simplified syngas cleaning configuration for microbial syngas conversion compared to conventional catalytic synthesis. Fermentation tests using ultra-cleaned syngas showed comparable microbial growth (1.3 g/L) and acetate production (22.3 g/L) to the benchmark fermentation of synthetic gases (1.2 g/L of biomass and 25.2 g/L of acetate). Additional fermentation trials on partially purified syngas streams identified H2S and HCN as the primary inhibitory compounds. They also indicated that caustic scrubbing is an adequate and simplified final gas cleaning step to facilitate extended microbial fermentation. Overall, this study shows the potential of gas fermentation to valorize crude gaseous feedstocks, such as industrial off-gases, into platform chemicals.

Enzymatic method for the conversion of carbon monoxide from industrial off-gases into formate

Enzymatic method for the conversion of carbon monoxide from industrial off-gases into formate

Molar-scale formate production via enzymatic hydration of industrial off-gases

Decarbonizing the steel industry, a major CO2 emitter, is crucial for achieving carbon neutrality. Escaping the grip of CO combustion methods, a key contributor to CO2 discharge, is a seemingly simple yet formidable challenge on the path to industry-wide net-zero carbon emissions. Here we suggest enzymatic CO hydration (enCOH) inspired by the biological Wood‒Ljungdahl pathway, enabling efficient CO2 fixation. By employing the highly efficient, inhibitor-robust CO dehydrogenase (ChCODH2) and formate dehydrogenase (MeFDH1), we achieved spontaneous enCOH to convert industrial off-gases into formate with 100% selectivity. This process operates seamlessly under mild conditions (room temperature, neutral pH), regardless of the CO/CO2 ratio. Notably, the direct utilization of flue gas without pretreatment yielded various formate salts, including ammonium formate, at concentrations nearing two molar. Operating a 10-liter-scale immobilized enzyme reactor feeding live off-gas at a steel mill resulted in the production of high-purity formate powder after facile purification, thus demonstrating the potential for decarbonizing the steel industry.

Identifying a key spot for electron mediator-interaction to tailor CO dehydrogenase’s affinity

Fe‒S cluster-harboring enzymes, such as carbon monoxide dehydrogenases (CODH), employ sophisticated artificial electron mediators like viologens to serve as potent biocatalysts capable of cleaning-up industrial off-gases at stunning reaction rates. Unraveling the interplay between these enzymes and their associated mediators is essential for improving the efficiency of CODHs. Here we show the electron mediator-interaction site on ChCODHs (Ch, Carboxydothermus hydrogenoformans) using a systematic approach that leverages the viologen-reactive characteristics of superficial aromatic residues. By enhancing mediator-interaction (R57G/N59L) near the D-cluster, the strategically tailored variants exhibit a ten-fold increase in ethyl viologen affinity relative to the wild-type without sacrificing the turn-over rate (kcat). Viologen-complexed structures reveal the pivotal positions of surface phenylalanine residues, serving as external conduits for the D-cluster to/from viologen. One variant (R57G/N59L/A559W) can treat a broad spectrum of waste gases (from steel-process and plastic-gasification) containing O2. Decoding mediator interactions will facilitate the development of industrially high-efficient biocatalysts encompassing gas-utilizing enzymes.

Process systems engineering perspectives on eco-efficient downstream processing of volatile biochemicals from fermentation

