Molecular modeling of asymmetric induction in heterogeneously catalyzed hydrogenation of the C=O bond

Modifiering av metallytor med starkt adsorberade kirala organiska molekyler är eventuellt den mest relevanta teknik man vet i dag för att skapa kirala ytor. Den kan utnyttjas i katalytisk produktion av enantiomeriskt rena kirala föreningar som behövs t.ex. som läkemedel och aromkemikalier. Trots många fördelar av asymmetrisk heterogen katalys jämfört med andra sätt för att få kirala föreningar, har den ändå inte blivit ett allmänt verktyg för storskaliga tillämpningar. Detta beror t.ex. på brist på djupare kunskaper i katalytiska reaktionsmekanismer och ursprunget för asymmetrisk induktion. I denna studie användes molekylmodelleringstekniker för att studera asymmetriska, heterogena katalytiska system, speciellt hydrering av prokirala karbonylföreningar till motsvarande kirala alkoholer på cinchona-alkaloidmodifierade Pt-katalysatorer. 1-Fenyl-1,2-propandion (PPD) och några andra föreningar, som innehåller en prokiral C=O-grupp, användes som reaktanter. Konformationer av reaktanter och cinchona-alkaloider (som kallas modifierare) samt vätebundna 1:1-komplex mellan dem studerades i gas- och lösningsfas med metoder som baserar sig på vågfunktionsteori och täthetsfunktionalteori (DFT). För beräkningen av protonaffiniteter användes också högst noggranna kombinationsmetoder såsom G2(MP2). Den relativa populationen av modifierarnas konformationer varierade som funktion av modifieraren, dess protonering och lösningsmedlet. Flera reaktant–modifierareinteraktionsgeometrier beaktades. Slutsatserna på riktning av stereoselektivitet baserade sig på den relativa termodynamiska stabiliteten av de diastereomeriska reaktant–modifierare-komplexen samt energierna hos π- och π*-orbitalerna i den reaktiva karbonylgruppen. Adsorption och reaktioner på Pt(111)-ytan betraktades med DFT. Regioselektivitet i hydreringen av PPD och 2,3-hexandion kunde förklaras med molekyl–yta-interaktioner. Storleken och formen av klustret använt för att beskriva Pt-ytan inverkade inte bara på adsorptionsenergierna utan också på de relativa stabiliteterna av olika adsorptionsstrukturer av en molekyl. Populationerna av modifierarnas konformationer i gas- och lösningsfas korrelerade inte med populationerna på Pt-ytan eller med enantioselektiviteten i hydreringen av PPD på Pt–cinchona-katalysatorer. Vissa modifierares konformationer och reaktant–modifierare-interaktionsgeometrier var stabila bara på metallytan. Teoretiskt beräknade potentialenergiprofiler för hydrering av kirala α-hydroxiketoner på Pt implicerade preferens för parvis additionsmekanism för väte och selektiviteter i harmoni med experimenten. De uppnådda resultaten ökar uppfattningen om kirala heterogena katalytiska system och kunde därför utnyttjas i utvecklingen av nya, mera aktiva och selektiva kirala katalysatorer.

Production of Biofuels by Fischer Tropsch Synthesis

Production of biofuel via biomass gasification followed by Fischer Tropsch synthesis is of considerable interest because of the high quality of fuels produced which do not contain sulphur and are free of carbon dioxide. The purpose of this Master’s thesis is to study feasibility production of biofuels integrated with Fischer Tropsch process using Aspen Plus simulation. The simulation results were used to size process equipment and carry out an economic evaluation. The results show that lowering the reactor temperature from 1000 oC - 850 oC and raising the water gas shift temperature from 500 oC - 600 oC can improve overall gas efficiency, which in turn leads to better production of ultra clean syngas for the Fischer Tropsch synthetic reactor. Similarly, the Fischer Tropsch offgas is converted into a gas turbine for power production, and finally biodiesel is produced as fuels for transportation.

