Thesis Proposal

UNDERGRADUATE THESIS PROJECT PROPOSAL Department of Chemical Engineering De La Salle University ± ManilaEfficiency of Carbon Capture by Aqueous Ammonia from Combustion of Semirara Industrial Grade Sub-bituminous Coal Submitted by: Stephanie Jane P. Siy Chemical Engineering Minor in Semiconductor Processing Janina Charisse Villanueva Chemical Engineering Alexis Pulhin Chemical Engineering MERECHE Section EA1 (8 a.m.) November 30, 2010 Thesis Adviser: PhD. Susan A. Roces Thesis Co-Adviser: PhD. Nathaniel P. Dugos On my honor as a University student, on this assignment I have neither given nor received unauthorized aid as defined by the Guidelines on Academic Honesty of the Student Handbook. Signed ___________________________________ Table of Contents List of Tables ............................................................................................................................... i List of Figures.............................................................................................................................ii Chapter 1: Introduction ............................................................................................................... 1 1.1 Background of the Study............................................................................................... 1 1.2 Problem Statement ........................................................................................................ 1 1.3 Objectives ..................................................................................................................... 2 1.3.1 General Objectives................................................................................................. 2 1.3.2 Specific Objectives ................................................................................................ 2 1.4 Significance of the Study .............................................................................................. 2 1.5 Scope and Limitations................................................................................................... 2 Chapter 2: Review of Related Literature ..................................................................................... 4 2.1 Coal: Its General Properties and its Uses ....................................................................... 4 2.1.1 World Coal Consumption ...................................................................................... 4 2.1.2 Environmental Impacts of Coal Consumption and Implemented Regulations ......... 6 2.1.3 Coal Consumption and CO2 Emission in the Philippines ........................................ 7 2.1.4 Coal in the Philippines ........................................................................................... 7 2.1.5 Regulations implemented on Reducing CO2 Emissions in the Philippines .............. 8 2.2 Carbon Capture Technologies ....................................................................................... 9 2.2.1 Chemical Looping Combustion or Chemical Looping Reforming .......................... 9 2.2.2 Adsorption ........................................................................................................... 10 2.2.3 Absorption ........................................................................................................... 11 2.3 Incorporation of Ammonia in Decarbonisation Absorption ......................................... 14 Chapter 3: Theoretical Framework ............................................................................................ 16 3.1 Chemical Properties of Ammonia ............................................................................... 16 3.2 Reactions Involved in Ammonia Decarbonization ....................................................... 17 3.3 NH3-CO2 ±H2O Equilibrium Diagram ......................................................................... 18 3.4 Absorption .................................................................................................................. 18 3.4.1 Material balance .................................................................................................. 18 3.4.2 Limiting Gas-Liquid Ratio ................................................................................... 19 3.4.3 Multicomponent Absorption ................................................................................ 19 3.5 Wetted-Wall Column .................................................................................................. 20 Chapter 4: Materials and Methodology ..................................................................................... 21 4.1 Materials ..................................................................................................................... 21 4.2 Experimental Setup ..................................................................................................... 21 4.3 Experimental Procedures ............................................................................................ 22 4.3.1 Combustion of Semirara Coal .............................................................................. 22 4.3.2 Preparation of Aqueous Ammonia Sample .......................................................... 23 References ................................................................................................................................ 24 Appendix .................................................................................................................................. 