Increasing concerns over environmental pollution, climate change and energy security are driving a necessary transition from fossil carbon sources to more sustainable alternatives. Due to lower environmental impact, biochemicals are rapidly gaining significance as a potential renewable solution, particularly of interest in Europe. In this context, process systems engineering (PSE) helps with the decision-making at multiple scales and levels, aiming for optimum use of (renewable) resources. Fermentation using waste biomass or industrial off-gases is a promising way for the production of these products. However, due to the inhibitory effects or low substrate concentrations, relatively low product concentrations can be obtained. Consequently, significant improvements in downstream processing are needed to increase the competitiveness of the overall bioprocesses. This paper supports sustainable development by providing new PSE perspectives on the purification of volatile bioproducts from dilute fermentation broths. Since purification significantly contributes to the total cost of biochemical production processes (20%–40% of the total cost), enhancing this part may substantially improve the competitiveness of the overall bioprocesses. The highly advanced downstream process offers the possibility of recovering high-purity products while enhancing the fermentation step by continuously removing inhibitory products, and recycling microorganisms with most of the present water. Besides higher productivity, the upstream process can be greatly improved by avoiding loss of biomass, enabling closed-loop operation and decreasing the need for fresh water. Applying heat pumping, heat integration and other methods of process intensification (PI) can drastically reduce energy requirements and CO2 emissions. Additionally, the opportunity to use renewable electricity instead of conventional fossil energy presents a significant step toward (green) electrification and decarbonization of the chemical industry.

Surface-Phosphorylated Ceria for Chlorine-Tolerance Catalysis.

An improved fundamental understanding of active site structures can unlock opportunities for catalysis from conceptual design to industrial practice. Herein, we present the computational discovery and experimental demonstration of a highly active surface-phosphorylated ceria catalyst that exhibits robust chlorine tolerance for catalysis. Ab initio molecular dynamics (AIMD) calculations and in situ near-ambient pressure X-ray photoelectron spectroscopy (in situ NAP-XPS) identified a predominantly HPO4 active structure on CeO2(110) and CeO2(111) facets at room temperature. Importantly, further elevating the temperature led to a unique hydrogen (H) atom hopping between coordinatively unsaturated oxygen and the adjacent P═O group of HPO4. Such a mobile H on the catalyst surface can effectively quench the chlorine radicals (Cl•) via an orientated reaction analogous to hydrogen atom transfer (HAT), enabling the surface-phosphorylated CeO2-supported monolithic catalyst to exhibit both expected activity and stability for over 68 days during a pilot test, catalyzing the destruction of a complex chlorinated volatile organic compound industrial off-gas.

Mechanism Study of Organic Sulfur Hydrogenation over Pt- and Pd-Loaded Alumina-Based Catalysts.

The hydrogenation of organic sulfur (CS2) present in industrial off-gases to produce sulfur-free hydrocarbons and H2S can be achieved by using noble-metal catalysts. However, there has been a lack of comprehensive investigation into the underlying reaction mechanisms associated with this process. In this study, we have conducted an in-depth examination of the activity and selectivity of Pt- and Pd-loaded alumina-based catalysts, revealing significant disparities between them. Notably, Pd/Al2O3 catalysts exhibit an enhanced performance at low temperatures. Furthermore, we have observed that CS2 displays a higher propensity for conversion to methane when employing Pt/Al2O3 catalysts, while Pd/Al2O3 catalysts demonstrate a greater tendency for coke deposition. By combining experimental observations with theoretical calculations, we revealed that the capability of H2 spillover along with the adsorption capacity of CS2, play pivotal roles in determining the observed differences. Moreover, the key intermediate species involved in the methanation and coke pathways were identified. The intermediate CH2S* is found to be crucial in the methanation pathway, while the intermediate CSH* is identified as significant in the coke pathway.

Bio-engineering of carbon adsorbents to capture CO2 from industrial sources: The cement case

