Entwicklung und Erprobung eines Wäschersystems zur CO2‐Abreinigung aus Rauchgasen mithilfe alkalischer Reststoffe

An innovative, technical approach for the reduction of CO₂ emissions is presented that utilizes alkaline wastes to capture CO₂ from flue gases in stable mineral form. Comprehensive pilot‐scale experiments were conducted with the developed flue gas scrubbing system at a power plant site. By optimizing the process parameters gas flux, CO₂ partial pressure, circulation flux and suspension liquid‐to‐solid ratio, a CO₂ binding of 40 – 90 g kg^–1 waste could be reached and up to 25 % of the CO₂ could be captured. The new technique is economically advantageous especially when both alkaline waste and CO₂ are produced on site and when the carbonated products can be used as secondary resources.     

Assessment of Industrial Greenhouse Gas Reduction Strategies Within Consistent System Boundaries

With respect to the climate goals of the greenhouse gas (GHG) neutrality in 2050, different GHG reduction strategies are discussed for industrial processes. For a comparison of the strategies carbon direct avoidance (CDA), carbon capture and storage, and carbon capture and utilization (CCU), the method system expansion is applied. Exemplarily, the CO₂ reduction potential and the energy demand are determined. The Carbon2Chem® project is described as an example of CCU for the steel and chemical production. The direct reduction with H₂ represents the CDA strategy for the steel industry.     

Standortplanung für die Herstellung CO2‐basierter Chemikalien am Beispiel der Olefinproduktion

The use of CO₂ as raw material is increasingly gaining in importance as an option for climate protection and as an alternative raw material feedstock. Both direct electrochemical syntheses and thermochemical processes are associated with a high demand for electrical energy. A contribution to climate protection is only possible in the case of low‐carbon power generation, as can be realized, e.g., by wind power or solar energy. This article presents a methodology for identifying suitable sites for the CO₂‐based production of olefins in Germany.     

Coal combustion in O2/CO2 mixtures compared with air

As part of CO₂ abatement strategies for climate change, we are investigating coal combusion behaviour in various O₂/CO₂ mixtures and in air. The goal is to simulate conditions of coal combustion with flue gas recirculation in order to maximize the CO₂ concentration in the flue gas prior to its recovery. A western Canadian sub‐bituminous coal and a U.S. eastern bituminous coal were investigated. Thermal input was set at 0.21 MW with a flue gas oxygen concentration of 5 vol%. Experiments were done using various O₂/CO₂ mixtures and air. The oxygen concentration ranged from 21% to 42%. Up to 95% CO₂ concentrations were achieved in the flue gas. This paper describes experimental results in terms of flame temperatures and pollutant emissions (NO_x', SO₂ and CO).     

Synthese von aliphatischen Aldehyden aus Alkanen und Kohlendioxid: Valeraldehyd aus Butan und CO2 – Machbarkeit und Grenzen

During the last decades, the engineering of chemical processes has focused more and more on energy efficiency and reduction of climate‐changing emissions. Regarding the synthesis of aldehydes, the photocatalytic dehydrogenation of alkanes to olefins, using visible (sun) light, and the subsequent hydroformylation of such olefins with CO₂ seem to be capable to achieve both targets. This work deals mainly with catalyst concepts for both reaction steps. Here, kinetic studies of the photocatalytic alkane dehydrogenation are presented, and the feasibility of hydroformylation using CO₂ is described in a continuous gas phase reaction. The problems that have to be solved befoe the technical application are discussed and an economic and ecological evaluation for both processes is carried out.     

Membranbasierte Bereitstellung von CO2 für die dezentrale Algenproduktion in einer Bioenergiefassade

This study emphasizes the importance of a sustainable energy supply with regard to climate change. A way is shown how a de-centralized heat supply in urban areas with renewable energies can be combined with algae production. The decentrally generated CO₂ emissions are made usable for biomass production by means of membrane separation technology. The operating behavior of the CO₂-selective membrane materials was observed over an operating period of almost 10 years. This provides solid evidence of the operability of the polymer membrane and membrane module technology. It enables further optimization of the separation process for future applications, also in a wider range of applications.     