Simulation and optimization of IGCC technique for power generation and hydrogen production by using lignite Thar coal and cotton stalk

The purpose of this study was to simulate and to optimize integrated gasification for combine cycle (IGCC) for power generation and hydrogen (H2) production by using low grade Thar lignite coal and cotton stalk. Lignite coal is abundant of moisture and ash content, the idea of addition of cotton stalk is to increase the mass of combustible material per mass of feed use for the process, to reduce the consumption of coal and to increase the cotton stalk efficiently for IGCC process. Aspen plus software is used to simulate the process with different mass ratios of coal to cotton stalk and for optimization: process efficiencies, net power generation and H2 production etc. are considered while environmental hazard emissions are optimized to acceptance level. With the addition of cotton stalk in feed, process efficiencies started to decline along with the net power production. But for H2 production, it gave positive result at start but after 40% cotton stalk addition, H2 production also started to decline. It also affects negatively on environmental hazard emissions and mass of emissions/ net power production increases linearly with the addition of cotton stalk in feed mixture. In summation with the addition of cotton stalk, overall affects seemed to negative. But the effect is more negative after 40% cotton stalk addition so it is concluded that to get maximum process efficiencies and high production less amount of cotton stalk addition in feed is preferable and the maximum level of addition is estimated to 40%. Gasification temperature should keep lower around 1140 °C and prefer technique for studied feed in IGCC is fluidized bed (ash in dry form) rather than ash slagging gasifier

Lujien hitsattavien terästen käyttäytyminen -60 °C:ssa

Opinnäytetyö on osa Arctic Materials Technologies Development -projektia, jonka tavoitteena on kehittää perusteita arktisten alueiden sovelluksiin suunnittelun ja valmistuksen kannalta. Arktisella alueella sijaitsee useita potentiaalisia öljy- ja maakaasuesiintymiä, joiden hyödyn-täminen tulee vuosi vuodelta kannattavammaksi ilmaston lämpenemisestä johtuvan merijään heikkenemisen vuoksi. Alin suunnittelulämpötila arktisilla alueilla on -60 °C, mikä aiheuttaa haasteita sekä materiaalinvalinnalle että hitsaukselle. Ferriittisillä teräksillä esiintyy lämpötilasta riippuvaa sitkeyden vaihtelua, jota kutsutaan transi-tiokäyttäytymiseksi. Lämpötilan laskiessa teräksen iskusitkeys sekä murtumissitkeys laske-vat. Arktisissa sovelluskohteissa käytetään yleisesti niukkaseosteisia, mikroseostettuja hie-noraeteräksiä, joille on ominaista erinomaiset sitkeys-, lujuus- sekä hitsattavuusominaisuudet vaativissakin olosuhteissa. Lujat termomekaanisesti valssatut ja nuorrutetut hienoraeteräkset kattavat myötölujuusluokat 355…700 MPa. Tutkimuksissa on saatu vaihtelevia tuloksia ma-teriaalien isku- ja murtumissitkeydestä -60 °C:ssa. Erityisesti sitkeysominaisuudet hitsiaineen ja muutosvyöhykkeen alueiden välillä ovat vaihtelevia. Pienemmällä lämmöntuonnilla ja seostetuilla lisäaineilla saavutetaan kuitenkin pääsääntöisesti parempia sitkeysarvoja. Asiku-laarinen ferriitti sekä alabainiitti ovat toivottavia mikrorakenteita liitoksessa, niiden pienen raekoon johdosta.

Aqueous-phase reforming of renewables for selective hydrogen production in the presence of supported platinum catalysts

The evolution of our society is impossible without a constant progress in life-important areas such as chemical engineering and technology. Innovation, creativity and technology are three main components driving the progress of chemistry further towards a sustainable society. Biomass, being an attractive renewable feedstock for production of fine chemicals, energy-rich materials and even transportation fuels, captures progressively new positions in the area of chemical technology. Knowledge of heterogeneous catalysis and chemical technology applied to transformation of biomass-derived substances will open doors for a sustainable economy and facilitates the discovery of novel environmentally-benign processes which probably will replace existing technologies in the era of biorefinary. Aqueous-phase reforming (APR) is regarded as a promising technology for production of hydrogen and liquids fuels from biomass-derived substances such as C3-C6 polyols. In the present work, aqueous-phase reforming of glycerol, xylitol and sorbitol was investigated in the presence of supported Pt catalysts. The catalysts were deposited on different support materials, including Al2O3, TiO2 and carbons. Catalytic measurements were performed in a laboratory-scale continuous fixedbed reactor. An advanced analytical approach was developed in order to identify reaction products and reaction intermediates in the APR of polyols. The influence of the substrate structure on the product formation and selectivity in the APR reaction was also investigated, showing that the yields of the desired products varied depending on the substrate chain length. Additionally, the influence of bioethanol additive in the APR of glycerol and sorbitol was studied. A reaction network was advanced explaining the formation of products and key intermediates. The structure sensitivity in the aqueous-phase reforming reaction was demonstrated using a series of platinum catalysts supported on carbon with different Pt cluster sizes in the continuous fixed-bed reactor. Furthermore, a correlation between texture physico-chemical properties of the catalysts and catalytic data was established. The effect of the second metal (Re, Cu) addition to Pt catalysts was investigated in the APR of xylitol showing a superior hydrocarbon formation on PtRe bimetallic catalysts compared to monometallic Pt. On the basis of the experimental data obtained, mathematical modeling of the reaction kinetics was performed. The developed model was proven to successfully describe experimental data on APR of sorbitol with good accuracy.