Pine cone leaves (PCL) and pine kernel shells (PKS), abundant by-products of the Spanish food industry, were selected as precursors for activated carbons (ACs) to adsorb CO2 selectively at industrial post-combustion capture conditions. The goal was to maximize the development of narrow microporosity in the final carbons to boost the CO2 adsorption capacity. We have designed kinetics and equilibrium of adsorption experiments with CO2/H2O/N2 on a selected AC derived from PCL in a thermogravimetric analyzer (TGA) at 50 °C and three partial pressures of CO2 to prove the suitability to capture CO2 from industrial off-gases. When humid flue gas streams were tested, competitive adsorption of CO2 and H2O occurred; however, the difference in the uptake rates favored CO2 adsorption in the early stages. The joint CO2 + H2O uptake was around 2 mmol g−1 at 50 °C in humid conditions, where CO2 reached the equilibrium uptake at the corresponding partial pressure for 15 and 32 vol% CO2 in the feed stream. Moreover, the dynamic performance was addressed by cyclic adsorption–desorption experiments representing different industrial post-combustion capture scenarios in a lab-scale fixed-bed rig. The selected AC showed a stable performance in adsorption-regeneration cycles and very remarkable CO2 capture capacity under dry conditions (up to 1.08 mmol g−1 at 50 ˚C for 30 vol% CO2). Kinetics analysis also supported the faster adsorption of CO2 under cement flue gas conditions.

Single-Cell Protein Production from Industrial Off-Gas through Acetate: Techno-Economic Analysis for a Coupled Fermentation Approach

Third-generation (3G) biorefineries harnessing industrial off-gases have received significant attention in the transition towards a sustainable circular economy. However, uncertainties surrounding their techno-economic feasibility are hampering widespread commercialization to date. This study investigates the production of single-cell protein (SCP), a sustainable alternative food and feed protein, from steel mill off-gas through an efficient coupled fermentation approach utilizing acetate as an intermediate. A comprehensive model that comprises both the gas-to-acetate and the acetate-to-SCP fermentation processes, as well as gas pretreatment and downstream processing (DSP) operations, was developed and used to perform a techno-economic analysis (TEA). Sensitivity analyses demonstrated that significant cost reductions can be achieved by the process intensification of the gas-to-acetate fermentation. As such, an increase in the acetate concentration to 45 g/L and productivity to 4 g/L/h could lead to a potential cost reduction from 4.15 to 2.78 USD/kg. In addition, the influence of the production scale and other economic considerations towards the commercialization of off-gas-based SCPs are discussed. Conclusively, this research sheds light on the practical viability of a coupled fermentation process for SCP production by identifying key cost-influencing factors and providing targets for further optimization of the acetate platform, fostering sustainable and economically feasible bio-based innovations.

Formate-induced CO tolerance and methanogenesis inhibition in fermentation of syngas and plant biomass for carboxylate production

BackgroundProduction of monocarboxylates using microbial communities is highly dependent on local and degradable biomass feedstocks. Syngas or different mixtures of H2, CO, and CO2 can be sourced from biomass gasification, excess renewable electricity, industrial off-gases, and carbon capture plants and co-fed to a fermenter to alleviate dependence on local biomass. To understand the effects of adding these gases during anaerobic fermentation of plant biomass, a series of batch experiments was carried out with different syngas compositions and corn silage (pH 6.0, 32 °C).ResultsCo-fermentation of syngas with corn silage increased the overall carboxylate yield per gram of volatile solids (VS) by up to 29% (0.47 ± 0.07 g gVS−1; in comparison to 0.37 ± 0.02 g gVS−1 with a N2/CO2 headspace), despite slowing down biomass degradation. Ethylene and CO exerted a synergistic effect in preventing methanogenesis, leading to net carbon fixation. Less than 12% of the electrons were misrouted to CH4 when either 15 kPa CO or 5 kPa CO + 1.5 kPa ethylene was used. CO increased the selectivity to acetate and propionate, which accounted for 85% (electron equivalents) of all products at 49 kPa CO, by favoring lactic acid bacteria and actinobacteria over n-butyrate and n-caproate producers. Inhibition of n-butyrate and n-caproate production by CO happened even when an inoculum preacclimatized to syngas and lactate was used. Intriguingly, the effect of CO on n-butyrate and n-caproate production was reversed when formate was present in the broth.ConclusionsThe concept of co-fermenting syngas and plant biomass shows promise in three aspects: by making anaerobic fermentation a carbon-fixing process, by increasing the yields of short-chain carboxylates (propionate and acetate), and by minimizing electron losses to CH4. Moreover, a model was proposed for how formate can alleviate CO inhibition in certain acidogenic bacteria. Testing the fermentation of syngas and plant biomass in a continuous process could potentially improve selectivity to n-butyrate and n-caproate by enriching chain-elongating bacteria adapted to CO and complex biomass.