Heterogen katalysierte Hydrierung von Kohlendioxid zu Methan unter erhöhten Drücken

Ni‐ and Ru‐containing supported catalysts were prepared and used for the CO₂ hydrogenation to methane (Sabatier reaction) in the gas phase. Tests on the effect of the reaction temperature and pressure were in the focus. ZrO₂ and γ‐Al₂O₃ were used as suitable catalyst supports. CO₂ and H₂ conversions of 70 – 80 % and selectivity to methane of > 99 % were reached. TiO₂ and SiO₂ based catalysts exclusively lead to CO and seem to be not suited for this reaction. The investigations on the pressure effect impressively demonstrated the influence on the chemical equilibrium. CO₂ and H₂ can be nearly completely converted with > 99.9 % selectivity to methane over Ru/ZrO₂.     

Optimization-based identification of CO2 capture and utilization processing paths for life cycle greenhouse gas reduction and economic benefits

This paper introduces a mathematical formulation to identify promising CO₂ capture and utilization (CCU) processing paths and assess their production rates by solving an optimization problem. The problem is cast as a multi-objective one by simultaneously maximizing a net profit and life cycle greenhouse gas (GHG) reduction. Three case studies are illustrated using an exemplary CCU processing network. The results indicate the optimal solution is greatly influenced by the scale of CO₂ emission source, market demand, and hydrogen availability. Moreover, with the current system of measuring the GHG reduction regarding a business-as-usual level, if the aim is to achieve a GHG reduction within a national boundary, the question of whether CCU plants producing a product of same functionality through conventional means, which the CO₂-based product can replace, exists in the country can come into consideration. This systematic identification will assist decision-making regarding future R&D investment and construction of large-scale CCU plants.     

Influence of Alkaline Additives and Buffers on Mineral Trapping of CO2 under Mild Conditions

Carbon dioxide (CO₂) gas is the main contributor to climate change. CO₂ storage in underground brines and oil‐field brines by mineral trapping has been considered as a promising alternative in order to reduce CO₂ emissions. However, permanent storage of CO₂ in stable carbonate minerals is greatly dependent on brine pH, being favored over an alkaline pH. The effect of alkaline additives (NaOH, KOH, CaO) and buffer solutions (NaHCO₃/NaOH, Na₂HPO₄/NaOH, NH₄Cl/NH₄OH) on the mineral trapping of CO₂ under mild conditions using a synthetic brine is investigated. The results indicate that both NaOH+NH₄Cl/NH₄OH and KOH+NH₄Cl/NH₄OH mixtures promote precipitation mainly of calcium carbonate (CaCO₃).     

Low temperature CO oxidation over Au/TiO2 and Au/SiO2 catalysts

After a high-temperature reduction (HTR) at 773 K, TiO₂-supported Au became very active for CO oxidation at 313 K and was an order of magnitude more active than SiO₂-supported Au, whereas a low-temperature reduction (LTR) at 473 K produced a Au/TiO₂ catalyst with very low activity. A HTR step followed by calcination at 673 K and a LTR step gave the most active Au/TiO₂ catalyst of all, which was 100-fold more active at 313 K than a typical 2% Pd/Al₂O₃ catalyst and was stable above 400 K whereas a sharp decrease in activity occurred with the other Au/TiO₂ (HTR) sample. With a feed of 5% CO, 5% O₂ in He, almost 40% of the CO was converted at 313 K and essentially all the CO was oxidized at 413 K over the best Au/TiO₂ catalyst at a space velocity of 333 h^–1 based on CO + O₂. Half the chloride in the Au precursor was retained in the Au/TiO₂ (LTR) sample whereas only 16% was retained in the other three catalysts; this may be one reason for the low activity of the Au/TiO₂ (LTR) sample. The reaction order on O₂ was approximately 0.4 between 310 and 360 K, while that on CO varied from 0.2 to 0.6. The chemistry associated with this high activity is not yet known but is presently attributed to a synergistic interaction between gold and titania.     