Production of Chemicals from Woody Biomass by Wet Oxidation

The production of chemicals from sawdust by wet oxidation has been investigated. Two different concentrations of sawdust; 54054 mg/l and 32683 mg/l were used in the study. The wet oxidation operating conditions were; 175 deg.C – 225 deg.C, 1MPa Oxygen, and 40 minutes to 120 minutes reaction time. Carboxylic acids were among the chemicals produced in the process. The total yield of carboxylic acids was found to increase with temperature. Also, higher yields of carboxylic acids were observed at a lower sawdust concentration. This was probably due to the high oxygen-biomass ratio at lower sawdust concentration. Higher oxygen availability at low sawdust concentration resulted in increased conversion of the sawdust; hence the higher yields of carboxylic acids. At lower sawdust concentration, a total carboxylic acid yield of 25.59 wt% was attained at 200 deg.C and 40 minutes reaction time. At higher sawdust concentration, a total carboxylic acid yield of 15.57 wt% was attained at 200 deg.C and 40-minutes reaction time. The carboxylic acids identified include formic acid, acetic acid, succinic acid and oxalic acid. The optimum temperature for the production of formic acid was found to be 200 deg.C, while the optimum temperature for the production of acetic acid was found to be 225 deg.C. A temperature of 225 deg.C and relatively short reaction time of 10 minutes was found to be the optimal condition for the production of succinic acid. Formic acid was produced in the highest yield, with an optimal yield of 13.69wt %, when the reaction temperature and time are 200 deg.C and 40 minutes respectively. The yield of formic acid was found to decrease significantly when further increasing the temperature to 225 deg.C. This was presumably due to thermal decomposition of formic acid at relatively higher temperature. However, the yield of acetic acid was found to steadily increase with temperature. This is because acetic is more thermally stable than formic acid. The yield of acetic acid did not decrease after the temperature was increased to 225 deg.C. Optimal yield of acetic acid (7.98wt %) was achieved at; 225 deg.C, and 40 minutes reaction time. Succinic acid was produced only at temperatures of 200 deg.C and 225 deg.C. Optimal yield of succinic acid (5.66wt %) was attained under the following conditions; 32683 mg/l, 225 deg.C, 1MPa O2, and 10-minutes reaction time. Oxalic acid was produced in the lowest yield and, less frequently. The optimal yield of oxalic acid (4.02 wt%) was attained at 175 deg.C and 80-minutes of reaction time The Total Organic Carbon (TOC) is found to be higher when increasing the operating temperature, thus suggesting that more organic compounds are formed at higher temperatures. The identified carboxylic acids could only account for less than 30% of the measured COD content of the various wet oxidation samples. This implies that some other unidentified compounds (reaction products) must have been present. In general, wet oxidation seems to be an effective method for converting lignocellulosic biomass into useful chemicals. Relatively higher temperatures have been found to favor the production of carboxylic acids from sawdust.

Industrial-Scale hydrothermal carbonization of waste sludge materials for fuel production

Hydrothermal carbonization (HTC) is a thermochemical process used in the production of charred matter similar in composition to coal. It involves the use of wet, carbohydrate feedstock, a relatively low temperature environment (180 °C-350 °C) and high autogenous pressure (up to 2,4 MPa) in a closed system. Various applications of the solid char product exist, opening the way for a range of biomass feedstock materials to be exploited that have so far proven to be troublesome due to high water content or other factors. Sludge materials are investigated as candidates for industrial-scale HTC treatment in fuel production. In general, HTC treatment of pulp and paper industry sludge (PPS) and anaerobically digested municipal sewage sludge (ADS) using existing technology is competitive with traditional treatment options, which range in price from EUR 30-80 per ton of wet sludge. PPS and ADS can be treated by HTC for less than EUR 13 and 33, respectively. Opportunities and challenges related to HTC exist, as this relatively new technology moves from laboratory and pilot-scale production to an industrial scale. Feedstock materials, end-products, process conditions and local markets ultimately determine the feasibility of a given HTC operation. However, there is potential for sludge materials to be converted to sustainable bio-coal fuel in a Finnish context.