High efficient separation of H2/CH4 using ZIF-8/glycol-water slurry: Process modelling and multi-objective optimization

Hydrogen (H2) is expected to play a vital role in future global energy system. The efficient and low-energy consumption process for H2/CH4 separation from hydrogen rich industrial off-gas is still a key challenge. The absorption-adsorption process for H2/CH4 separation using ZIF-8/glycol-water slurry is a promising alternative technique due to its high separation efficiency, mild operation conditions and continuous operation mode. We proposed two process configurations: a decompression desorption process A to obtain 99.5 mol% H2; and a process B combined with decompression and H2 stripping desorption to attain 99.99 mol% H2. The detailed process modelling and multiple objective optimizations for two processes are conducted to determine optimal operation conditions, stream characteristics, and unit energy requirements. Results show that the H2 recovery ratio and total unit energy consumption reaches 99.70% and 0.3876 kW·h/Nm3 for Process A; 99.47% and 0.4608 kW·h/Nm3 for Process B, respectively. It indicates the novel process can simultaneously achieve high purity and high H2 recovery with low energy consumption.

Catalysts for gaseous organic sulfur removal.

Organic sulfur gases (COS, CS2 and CH3SH) are widely present in reducing industrial off-gases, and these substances pose difficulties for the recovery of carbon monoxide and other gases. The reaction pathways and reaction mechanisms of organic sulfur on different catalyst surfaces have yet to be fully summarized. The literature shows that many factors, such as catalyst synthesis method, loaded metal composition, number of surface hydroxyl groups, number of acid-base sites and methods of surface modification, have important effects on the catalytic performance of metal catalysts. Therefore, this paper presents a comprehensive review of the research on the application of catalysts such as zeolites, metal oxides, carbon-based materials, and hydrotalcite-like derivatives in the field of organic sulfur removal. Future research prospects are summarized, more in situ characterization experiments and theoretical calculations are needed for the catalytic decomposition of methanethiol to analyze the coke generation pathways at the microscopic level, while the simultaneous removal of multiple organic sulfur gases needs to be focused on. Based on previous catalyst research, we propose possible innovations in catalyst design, desulfurization technology and organic sulfur resource utilization technology.

Model-driven approach for the production of butyrate from CO2/H2 by a novel co-culture of C. autoethanogenum and C. beijerinckii.

One-carbon (C1) compounds are promising feedstocks for the sustainable production of commodity chemicals. CO2 is a particularly advantageous C1-feedstock since it is an unwanted industrial off-gas that can be converted into valuable products while reducing its atmospheric levels. Acetogens are microorganisms that can grow on CO2/H2 gas mixtures and syngas converting these substrates into ethanol and acetate. Co-cultivation of acetogens with other microbial species that can further process such products, can expand the variety of products to, for example, medium chain fatty acids (MCFA) and longer chain alcohols. Solventogens are microorganisms known to produce MCFA and alcohols via the acetone-butanol-ethanol (ABE) fermentation in which acetate is a key metabolite. Thus, co-cultivation of an acetogen and a solventogen in a consortium provides a potential platform to produce valuable chemicals from CO2. In this study, metabolic modeling was implemented to design a new co-culture of an acetogen and a solventogen to produce butyrate from CO2/H2 mixtures. The model-driven approach suggested the ability of the studied solventogenic species to grow on lactate/glycerol with acetate as co-substrate. This ability was confirmed experimentally by cultivation of Clostridium beijerinckii on these substrates in batch serum bottles and subsequently in pH-controlled bioreactors. Community modeling also suggested that a novel microbial consortium consisting of the acetogen Clostridium autoethanogenum, and the solventogen C. beijerinckii would be feasible and stable. On the basis of this prediction, a co-culture was experimentally established. C. autoethanogenum grew on CO2/H2 producing acetate and traces of ethanol. Acetate was in turn, consumed by C. beijerinckii together with lactate, producing butyrate. These results show that community modeling of metabolism is a valuable tool to guide the design of microbial consortia for the tailored production of chemicals from renewable resources.