29 A. Calculations ................................................................................................................ 29 B. Materials Safety Data Sheet............................................................................................ 30 List of Tables Chapter 2 Table 2.1 Updated coal consumption statistics (in thousand short tons) of the world and top 40 countries as conducted by the Energy Information Administration during the year 2008 ................................................. 5 Table 2.2 Update coal CO2 emission statistics (in million metric tons) of the world and top 40 countries as conducted by the Energy Information Administration during the year 2008............................................................ 6 Table 2.3 Industrial grade Semirara coal constituents obtained from the Semirara Mining Corporation ......................................................................... 8 Chapter 3 Table 3.1 Physical properties of ammonia (NH3) obtained from Perry¶s Chemical Engineering Handbook ........................................................... 16 Table 3.2 Vapor pressure of ammonia (NH3) and corresponding temperature as obtained from Perry¶s Chemical Engineering Handbook ....................................................... 16 Table 3.3 List of equilibrium reactions involved in ammonia absorption .............................................................................................................. 17 i .......................1 Qian¶s wetted-wall column design......................................................................... 2010).....................................1 Ternary diagram of NH3-CO2 ±H2O system at 40ÛC and 1 bar as presented in UNIQUAC model ..............................2 Overall volumetric mass transfer coefficient vs...... 21 ii ..............List of Figures Chapter 2 Figure 2.................................. 21 Figure 4.......................... gas-liquid ratio (Qiu et al...2 Schematic diagram of the procedures used by Puxty et al........................... 19 Chapter 4 Figure 4......................... and Ma¶mun et al............ 14 Chapter 3 Figure 3.......... as obtained from Aronu et al....... (2009) ..................................................................... 18 Figure 3.....1 Rapid screening apparatus incorporated in the methodologies of Aronu et al.................................... 13 Figure 2.............................................................2 Experimental setup ................. (2010) in determining the load capacities of ammonia and MEA ......... Chapter 1: Introduction 1. CO2 capture and storage (CCS) is currently available for large companies that produce large emissions(Kirchsteiger. various researches are conducted to determine the sources that caused this and to find solutions that would prevent further degradation of the environment. there devised methods of controlling. this method could potentially amount to grave hazards. One of which is what this paper focuses on. However. 2008) and chemical looping reforming (CLR) which are done whilst producing synthesis gas (Rydén. Among the said methods are membrane technology. 2008). Furthermore. Just recently. In addition to that. carbon dioxide capture is opted as a means of preventing air pollution while the presence of said fuels is still abundant. thus this paper will involve the combustion of Semirara sub1 . Lyngfelt. CCS involves storing the collected CO2 underground and that requires transport through pipes. carbon capture using aqueous ammonia. & Mattisson. absorption. Considering this situation. carbon extraction. As the preservation of the stability of nature is deemed crucial at these times. scientist are growing more aware about the consequences that result from technological advancement. kinds of fuel and the properties of the flue gas produced before. adsorption. biotechnology (cyanobacteria) and energy conversion (Feron & Hendriks. Moreover. due to economic and political means. the fact that the CO2 gas does not undergo any significant reaction would only lead to its accumulation over the years (Kirchsteiger. 2008). 1. cryogenics. Previous studies so far elucidate absorption capacities of aqueous ammonia through the generation of artificial flue gas. Researches were conducted in order to find the solution to this problem and thus lead to the emergence of green technologies. coal and fossil fuels still play a big role in generating energy in industrial sectors since it is made a spectacle in the international market. 2006). Efficiency of each method will depend on the different parameters applied on the medium. 2008). this paper shall disseminate information about one of the clean coal technologies that can be used in third world countries such as the Philippines. But since solutions are called for at a sooner time. Recently. CCS may serve as an off-setter for the time being. there are uncertainties of situations that may arise from accidental release of CO2 from pipe leaks and what¶s worse is that effects may reach globally(Kirchsteiger. So far. during or after combustion. among these also include the new carbon capture methods namely chemical looping cycle (CLC) which involves the transfer of oxygen with both the gas and fuel separated (Yang et al. even highly recommended the total elimination of greenhouse gases.2 Problem Statement In fulfilment of alleviating the effects of greenhouse gases and to increase awareness of this issue. 