Deoxygenation of fatty acids for production of fuels and chemicals

The decreasing fossil fuel resources combined with an increasing world energy demand has raised an interest in renewable energy sources. The alternatives can be solar, wind and geothermal energies, but only biomass can be a substitute for the carbon–based feedstock, which is suitable for the production of transportation fuels and chemicals. However, a high oxygen content of the biomass creates challenges for the future chemical industry, forcing the development of new processes which allow a complete or selective oxygen removal without any significant carbon loss. Therefore, understanding and optimization of biomass deoxygenation processes are crucial for the future bio–based chemical industry. In this work, deoxygenation of fatty acids and their derivatives was studied over Pd/C and TiO2 supported noble metal catalysts (Pt, Pt–Re, Re and Ru) to obtain future fuel components. The 5 % Pd/C catalyst was investigated in semibatch and fixed bed reactors at 300 °C and 1.7–2 MPa of inert and hydrogen–containing atmospheres. Based on extensive kinetic studies, plausible reaction mechanisms and pathways were proposed. The influence of the unsaturation in the deoxygenation of model compounds and industrial feedstock – tall oil fatty acids – over a Pd/C catalyst was demonstrated. The optimization of the reaction conditions suppressed the formation of by–products, hence high yields and selectivities towards linear hydrocarbons and catalyst stability were achieved. Experiments in a fixed bed reactor filled with a 2 % Pd/C catalyst were performed with stearic acid as a model compound at different hydrogen–containing gas atmospheres to understand the catalyst stability under various conditions. Moreover, prolonged experiments were carried out with concentrated model compounds to reveal the catalyst deactivation. New materials were proposed for the selective deoxygenation process at lower temperatures (~200 °C) with a tunable selectivity to hydrodeoxygenation by using 4 % Pt/TiO2 or decarboxylation/decarbonylation over 4 % Ru/TiO2 catalysts. A new method for selective hydrogenation of fatty acids to fatty alcohols was demonstrated with a 4 % Re/TiO2 catalyst. A reaction pathway and mechanism for TiO2 supported metal catalysts was proposed and an optimization of the process conditions led to an increase in the formation of the desired products.

Utilization of steelmaking waste materials for production of calcium carbonate (CaCO3)