From a Metal-Organic Square to a Robust and Regenerable Supramolecular Self-assembly for Methane Purification.

Porous supramolecular assemblies constructed by noncovalent interactions are promising for adsorptive purification of methane because of their easy regeneration. However, the poor stability arising from the weak noncovalent interactions has obstructed their practical applications. Here, we report a robust and easily regenerated polyhedron-based cationic framework assembled from a metal-organic square. This material exhibits a very low affinity for CH4 and N2 , but captures other competing gases (e.g. C2 H6 , C3 H8 , and CO2 ) with a moderate affinity. These results underpin highly selective separation of a range of gas mixtures that are relevant to natural gas and industrial off-gas. Dynamic breakthrough studies demonstrate its practical separation for C2 H6 /CH4 , C3 H8 /CH4 , CO2 /N2 , and CO2 /CH4 . Particularly, the separation time is ≈11 min g-1 for the C2 H6 /CH4 (15/85 v/v) mixture and ≈49 min g-1 for the C3 H8 /CH4 (15/85 v/v) mixture (under a flow of 2.0 mL min-1 ), respectively, enabling its capability for CH4 purification from light alkanes.

Intensification of hydrogen sulfide absorption by diethanolamine in industrial scale via combined simulation and data-based optimization strategies

A novel combinatorial approach including computer-aided simulation and robust statistical data-based methods was introduced to intensify the chemical absorption process of H2S by diethanolamine (DEA) from sour industrial off-gas. Effects of three parameters (lean amine H2S impurity (LAHI), lean amine temperature (LAT) and column pressure (CP) on the alteration trends and sensitivity of H2S removal were studied using response surface methodology (RSM) and Sobol’s sensitivity analysis (SA). Then, the optimal conditions for maximizing the H2S removal were determined. Results depicted that H2S removal will be decreased at higher LAHI and LAT. SA showed that LAHI (83%) was the most impactful factor on H2S removal. LAT (15%) and CP (2%) showed a relatively-low and negligible effects on the removal efficiency, respectively. It was shown that low impact of LAT and CP on H2S removal arised from weak variations of thermodynamic parameters of H2S absorption (H2S solubility, equilibrium constant, and enthalpy of absorption) with those factors. Maximum H2S removal of 99.995% was resulted at the optimal values of LAHI = 0.01 molH2S/molDEA, LAT = 53.7 °C, and CP = 1500 kPa.

Fabrication of a Porous Flow-Through Electrode for CO2 Reduction to CO in Organic Electrolyte with HCl Oxidized to Cl2 on Anode

Carbon dioxide (CO2) can be electrochemically reduced to value-added fuels and chemicals, which offers a promising way for CO2 recycling utilization. In the present work, we have designed a membrane electrolyzer for CO2 reduction to carbon monoxide (CO) in organic electrolyte, with hydrochloric acid (HCl) oxidized to chlorine (Cl2) on the anode. The obtained CO and Cl2 can be used as feedstock to produce phosgene. Using this method, CO2 can be converted into high-value products, and Cl2 can be recovered from industrial off-gases, which contain HCl. To substantially increase the current density of CO2 electroreduction, we have proposed a novel noncyanide electroplating method to deposit Au on Cu foam to fabricate a porous flow-through electrode. By enlarging the specific surface area of the cathode, and providing a large amount of Au nanoparticles for CO2 electroreduction, the cathodic current density has been increased to 106 mA·cm–2, with faradic efficiency of CO formation stabilized at 90%. On the anode, the faradic efficiency of Cl2 generation is stabled at 92%, with the anodic current density archived to 42 mA·cm–2. Such designed electrolysis cell has a broad application prospect in the chemical industry.