Porosity engineering of biochar-based single-atom Ni catalysts to promote CO2 electroreduction over a broad potential window

Developing electrocatalysts for CO₂ electroreduction with high activity and superior selectivity is extremely important and desirable from both academic and industrial perspectives. However, owing to competition with hydrogen evolution, highly efficient CO₂ reduction is mostly achieved with high CO selectivity in a narrow potential range, which is incompatible with a large cell voltage required for industrial-level CO₂ reduction. Herein, we report an effective strategy to regulate CO₂ reduction performances of single-atom Ni electrocatalysts over a broad potential window by engineering their pore structures (micropores, mesopores, or hierarchical pores with both micropores and mesopores). It is revealed that hierarchically pores can significantly promote CO₂ reduction efficiency of single-atom Ni electrocatalysts. The hierarchically porous electrocatalyst achieves a maximum CO Faradaic efficiency (FE_CO) of 97.4% at −1.2 V (vs. RHE) and shows high FE_CO of >85% over a broad potential window from −0.7 to −1.7 V, much superior to electrocatalysts with other pore structures. More impressively, turnover frequency of the hierarchically porous electrocatalyst increases rapidly with increasing the applied potential and reaches 50,067 h⁻¹ at −1.7 V. Such CO₂ electroreduction promotion could be attributed to a synergistic effect of micropores for enhancing CO₂ adsorption and mesopores for facilitating rapid release of product bubbles, which significantly improves CO₂ reduction and suppresses hydrogen evolution.     

Direct reduction of diluted CO2 gas to C2 products by copper hydroxyphosphate microrods

Electrochemical reduction of CO₂ is widely researched in recent years. However, direct electro-reduction of diluted CO₂ to C₂ products is seldomly studied. In this work, electrocatalytic reduction of CO₂ with different concentrations were conducted on Cu₂(PO₄)(OH) catalysts. The catalytic performance in diluted CO₂ is comparable with that in pure CO₂ by using Cu₂(PO₄)(OH) as catalyst. Besides, the selectivity of C₂ product is still as high as 64.6% in 50%CO₂ concentration. The normalized C₂ current density of Cu₂(PO₄)(OH) was over 6.8 times higher than that of commonly used Cu₂O–Cu catalyst with similar size. In situ Raman spectroscopy proved that Cu⁺ is the main active site at higher potentials. More importantly, a higher local pH is realized under diluted CO₂ test conditions which is favorable for promoting C–C coupling. Finally, in situ ATR-FTIR spectroscopy was performed to further monitor and identify the adsorbed intermediates and help reveal the mechanism for the catalysts.     

Polyurethane/polyethersulfone dual-layer anisotropic membranes for CO2 removal from flue gas

Removing CO₂ from flue gas streams has been a permanent challenge regarding environmental issues. Membrane technology is a solution for this problem but more efficient membranes are required. The fabrication of dual-layer polyurethane/polyethersulfone membrane by the co-casting technique is undertaken and the effects of previous evaporation time and coagulation water bath temperature on membrane morphology are explored. Uniform layers with excellent adhesion are obtained. The effect of feed pressure and temperature on membrane permeability and selectivity for CO₂, N₂, and O₂ are studied. Increasing the pressure from 1 to 8 bar results in a reduction of CO₂ permeability and CO₂/N₂ ideal selectivity from 19.6 to 13.0 barrer, and from 66 to 60, respectively. Temperature in the range of 25–45°C enhances CO₂ permeability from 19.6 to 28.9 barrer, although CO₂/N₂ selectivity decreases from 66 to 43, yet showing good potential for applications.     

Transformations of Iron (III) Precursors in a Wave of Flameless RDX Combustion

Flameless combustion of 40% Fe₂O₃ – 40% RDX – 20% HDI (mix I) and 30% CoCO₃ – 15% iron formate – 40% RDX – 15% HDI (mix II) systems was explored by time-resolved X-ray diffraction (TRXRD). In case of mix I, the reaction was found to proceed via the formation of FeO intermediate: Fe₂O₃ → FeO → Fe₃O₄. Variation in the extent of iron reduction was associated with dynamic temperature change and a reductant content of the reaction zone. The reduction proceeded as a solid-state reaction, without amorphization of the structure. The process in system II involved the formation of CoO and FeO intermediates. Further reduction – up to metals – takes place behind the combustion front and yields a mixture of nanosized Co, Fe, and Co_0.7Fe_0.3 particles. Exposure of hot reaction products – nano-sized Co and Fe – to the air leads to their self-ignition and formation of Co₃O₄ and Fe₃O₄, respectively.     

Economic Assessment of the Hydrogenation of CO2 to Liquid Fuels and Petrochemical Feedstock

To remove high concentrations of CO₂ from the off‐gas of coal‐driven power plants, a new process was proposed. The catalytic hydrogenation of the CO₂ leads to the production of C₂ – C₄ (petrochemical feedstock) and liquid C₅₊ hydrocarbons (fuel). Thus, environmentally harmful CO₂ may be converted sustainably to useful products. On the basis of a process flow sheet, the costs for processing the CO₂ are estimated for different plant sizes. The price of hydrogen contributes significantly to the overall production costs. Further price reductions may be achieved by final engineering optimization of the process as a whole and specific unit operations.     