2005). Although promising as it sounds.. hiding and.1 Background of the Study As the world is experiencing the dilemmas brought about by global warming. applying it at a global scale may yet be costly for most to afford. methods involved in sequestration of carbon dioxide can be applied before (precombustion) or after (post-combustion). 3. The amount of other fuel constituents such as sulphur and hydrogen and their products shall be taken into account since they are absorbable as well. Comparison of gas composition before and after absorption process will indicate the efficiency solvent given its corresponding concentration. 1.1 General Objectives This paper aims to prove and evaluate the effectiveness of aqueous ammonia in absorbing carbon dioxide from multi-component flue gas such as combustion products from coal. 2.2 Specific Objectives 1. small amounts of samples (10 grams of coal and 10 grams of solvent) and a small scale design of the wet wall column of which dimensions vary from existing literature will be utilized. absorption principles shall be applied. abundant. 3. Compute for the pressure of flue gas prior to achieving CO2 partial pressure of 20 kPa. O2. Obtain CO2 content before and after flue gas is made to pass through absorption column. practical and economical techniques which may be easily available to the country¶s industries. Hence. This time natural flue gas is used to simulate actual combustion of coal in power plants. It is designed for lessening carbon emissions (on a large scale) using processes and materials suitable for the Philippine setting. studies had gone as far as using mixed CO2 and N2 in order to simulate the flue gas. To conform to the space provided by the laboratory. CO.5 Scope and Limitations The research shall cover the use of ammonium absorption decarbonisation technology in the post combustion setting. Determine the percent conversion of coal fuel to flue gas by the analysis of the contents of the following gases: CO2. Variables such as different concentrations of ammonia shall be used against the combustion of Semirara industrial grade coal. 1. Absorption of different aqueous ammonia concentrations shall be determined through the material balance of input and output fluids. H2O.3. A small sample of Semirara coal shall be combusted to test the CO2 absorption capacities of aqueous ammonia in different concentrations. This will determine whether prior processes have to be done to isolate CO2 or CO2 absorption from mixed flue gas is efficient that additional process need not be added. low-cost. and SO2. So far. N2. It aims to discover ways to capture carbon efficiently and effectively.bituminous industrial grade coal to produce the flue gas for testing the absorption of aqueous ammonia at different concentrations. Since other coal constituents will be 2 .4 Significance of the Study This main purpose of the study is to help in alleviating pollution and global warming. 1.3 Objectives 1. H2. 1. Furthermore. preloading of CO2 gas shall not be included in the procedures. Then after the production of flue gas from combustion. and through the calculation of the mass fraction of flue gas components at the inlet and outlet. Hence this might yet exclude the determination of the mass transfer coefficient. Absorption will be indicated by the change of pressure. The wet wall column shall be fabricated such that dimensions that simply allow contact between solvent and solute. Factors excluded in this research are the rate of absorption and the gas used for stripping the absorbent of CO2 content for regeneration.included as previously mentioned. absorption capacity shall be determined from the CO2 content and other absorbed gas content from circulated solvent. Also. temperature at the absorption part will have to be maintained at 20ÛC to prevent the vaporization of ammonia as suggested by literature. 3 . analysis of the actual conversion of fuel into flue gas is required before doing the analysis of the absorbent. China was the top producer of hard coal. It was at the 70¶s when coal made a turning point. the coal will have to be heated to allow the polymerization of aromatics. In order to rank coal by its quality. Lignite has a calorific value of 4000 to 8300 Btu/lb and this is sufficient to provide energy for generating electricity (Kentucky Educational Television). coal can also be processed manually. while Japan was the top importer of coal. 2010). according to the latest statistics conducted by the World Coal Association (2010) during 2008. Properties of coal such as their carbon content. while bituminous coal has a calorific value of 10000 to 15500 Btu/lb is highly favourable enough to supply intense heat for metallurgic processes (Kentucky Educational Television). temperature and pressure related to the depth of the coal¶s burial. the hardest coal yielding a calorific value of more or less 15000 Btu/lbm and is rarely used in any operations but house heating. Coal mainly starts with peat which is usually an immature coal that is previously left to coalify for more or less a million years (Roces.1 World Coal Consumption The following history is as stated by the National Energy Education Development Project. combustible sedimentary rock that is formed from accumulated fossilized remains of prehistoric colossal life forms. until its consumption broke the average record until year 2008. coal was long used by indigenous people such as the native North Americans.Chapter 2: Review of