The steel industry produces, besides steel, also solid mineral by-products or slags, while it emits large quantities of carbon dioxide (CO2). Slags consist of various silicates and oxides which are formed in chemical reactions between the iron ore and the fluxing agents during the high temperature processing at the steel plant. Currently, these materials are recycled in the ironmaking processes, used as aggregates in construction, or landfilled as waste. The utilization rate of the steel slags can be increased by selectively extracting components from the mineral matrix. As an example, aqueous solutions of ammonium salts such as ammonium acetate, chloride and nitrate extract calcium quite selectively already at ambient temperature and pressure conditions. After the residual solids have been separated from the solution, calcium carbonate can be precipitated by feeding a CO2 flow through the solution. Precipitated calcium carbonate (PCC) is used in different applications as a filler material. Its largest consumer is the papermaking industry, which utilizes PCC because it enhances the optical properties of paper at a relatively low cost. Traditionally, PCC is manufactured from limestone, which is first calcined to calcium oxide, then slaked with water to calcium hydroxide and finally carbonated to PCC. This process emits large amounts of CO2, mainly because of the energy-intensive calcination step. This thesis presents research work on the scale-up of the above-mentioned ammonium salt based calcium extraction and carbonation method, named Slag2PCC. Extending the scope of the earlier studies, it is now shown that the parameters which mainly affect the calcium utilization efficiency are the solid-to-liquid ratio of steel slag and the ammonium salt solvent solution during extraction, the mean diameter of the slag particles, and the slag composition, especially the fractions of total calcium, silicon, vanadium and iron as well as the fraction of free calcium oxide. Regarding extraction kinetics, slag particle size, solid-to-liquid ratio and molar concentration of the solvent solution have the largest effect on the reaction rate. Solvent solution concentrations above 1 mol/L NH4Cl cause leaching of other elements besides calcium. Some of these such as iron and manganese result in solution coloring, which can be disadvantageous for the quality of the PCC product. Based on chemical composition analysis of the produced PCC samples, however, the product quality is mainly similar as in commercial products. Increasing the novelty of the work, other important parameters related to assessment of the PCC quality, such as particle size distribution and crystal morphology are studied as well. As in traditional PCC precipitation process, the ratio of calcium and carbonate ions controls the particle shape; a higher value for [Ca2+]/[CO32-] prefers precipitation of calcite polymorph, while vaterite forms when carbon species are present in excess. The third main polymorph, aragonite, is only formed at elevated temperatures, above 40-50 °C. In general, longer precipitation times cause transformation of vaterite to calcite or aragonite, but also result in particle agglomeration. The chemical equilibrium of ammonium and calcium ions and dissolved ammonia controlling the solution pH affects the particle sizes, too. Initial pH of 12-13 during the carbonation favors nonagglomerated particles with a diameter of 1 μm and smaller, while pH values of 9-10 generate more agglomerates of 10-20 μm. As a part of the research work, these findings are implemented in demonstrationscale experimental process setups. For the first time, the Slag2PCC technology is tested in scale of ~70 liters instead of laboratory scale only. Additionally, design of a setup of several hundreds of liters is discussed. For these purposes various process units such as inclined settlers and filters for solids separation, pumps and stirrers for material transfer and mixing as well as gas feeding equipment are dimensioned and developed. Overall emissions reduction of the current industrial processes and good product quality as the main targets, based on the performed partial life cycle assessment (LCA), it is most beneficial to utilize low concentration ammonium salt solutions for the Slag2PCC process. In this manner the post-treatment of the products does not require extensive use of washing and drying equipment, otherwise increasing the CO2 emissions of the process. The low solvent concentration Slag2PCC process causes negative CO2 emissions; thus, it can be seen as a carbon capture and utilization (CCU) method, which actually reduces the anthropogenic CO2 emissions compared to the alternative of not using the technology. Even if the amount of steel slag is too small for any substantial mitigation of global warming, the process can have both financial and environmental significance for individual steel manufacturers as a means to reduce the amounts of emitted CO2 and landfilled steel slag. Alternatively, it is possible to introduce the carbon dioxide directly into the mixture of steel slag and ammonium salt solution. The process would generate a 60-75% pure calcium carbonate mixture, the remaining 25-40% consisting of the residual steel slag. This calcium-rich material could be re-used in ironmaking as a fluxing agent instead of natural limestone. Even though this process option would require less process equipment compared to the Slag2PCC process, it still needs further studies regarding the practical usefulness of the products. Nevertheless, compared to several other CO2 emission reduction methods studied around the world, the within this thesis developed and studied processes have the advantage of existing markets for the produced materials, thus giving also a financial incentive for applying the technology in practice.

Feasibility of the use of recycled nutrients in fast growing pulpwood production

The application of pulp and paper mill (PPM) sludge in agriculture and forestry has been acknowledged as soil amendments and a plant nutrient source. The main objectives of this study were to evaluate the total cost of the use of recycled nutrients from PPM sludge in fast growing pulpwood production, and the financial profitability of fast growing pulpwood production with the use of these recycled nutrients. The investment and production costs of fast growing pulpwood plantation were directly acquired from a previous research, while the other data was compiled through different studies. The total cost of the use of PPM sludge was evaluated based on assumed factors. Discounted cash flow method was used to evaluate the financial profitability, using NPV and IRR as indicators. The results of estimated sludge nutrient contents were 16.2 g N, 2.9 g P, and 2.4 g K kg-1 of dry sludge. The sludge application rate was estimated at 1.36 Mg/ha in the first year. The total cost of the use of PPM sludge involved transport and spreading cost of US$49.15/dry ton. The fertilization cost applied in the financial model was designed in 3 different options and their results were as follows: option (1) was taken directly from the reference research (US$97/ha); option (2) was the use of sludge alone (US$66.75/ha); and option (3) was the use of sludge and TSP fertilizer (US$83.80/ha). The average NPV without discounting was US$248,180 while the IRRs ranged between approximately 3-4% with an average of 3.63%. Although option (2) and (3) contributed to higher IRRs compared to option (1), this increase was still not significant as the IRR was not sensitive to the total fertilization cost. The advantages are that this practice can be performed at a lower cost and the application rate can be still increased if necessary. It is better for forest plantations compared to agriculture and consequently supports reforestation program. In addition, it can be similarly applied in wood biomass production. A disadvantage is that the IRRs were not very favorable compared to the criterion of 11%. The sludge high in C:N ratio can cause nitrogen immobilization, and regulatory concerns may restrict and complicate the use of sludge landspreading and contribute to additional costs and processes.