CO2 utilization for methanol production; Optimal pathways with minimum GHG reduction cost

Mitigating CO₂ emissions from industries and other sectors of our economy is a critical component of building a sustainable economy. This paper investigates two different methanol synthesis routes based on CO₂ utilization (CO₂ capture and utilization [CCU], and tri-reforming of methane [TRM]), and compares the results with the conventional methanol production using natural gas as the feedstock (NG-MeOH). A comprehensive techno-economic analysis (TEA) model that includes the findings of the life cycle assessment (LCA) models of methanol production using various CO₂ utilization pathways is conducted. Economic analysis is conducted by developing a cost model that is connected to the simulation models for each production route. Compared to the conventional process (with a GHG emission of 0.6 kg CO₂/kg MeOH), the lifecycle GHG reduction of 1.75 and 0.41 kg CO₂/kg MeOH are achievable in the CCU and TRM pathways, respectively. Furthermore, the results indicate that, under current market conditions and hydrogen production costs, methanol production via CO₂ hydrogenation will result in a cost approximately three times higher than that of the conventional process. The integrated TEA–LCA model shows that this increased cost of production equates to a required life cycle GHG reduction credit of $279 to $422 per tonne of CO₂ utilized, depending on construction material and selected pathway. Additionally, when compared to the CO₂ hydrogenation route, the tri-reforming process (TRM-MeOH) can result in a 42% cost savings. Furthermore, a minimum financial support of $56 per tonne utilized CO₂ will be required to make the TRM-MeOH process economically viable.     

The effects of bimetallic interactions for CO2-assisted oxidative dehydrogenation and dry reforming of propane

The catalytic reduction of CO₂ by propane may occur via dry reforming to produce syngas (CO + H₂) or oxidative dehydrogenation to yield propylene. Utilizing propane and CO₂ as coreactants presents several advantages over conventional methane dry reforming or direct propane dehydrogenation, including lower operating temperatures and less coke formation. Thus, it is of great interest to identify catalytic systems that can either effectively break the C C bond to generate syngas or selectively break C H bonds to produce propylene. In this study, several precious and nonprecious bimetallic catalysts supported on reducible CeO₂ were investigated using flow reactor studies at 823 K to identify selective catalysts for CO₂-assisted reforming and dehydrogenation of propane.     

Thermodynamic Properties of CO2 Conversion by Sodium Borohydride

In order to verify the resource utilization of CO₂ from coal‐fired flue gas, the conversion of CO₂ by sodium borohydride was investigated under atmospheric pressure and moderate temperature. According to the product analysis results of mass spectrometry and ion chromatography, combined with the comparison of electrode potentials, the mechanism of CO₂ reaction with sodium borohydride was deduced, in which formate was confirmed as the main reduction product, and the intermediates of [BH_i(HCO₂)(OH)_3–i]^?1 were considered as the essential mediums for the formation of formate. The feasibility of this conversion was studied thermodynamically.     

High pressure phase equilibria in the carbon dioxide - n-Hexadecane and carbon dioxide — water systems

Phase equilibria in the carbon dioxide - n-hexadecane and carbon dioxide – water systems have been measured at temperatures between 314 K and 353 K and pressures between 8.53 and 16.12 MPa. The results have been correlated using two cubic equations of state and also compared with measurements reported in the literature.     

Compost from Municipal Solid Wastes as a Source of Biochar for CO2 Capture

Increasing greenhouse gas emissions contributing to the global climate change are a major concern of environmental protection. Developing adsorbents from low-cost and renewable resources is an attractive strategy. On the other hand, the high capacity of production rates of municipal solid waste, besides high methane emissions, is the origin of some eco-systemic challenges. The combination of the two environmental problems is considered by introducing the compost from a mechanical biological treatment of municipal solid wastes as a low-cost source of adsorbent for CO₂ capture. The obtained compost was thermally and chemically activated and the CO₂ adsorption capacities of prepared samples were evaluated. Samples prepared sequentially with sulfuric acid and heated at 800 °C and vice versa, respectively, had the highest uptake capacities and were comparable with commercial adsorbents.