Related Literature 2. therefore lowering its demands in the market (Kentucky Educational Television). Lastly. Currently. anthracite. sub-bituminous and lignite.1. Australia was the top exporter of coal. coal is classified into four categories namely anthracite. bituminous. Upon the discovery of the European colonizers. Besides obtaining coal from mines that contain natural reserves of fossil fuels. Therefore. it comprises 23% of the America¶s energy supply. Also. inorganic traces and calorific value may vary from the way fossil fuel coalifies. Before coal was discovered by the European colonizers. Sub-bituminous coal¶s calorific value of 8300 to 13000 Btu/lb is considered to give a cleaner flue gas with its high energy. However during the 20th century the demand for coal began its decline as there appeared an increased in demand for petroleum as America enters the ³motorized´ trend in machinery (Smiley. otherwise known as fossil fuel (National Energy Education Development Project). bituminous and then anthracite. it was not given much significance until it became widely used in mass production during the 1800¶s. If given a few million more years. and the length of time it was left to coalify (World Coal Association).1 Coal: Its General Properties and its Uses Coal is a carbon rich. Quality of coalification depends on the organic composition of the material. Then billion years more could gradually coalify the once lignite into sub-bituminous. 4 . It is important to consider the impurities and non-organic traces that would lower the energy value that coal produces. The more immature coal contains more combined water. the coal may become lignite which is characterized with a dark brown to black color. 2. 2010). releasing impurities and retaining the volatile carbon content (Menendez & Alvarez). 45 23 Bulgaria Germany 267881.94 14257.68 9249.85 38282. Currently.47 32 Israel Kazakhstan 75922. which are estimated to last for only about 42 and 60 years based on the current rate of consumption (World Coal Institute.75 40 Chile 5 43805.16 21119.20 34 Philippines Indonesia 71497.16 37 Hong Kong Canada 61858.Coal is widely used by the domestic and industrial sectors to provide energy in daily operations. coal has reserves that could last for about 122 years which is longer compare to other fuel sources like oil and gas.18 28 Vietnam Poland 148914.71 36385.88 25 Spain Africa 227447.66 8589.20 24588. Being an abundant high energy source.10 39 Slovakia Romania 44472. South 110522. the United States.1 shows the coal consumption of some countries and the total world consumption during the year 2008. coal was priced to be one of the cheapest fuels since the 70¶s.02 35 Hungary Taiwan 69396.04 27 Brazil Australia 157896.1 Updated coal consumption statistics (in thousand short tons) of the world and top 40 countries as conducted by the Energy Information Administration during the year 2008 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 China 3004414. the world consumes a total of about 7. Reasons like these plus the demand for energy makes coal an object of politics. Another factor that contributed to its low market price would be the expansion of coal markets which was once initiated by European countries and colonies and the improvement of transnational transportation (Ellerman.42 16709.08 13099.50 24 Korea.18 17415. 1995).65 21 Serbia United States 1120548.15 30 Estonia Turkey 108836. Table 2.30 14061.93 28553. therefore leading to the lowering of transportation costs and then the price of oil.71 31 Mexico Ukraine 78009.94 24610. being the residual supplier of coal.52 12505.17 27203. given the fact that it also readily provides energy in its raw form by being burned directly into combustion engines.82 .80 33 Netherlands Greece 71822.09 33161. The increasing demand made coal one of the bases of evaluating the GDP of countries since this vein of black gold is what makes a country capable of circulating its economy through the industries that rely on this energy and the exports that will yet supply other industries offcoast. is the one dictating the price of coal in the market.41 38 Pakistan Czech Republic 59851.3 billion short tons of coal. Table 2.49 8992. 2010).55 29 France Korea.03 36 Bosnia and Herzegovina United Kingdom 64506.44 22 Thailand India 632357. According to the table. Also this requires tremendous amount of labor force to obtain it.62 26 Italy Japan 203803.87 12760. North Russia 249795.36 12697. Furthermore. 02891 28 Greece Poland 204. South 248. Among the mechanisms involved was the Clean Development Mechanism wherein countries are highly encouraged to implement projects that will help reduce the emission of greenhouse gases (United Nations Framework Convention on Climate Change).54101 45.19382 14.412 41.2 Update coal CO2 emission statistics (in million metric tons) of the world and top 40 countries as conducted by the Energy Information Administration during the year 2008 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 China 5381.1675 22 Brazil India 1025.57542 38 Slovakia Thailand 61.2 (which shows the emissions taken by the same source as that of the previous during the same year) 7 billion short tons of coal during the year 2008 and in turn produced CO2 emission that amounted to over 12 billion metric tons.17582 31.43991 35 Belgium Turkey 115.60041 29. which in effect led to global warming.69187 28.29348 The Kyoto Protocol has long fulfilled its part as a policy governing the regulation of greenhouse gases in