Twenty-eight two-, three-, four-, and five-component amine mixtures have been evaluated as possible activators of CO2 absorption into aqueous carbonate/bicarbonate solutions. Measurements were per- formed using a pressure autoclave with a sparger at conditions close to industrial ones. On the basis of these results, a formula for a new, more efficient amine activator named INS13 was developed. The activator was tested both in a pilot plant and on an industrial scale in an ammonia plant producing 300 tons/day of ammonia. Activator INS13 was applied in a number of ammonia plants in Poland and abroad.
Measurements of CO2 concentrations in soil air were taken in the summer seasons of 1998 and 2001 in SW Spitsbergen. The measurements were carried out in three small non-glaciated catchments in the Hornsund region close to the Polish Polar Station. The preliminary measurements were made using a Dräger's pump and ampules which contained an alkaline absorbent (1998). Later (2001), a new more accurate apparatus which uses a gravimetric method was tested. A variety of different geographical situations was chosen for the CO2 measurements. These included areas which differed in respect of the local hydrology, terrain relief, exposure to solar radiation, distance from the sea and quantity of seabird excrements in the soil. The measured concentrations of soil CO2 varied between 0.05 and 0.3% (with one exceptionally high value close to 0.5%). Owing to the local conditions, the differences between CO2 concentrations seem closely to relate to the specific properties of each catchment. Much of the biogenic CO2 present in water that circulates in tundra catchments which have a limestone foundation becomes involved in the dissolution of that limestone. In July 2001, about 40% of the CO2 was used in the dissolution of the carbonate rocks (30.3 kg/km2 month), the “free” CO2 being transported to the sea at Isbjřrnhamna Bay (40.4 kg/km2 month). In contrast, the water flowing through acidic rocks are rich in “free” CO2. The concentrations of dissolved and transported HCO3– ions from the polar catchments are closely correlated with variations in the daily production of biogenic CO2.
Binary vapour-liquid equilibrium of thymoquinone and carbon dioxide at the isothermal conditions was carried out at temperature 323.15 K and pressures from 6 to 10 MPa. The experimental data were fitted to the Soave-Redlich-Kwong equation of state. Results could be used for selection of process parameters in separation of volatiles from raw oil or for evaluation of existing separation technologies.
Measurements of the absorption rate of carbon dioxide into aqueous solutions of N-methyldiethanoloamine (MDEA) and 2-ethylaminoethanol (EAE) have been carried out. On this basis a mathematical model of the performance of an absorption column operated with aqueous solution of a blend of the above amines at elevated temperatures and pressures have been proposed. The results of simulations obtained by means of this model are described. The work is a part of a wider program, aimed at the development of a new process.
The process of carbon dioxide removal from monoethanolamine (MEA) - water solution was investigated on Poly Di Methyl Siloxane (PDMS) hydrophobic tubular membrane with a ceramic support. The effects of feed temperature, liquid flow rate and MEA concentration on CO2 mass transfer and selectivity were examined and found to be with a reasonable deviation (±25%) with predictions based on the multilayer film model. The membrane resistance was evaluated in separate experiments. The measured CO2 mass fluxes (0.17-0.45 kg/(m2h)) were found to be independent of the MEA concentration in the feed.
The reports of Intergovernmental Panel for Climate Change indicate that the growing emission of greenhouse gases, produced from the combustion of fossil fuels, mainly carbon dioxide, leads to negative climate changes. Therefore, the methods of mitigating the greenhouse gases emission to the atmosphere, especially of carbon dioxide, are being sought. Numerous studies are focused on so-called geological sequestration, i.e. injecting carbon dioxide to appropriate geological strata or ocean waters. One of the methods, which are not fully utilized, is the application of appropriate techniques in agriculture. The plant production in agriculture is based on the absorption of carbon dioxide in the photosynthesis process. Increasing the plant production directly leads to the absorption of carbon dioxide. Therefore, investigation of carbon dioxide absorption by particular crops is a key issue. In Poland, ca. 7.6 mln ha of cereals is cultivated, including: rye, wheat, triticale, oat and barley. These plants absorb approximately 23.8 mln t C annually, including 9.8 mln t C/yr in grains, 9.4 mln t C/yr in straw and 4.7 mln t C/yr in roots. The China, these cereals are cultivated on the area over 24 mln ha and absorb 98.9 mln t C/yr, including 55 mln tC/yr in grains, 36 in straw, and 7.9 mln t C/yr in roots. The second direction for mitigating the carbon dioxide emission into the atmosphere involves substituting fossil fuels with renewable energy sources to deliver primary energy. Cultivation of winter cereals as cover crops may lead to the enhancement of carbon dioxide removal from the atmosphere in the course of their growth. Moreover, the produced biomass can be used for energy generation.