Production of magnesium carbonates from serpentinites for CO2 mineral sequestration : optimisation towards industrial application

Global warming is one of the most alarming problems of this century. Initial scepticism concerning its validity is currently dwarfed by the intensification of extreme weather events whilst the gradual arising level of anthropogenic CO2 is pointed out as its main driver. Most of the greenhouse gas (GHG) emissions come from large point sources (heat and power production and industrial processes) and the continued use of fossil fuels requires quick and effective measures to meet the world’s energy demand whilst (at least) stabilizing CO2 atmospheric levels. The framework known as Carbon Capture and Storage (CCS) – or Carbon Capture Utilization and Storage (CCUS) – comprises a portfolio of technologies applicable to large‐scale GHG sources for preventing CO2 from entering the atmosphere. Amongst them, CO2 capture and mineralisation (CCM) presents the highest potential for CO2 sequestration as the predicted carbon storage capacity (as mineral carbonates) far exceeds the estimated levels of the worldwide identified fossil fuel reserves. The work presented in this thesis aims at taking a step forward to the deployment of an energy/cost effective process for simultaneous capture and storage of CO2 in the form of thermodynamically stable and environmentally friendly solid carbonates. R&D work on the process considered here began in 2007 at Åbo Akademi University in Finland. It involves the processing of magnesium silicate minerals with recyclable ammonium salts for extraction of magnesium at ambient pressure and 400‐440⁰C, followed by aqueous precipitation of magnesium in the form of hydroxide, Mg(OH)2, and finally Mg(OH)2 carbonation in a pressurised fluidized bed reactor at ~510⁰C and ~20 bar PCO2 to produce high purity MgCO3. Rock material taken from the Hitura nickel mine, Finland, and serpentinite collected from Bragança, Portugal, were tested for magnesium extraction with both ammonium sulphate and bisulphate (AS and ABS) for determination of optimal operation parameters, primarily: reaction time, reactor type and presence of moisture. Typical efficiencies range from 50 to 80% of magnesium extraction at 350‐450⁰C. In general ABS performs better than AS showing comparable efficiencies at lower temperature and reaction times. The best experimental results so far obtained include 80% magnesium extraction with ABS at 450⁰C in a laboratory scale rotary kiln and 70% Mg(OH)2 carbonation in the PFB at 500⁰C, 20 bar CO2 pressure for 15 minutes. The extraction reaction with ammonium salts is not at all selective towards magnesium. Other elements like iron, nickel, chromium, copper, etc., are also co‐extracted. Their separation, recovery and valorisation are addressed as well and found to be of great importance. The assessment of the exergetic performance of the process was carried out using Aspen Plus® software and pinch analysis technology. The choice of fluxing agent and its recovery method have a decisive sway in the performance of the process: AS is recovered by crystallisation and in general the whole process requires more exergy (2.48–5.09 GJ/tCO2sequestered) than ABS (2.48–4.47 GJ/tCO2sequestered) when ABS is recovered by thermal decomposition. However, the corrosive nature of molten ABS and operational problems inherent to thermal regeneration of ABS prohibit this route. Regeneration of ABS through addition of H2SO4 to AS (followed by crystallisation) results in an overall negative exergy balance (mainly at the expense of low grade heat) but will flood the system with sulphates. Although the ÅA route is still energy intensive, its performance is comparable to conventional CO2 capture methods using alkanolamine solvents. An energy‐neutral process is dependent on the availability and quality of nearby waste heat and economic viability might be achieved with: magnesium extraction and carbonation levels ≥ 90%, the processing of CO2‐containing flue gases (eliminating the expensive capture step) and production of marketable products.