an international scale.28 2.42308 27 Serbia Australia 239.45375 33 Philippines Ukraine 140.98659 34.50847 26 Malaysia Korea. Also.49116 17. Table 2.45556 25.16074 15. In comparison of the data in Table 2.85313 31 Bulgaria United Kingdom 147.7496 32 Mexico Kazakhstan 141.69026 17.99814 21 France United States 2125.54865 23 Spain Russia 447.34512 19.16124 30 Israel Taiwan 162. North 67.02507 29 Hong Kong Indonesia 179.20269 25 Romania Germany 318. the same top 40 countries appeared in both tables with the first three having the same order of coal consumption and CO2 emission.69332 49.0485 35.1 and Table 2.58739 40 Bosnia and Herzegovina World 12897.31154 39 Finland Czech Republic 57.83643 50.73217 32. it is clearly implied that the increase of emission is dependent of the amount of coal burned.2 Environmental Impacts of Coal Consumption and Implemented Regulations The increase consumption of fossil fuels amounted to an increase in the production of greenhouse gases. The abrupt change in climate raised the awareness of many nations and therefore began the search for alternatives and strategies to prevent the total degradation of the environment.76601 14. Although the rest of the countries are not the same as that of the first three. This includes the application of scientific research.1.87302 32.17408 34 Pakistan Canada 128.59087 37 Chile Italy 62.70069 24 Netherlands Japan 441.72546 31.World 7345641. breaking ground for 6 .21266 36 Denmark Korea.92507 51. which contributes about 92% of the local coal production. Surigao and in the Negros Provinces. The coal to be used in this research is that mined by Semirara (Semirara Mining Corporation). and in Batan Island by Rock Energy International Corporation (REIC). there emerged several green innovations that were proven to reduce global warming. even if it will contribute to global warming.75% is used by other industries.1. However. our country¶s reserves are scattered all over the Philippines. reluctance in releasing these products due to economical and political causes (Sy.5 million metric tons of coal. thereby also having the largest coal producer is Semirara Mining Corporation (SMC). According to the DOE of the Philippines. Philippines is among the countries that consume considerable amounts of coal without being able to implement effective methods that could either way reduce or eliminate greenhouse gases. Other contents that comprise the coal 7 . most companies find it difficult to give up the cheapest means of producing energy and resort to it. otherwise known as the group of big eight countries have been supporting the improvement of coal fired power-stations in its efficiency through the help of modern technology. hence resorting to ³capturing carbon dioxide´ 2. In other words.0 MMMT in 2003 to 2.1 and Table 2.5% which came from small-scale coal mining operations.4 Coal in the Philippines According to the Department of Energy (DOE) of the Philippines. Coal production in 2006 as of December 12 stands 2.1.3 Coal Consumption and CO2 Emission in the Philippines Based on the latest updated statistics on coal consumption presented by Table 2. in Southern Cebu by Ibalong Resources and Development Corporation (IRDC).innovations that could introduce solutions that are not only effective but also economically friendly. industries that cater cement. A pound of this fuel harnesses energy that amounts to around 8600 Btu to 10450 Btu.2. 22.5% is used for the processing of cement while the rest of the 3. Zamboanga Sibuguey. 2. and basing it on the 2006 Update of the Philippine Energy Plan (PEP). In the long run. 2006) show that out of the 9. 73% is used for the generation of energy. like the coal deposits from Malangas by the Philippine National Oil Company (PNOC) with its Taiwanese partner. the G8. According to the DOE. coal production in 2004 surpassed the 2003 level by 34% from 2. Antique. Philippines ranked 34th in global coal consumption and 33rd in CO2 emissions respectively. Albay. owing to improved coal production of big mining companies as well as good weather conditions. Their recent studies (as of December 12.7 MMMT in 2004.3 MMT run-of-min. Considering this fact. The DOE claims that there are Philippines coals which are of such high quality that they can be used without the need for coal preparation or blending with imported coals. 2008) only nullified the efforts made by the UN to achieve the said objective. but the largest deposit is located in Semirara Island. but there are also coal mines located in Cebu. As mentioned in Kirchsteiger¶s (2008) paper. energy generators and other processes are the major coal consumers. Semirara coal is classified as sub-bituminous. 2. 5 Regulations implemented on Reducing CO2 Emissions in the Philippines Laws and/or acts have been passed in the Philippines concerning the control of carbon dioxide emissions and of other gases (greenhouse gases) imposing harm to Filipinos and to the country¶s physical nature.00 2.00 1. Table 2.3. C Initial deformation temperature. ASTMD3172) Ash.3 Industrial grade Semirara coal constituents obtained from the Semirara Mining Corporation Gross calorific value. % (air dried. It is also stated in the policy that participation of other industries and institutions in the realization of this act is a must. 5-10% ash.% Ash fusion temperature. land.90 20-28 11-15 40-50 1120-1300 1140-1380 1170-1490 2. projects and plans on climate change-related disasters must be implemented. RA 9729 has been established to protect the climate system and for its risk management. C Hemispherical temperature. 