Carbon dioxide (CO2) is a compound responsible for the greenhouse effect. One of the methods of CO2 capture from the gas stream is adsorption process. In this paper, the adsorption equilibrium isotherms of CO2 on zeolite 13X were measured at different temperatures (293.15 K, 303.15 K, 313.15 K, 323.15 K, 333.15 K, 348.15 K, 373.15 K, 393.15 K) and under pressures up to 2 MPa. These data were obtained using an Intelligent Gravimetric Analyzer (IGA-002, Hiden Isochema, UK). Selected multitemperature adsorption isotherm equations, namely Toth, Langmuir–Freundlich, and, Langmuir were correlated with experimental data.
Results of an extensive research program, aimed at finding new, more efficient activators of carbon dioxide absorption into aqueous carbonate/bicarbonate solutions are presented. Both single amines (2-ethyl-aminoethanol, 2-isopropyl aminoethanol, piperazine, tetraethylenepentamine, N-ethyl-piperazine and glicyne) and amine mixtures have been investigated. Absorption rate measurements were conducted in a laminar-jet absorber. Reaction rate constants for the particular activators were determined. Mixtures of aliphatic amines with cyclic amines, as well as mixtures of cyclic amines with cyclic amines were found to exhibit synergetic effect. Such amine mixtures might be used as new promoters for CO2 absorption in carbonate solutions in the modified Benfield process.
In the paper the results of measurements of CO2 absorption rate in aqueous potassium carbonate solutions containing cyclohexylamine, diethanolamine, 2-methylaminoethanol and triethylenetetramine as activators have been presented. Enhnancement mass transfer factors as well as reaction rate constants have been determined. Results show that among the tested activators triethylenetetramine and 2-methyl-aminoethanol may be used (instead of diethanolamine) as new promotors in a modified BENFLIELD process.
Three commercially available intercooled compression strategies for compressing CO2 were studied. All of the compression concepts required a final delivery pressure of 153 bar at the inlet to the pipeline. Then, simulations were used to determine the maximum safe pipeline distance to subsequent booster stations as a function of inlet pressure, environmental temperature, thickness of the thermal insulation and ground level heat flux conditions. The results show that subcooled liquid transport increases energy efficiency and minimises the cost of CO2 transport over long distances under heat transfer conditions. The study also found that the thermal insulation layer should not be laid on the external surface of the pipe in atmospheric conditions in Poland. The most important problems from the environmental protection point of view are rigorous and robust hazard identification which indirectly affects CO2 transportation. This paper analyses ways of reducing transport risk by means of safety valves.
In the paper presented are the results of calculations using authors own model to predict heat transfer coefficient during flow boiling of carbon dioxide. The experimental data from various researches were collected. Calculations were conducted for a full range of quality variation and a wide range of mass velocity. The aim of the study was to test the sensitivity of the in-house model. The results show the importance of taking into account the surface tension as the parameter exhibiting its importance in case of the flow in minichannels as well as the influence of reduced pressure. The calculations were accomplished to test the sensitivity of the heat transfer model with respect to selection of the appropriate two-phase flow multiplier, which is one of the elements of the heat transfer model. For that purpose correlations due to Müller-Steinhagen and Heck as well as the one due to Friedel were considered. Obtained results show a good consistency with experimental results, however the selection of two-phase flow multiplier does not significantly influence the consistency of calculations.
A commercially available ASPEN PLUS simulation using a pipe model was employed to determine the maximum safe pipeline distances to subsequent booster stations as a function of carbon dioxide (CO2) inlet pressure, ambient temperature and ground level heat flux parameters under three conditions: isothermal, adiabatic and with account of heat transfer. In the paper, the CO2working area was assumed to be either in the liquid or in the supercritical state and results for these two states were compared. The following power station data were used: a 900 MW pulverized coal-fired power plant with 90% of CO2recovered (156.43 kg/s) and the monothanolamine absorption method for separating CO2from flue gases. The results show that a subcooled liquid transport maximizes energy efficiency and minimizes the cost of CO2transport over long distances under isothermal, adiabatic and heat transfer conditions. After CO2is compressed and boosted to above 9 MPa, its temperature is usually higher than ambient temperature. The thermal insulation layer slows down the CO2temperature decrease process, increasing the pressure drop in the pipeline. Therefore in Poland, considering the atmospheric conditions, the thermal insulation layer should not be laid on the external surface of the pipeline.
