Carponate precipitation with carbon dioxide gas

The aim of this thesis research work focused on the carbonate precipitation of magnesium using magnesium hydroxide Mg(OH)2 and carbon dioxide (CO2) gas at ambient temperature and pressure. The rate of dissolution of Mg(OH)2 and precipitation kinetics were investigated under different operating conditions. The conductivity and pH of the solution were inline monitored by a Consort meter and the solid samples gotten from the precipitation reaction were analysed by a laser diffraction analyzer Malvern Mastersizer to obtain particle size distributions (PSD) of crystal samples. Also the Mg2+ concentration profiles were determined from the liquid phase of the precipitate by ion chromatography (IC) analysis. Crystal morphology of the obtained precipitates were also investigated and discussed in this work. For the carbonation reaction of magnesium hydroxide in the present work, it was found that magnesium carbonate trihydrate (nesquehonite) was the main product and its formation occurred at a pH of around 7-8. The stirrer speed has a significant effect on the dissolution rate of Mg(OH)2. The highest obtained Mg2+ concentration level was 0.424 mol L-l for the 470 rpm and 0.387 mol L-1 for the 560 rpm which corresponded to the processing time of 45 mins and 40 mins respectively. The particle size distribution shows that the average particle size keeps increasing during the reaction as the CO2 is been fed to the system. The carbonation process is kinetically favored and simple as nesquehonite formation occurs in a very short time. It is a thermodynamically and chemically stable solid product, which allows for a long-term storage of CO2. Since the carbonation reaction is a complex system which includes dissolution of magnesium hydroxide particles, absorption of CO2, chemical reaction and crystallization, the dissolution of magnesium hydroxide was studied in hydrochloric acid (HCl) solvent with and without nitrogen (N2) inert gas. It was found on the dissolution part that the impeller speed had effect on the dissolution rate. The higher the impeller speed the higher the pH of the solution, although for the highest speed of 650rpm it was not the case. Therefore, it was concluded that the optimum speed of the stirrer was 560rpm. The influence of inert gas N2 on the dissolution rate of Mg(OH)2 particles could be seen based on measured pH, electric conductivity and Mg2+ concentration curves.

New aspects in limestone dissolution for wet flue gas desulfurization

Fortsättningsvis tillgodoses största delen av världens energibehov genom förbränning av fossila bränslen, dessutom forsätter världens totala energibehov att öka. Eftersom förbränning av fossila bränslen som t.ex. olja och kol orsakar utsläpp av svaveldioxid som är skadligt för både människa och natur, finns det fortfarande ett akut behov av forskning och utveckling av metoder för svavelrening. De vanligaste teknikerna för svavelrening är våt- och semitorrskrubbning, där svaveldioxiden absorberas av en skrubbervätska. Det är allmänt känt att våtskrubbning är en av de effektivaste teknikerna för svavelrening både ekonomiskt och tekniskt sett samt den mest använda. Våtskrubbningsprocessen har dock flera nackdelar, som dess höga vatten- och energiförbrukning. I större kraftverk går ca 1-3% av dess eleffekt åt till rökgasreningsprocessen, vilket kraftigt motiverar utveckling av nya reningsprocesser samt effektivering av existerande reningsanläggningar. Skrubbervätskan som till huvudsak består av vatten innehåller vanligtvis även kalcium vars syfte är att binda svavlet. Kalciumet kan tillsättas i flera former varav bränd kalk och kalksten är de vanligaste formerna. Kalksten används ofta i svavelreningsprocessen p.g.a. dess låga pris och för att den ger upphov till den användbara biprodukten gips. Kalkstenens upplösningshastighet är en de av faktorer som kraftigast påverkar reningsprocessen. En detaljerad experimentell karakterisering och analys av kalkstenspartiklar i fast form och i vätskeform har utförts i detta arbete. En experimentell metod för att studera kalkstenens upplösningshastighet vid låg till obegränsad massöverföring har även utvecklats i detta arbete. Metoden möjliggör identifieringen av systemoberoende kinetiska parametrar, vilka kan användas för att undersöka reningsprocesser samt för att planera nya reningsanläggningar. Kinetiska modeller utvecklades genom att använda kalkstenpartiklars specifika yta, som mättes genom kväveadsorption. Efter att de kinetiska parametrarna bestämts experimentellt utvecklades en skrubbermodell för att optimera en i driftvarande skrubber. Genom att kombinera experimentellt bestämda modeller med matematisk optimering erhölls en djupare insikt i hur olika råmaterial påverkar processen och hur driftparameterar bör justeras för att minska elförbrukningen.

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.

Dynamic Modelling of Circulating Fluidized Bed Plant with Gas Turbine Repowering

Increasing amount of renewable energy source based electricity production has set high load control requirements for power grid balance markets. The essential grid balance between electricity consumption and generation is currently hard to achieve economically with new-generation solutions. Therefore conventional combustion power generation will be examined in this thesis as a solution to the foregoing issue. Circulating fluidized bed (CFB) technology is known to have sufficient scale to acts as a large grid balancing unit. Although the load change rate of the CFB unit is known to be moderately high, supplementary repowering solution will be evaluated in this thesis for load change maximization. The repowering heat duty is delivered to the CFB feed water preheating section by smaller gas turbine (GT) unit. Consequently, steam extraction preheating may be decreased and large amount of the gas turbine exhaust heat may be utilized in the CFB process to reach maximum plant electrical efficiency. Earlier study of the repowering has focused on the efficiency improvements and retrofitting to maximize plant electrical output. This study however presents the CFB load change improvement possibilities achieved with supplementary GT heat. The repowering study is prefaced with literature and theory review for both of the processes to maximize accuracy of the research. Both dynamic and steady-state simulations accomplished with APROS simulation tool will be used to evaluate repowering effects to the CFB unit operation. Eventually, a conceptual level analysis is completed to compare repowered plant performance to the state-of-the-art CFB performance. Based on the performed simulations, considerably good improvements to the CFB process parameters are achieved with repowering. Consequently, the results show possibilities to higher ramp rate values achieved with repowered CFB technology. This enables better plant suitability to the grid balance markets.

The relationship between b2b branding and industrial buying in the digital era: evidence from Finnish gas industry

The aim of this study is to understand the importance of b2b brands in different phases of the industrial buying process in the digital era. The research problem is approached by examining a b2b supplier brand in the context of gas supplier selection. The data was collected by interviewing individuals from ten different companies. The findings contribute to previous theory by showing that as industrial buying behaviour is eventually individual behaviour, brands can influence decision making. The relevance of a brand depends on individual’s personality and preferences. Digital media cannot be ignored in managing brand image as buyers are present in the online environment. The results reveal that traditional personal selling is, nevertheless, in a key role in brand image building and is a source of added value. The salesperson influences buyers’ perceived associations of a brand and gives the brand a face.

Screening of power to gas projects

The purpose of this thesis was the screening of power to gas projects worldwide and reviewing the technologies used and applications for the end products. This study focuses solely on technical solutions and feasibility, economical profitability is excluded. With power grids having larger penetrations of intermittent sources such as solar and wind power, the demand and production cannot be balanced in conventional methods. Technologies for storing electric power in times of surplus production are needed, and the concept called power to gas is a solution for this problem. A total of 57 projects mostly located in Europe were reviewed by going through publications, presentations and project web pages. Hydrogen is the more popular end product over methane. Power to gas is a viable concept when power production from intermittent sources needs to be smoothed and time shifted, when carbon free fuels are produced for vehicles and when chemical industry needs carbon neutral raw materials.