The paper deals with numerical modelling of carbon dioxide capture by amine solvent from flue gases in post-combustion technology. A complex flow system including a countercurrent two-phase flow in a porous region, chemical reaction and heat transfer is considered to resolve CO2 absorption. In order to approach the hydrodynamics of the process a two-fluid Eulerian model was applied. At the present stage of model development only the first part of the cycle, i.e. CO2 absorption was included. A series of parametric simulations has shown that carbon dioxide capture efficiency is mostly influenced by the ratio of liquid (aqueous amine solution) to gas (flue gases) mass fluxes. Good consistency of numerical results with experimental data acquired at a small-scale laboratory CO2 capture installation (at the Institute for Chemical Processing of Coal, Zabrze, Poland) has proved the reliability of the model.
In the Polish sector of the Magura Nappe have long been known and exploited carbonate mineral waters, saturated with carbon dioxide, known as the “shchava (szczawa)”. These waters occur mainly in the Krynica Subunit of the Magura Nappe, between the Dunajec and Poprad rivers, close to the Pieniny Klippen Belt (PKB). The origin of these waters is still not clear, this applies to both “volcanic” and “metamorphic” hypotheses. Bearing in mind the case found in the Szczawa tectonic window and our geological and geochemical studies we suggest that the origin of the carbon dioxide may be linked with the thermal/pressure alteration of organic matter of the Oligocene deposits from the Grybów Unit. These deposits, exposed in several tectonic windows of the Magura Nappe, are characterized by the presence of highly matured organic matter – the origin of the hydrocarbon accumulations. This is supported by the present-day state of organic geochemistry studies of the Carpathian oil and gas bed rocks. In our opinion origin of the carbon-dioxide was related to the southern, deep buried periphery of the Carpathian Oil and Gas Province. The present day distribution of the carbonated mineral water springs has been related to the post-orogenic uplift and erosion of the Outer (flysch) Carpathians.
Thermodynamic principles for the dissolution of gases in ionic liquids (ILs) and the COSMO-SAC model are presented. Extensive experimental data of Henry’s law constants for CO2, N2 and O2 in ionic liquids at temperatures of 280-363 K are compared with numerical predictions to evaluate the accuracy of the COSMO-SAC model. It is found that Henry’s law constants for CO2 are predicted with an average relative deviation of 13%. Both numerical predictions and experimental data reveal that the solubility of carbon dioxide in ILs increases with an increase in the molar mass of ionic liquids, and is visibly more affected by the anion than by the cation. The calculations also show that the highest solubilities are obtained for [Tf2N]ˉ. Thus, the model can be regarded as a useful tool for the screening of ILs that offer the most favourable CO2 solubilities. The predictions of the COSMOSAC model for N2 and O2 in ILs differ from the pertinent experimental data. In its present form the COSMO-SAC model is not suitable for the estimation of N2 and O2 solubilities in ionic liquids.
The paper looks at an analysis of the tendency of changes in the fuel structure of electricity generation and thus resulting changes in carbon dioxide emissions. Forecasts drawn up by various institutions and organizations were selected for the analysis. Firstly, on the basis of statistical data contained in (IEA 2017a, IEA 2008) and with the use of Kay’s indicators, the impact of changes in energy intensity of the national income and energy mix on changes in carbon dioxide emissions per capita in 2006–2015 for the OECD countries and Poland were analyzed. A small effect of changes was found in the fuel mix in this period of time on the emissions. The main impact was due to changes in the energy intensity of the national income and changes in the national income per capita. Next, selected fuel scenarios for the period up to 2050 (60) were discussed – WEC, IEA, EIA, BP, Shell, with a focus on the WEC scenarios. These have been developed for various assumptions with regard to the pace of economic development, population growth, and developments of the political situation and the situation on the fuel market. For this reason, it is difficult to assess the reliability thereof. The subject of the discussion was mainly the data on the fuel structure of electricity generation and energy intensity of national income and changes in carbon dioxide emissions. The final part of the paper offers a general analysis of forecasts drawn up for Poland. These are quite diverse, with some of them being developed as part of drawing up the Energy Policy for Poland until 2050, and some covering the period up to 2035. An observation has been made that some forecasts render results similar to those characteristic of the WEC Hard Rock scenario.