9729 affirms that it is the duty of the state to create policies protecting the people and providing them a clean and healthy environment. the Philippines is susceptible to the consequences brought by climate change (Klima Climate Change Center). Furthermore. to prevent damage and destruction of natural resources and maintain clean. This policy is also in line with the global community¶s policy towards climate change. % Hardgrove grindability index. C Elemental ash analysis. % (dry basis) Sodium (Na2O) Potassium (K2O) 8650-9600 9-18 32-41 34-41 0.40-0. % (as received) Residual moisture. It is important to control climate change because as the section two of this RA recognizes. ASTMD2015) Total Moisture. socially and economically. % Volatile combustible matter Total sulfur. Section 2 of the Climate Change Act of 2009 or Republic Act No. 8 . C Flow temperature.00-4.00-2. 0. green and healthy surroundings. One of the primary objectives of this act is to stabilize greenhouse gases to prevent the harm they cause ± ecologically. Btu/lb (air dried) Proximate anlaysis (air dried. % Fixed carbon. (air dried).9% sulphur. The industrial grade of Semirara coal particularly contains the following components as shown in table 2. water resources). They have been formulated to directly serve the Philippines¶ environment (air.exist in the following ratio: 11-15% moisture.1. In line with this.3-0. The Philippine Agenda 21 allows for the fulfillment of this duty and maintenance of a well and orderly environment. carbon capture technologies that are inclined to the incorporation of thermodynamic chemical reactions. 2008). principles and processes are the scope of discussion. 2.2 Carbon Capture Technologies Due to the impending degradation that coal consumption brought about. development and protection of the environment. alleviate greenhouse gases emissions. Through the cyclic utilization of metal oxides to bring oxygen to the fuel itself. innovations resulted to numerous carbon capture technologies that have various affects depending on the properties of gas and parameters applied on the capturing medium. 2. Many environmental laws are leaning on the deterrence and/or treatment of toxic elements found in our surroundings ± gases. This section also writes that there must be national and comprehensive programs for air pollution management. and increase in levels of income and employment. making clean alternative sources of energy (apart from imported oil) abundant and available to all.The Biofuels Act of 2006 or Republic Act No. adsorption and absorption are given focus in order to gain prior knowledge about the proceeding studies.2. Which means that energy requirements are much lower that for pre.or post combustion capture or for oxyfuel combustion. the search for clean coal technologies began. It also is the preventive measure for pollution but at the same time recognizes measures which are going to help achieve the objectives of the policy. programs which encourage cooperation and participation of the citizenry and industries in the management of air pollution and which teach proper public information on air quality and on the ways to maintain cleanliness and prevent air pollution (Environmental Management Bureau).1 Chemical Looping Combustion or Chemical Looping Reforming Chemical looping combustion (CLC) and reforming (CLR) are novel fuel conversion technologies allowing inherent CO2 separation. 9 . Among the clean coal technologies discovered. The Philippine Clean Air Act of 1999 or Republic Act No. harmonious environment. Section 3 of RA 8749 must pursue frameworks for sustaining balance. chemical looping combustion and reforming (CLC/CLR). the main advantage of this method is that there is no gas separation step needed to get a concentrated CO2 stream since air and gaseous products produced after combustion of fuel were not mixed together (Yang. Its principles are resting on the provision of clean air. et al. carbon dioxide sequestration is proved to be most suitable to allow the continuation of the demand and usage of coal. In this proposal. Among the technologies known. It also focuses on improvement of livelihood with biofuels such as development of indigenous sources of renewable energy. 8749 is an act concerning the control of air pollution. The policy is in charge of lessening reliance on non-domestic fuels regarding the country¶s environment and human protection and economic growth.. 9367 is an act concerning Biofuel usage in the country. There are many laws that capture caring for the environment and provide support for projects which have potentials in helping the government to achieve their goals. The act encourages use of biofuels as a better alternative than gasoline and because of its healthy benefits for the whole state (Senate of the Philippines). healthy ecology and the human right to a clean surrounding and nature. As mentioned earlier. Ni is the most effective oxygen carrier to convert hydrocarbons. (1987) primarily to increase reversibility of combustion processes so as to utilize materials more effectively. which is called the air reactor. which is really the main advantage of CLC because it avoids usage of too much energy. Another study. which leaves a high potential for CO2 capture. based on NiO. (2009). (Jerndal. (2009). which suggested the popular notion today that Nickel has a very high durability. fuel is oxidized by the metal oxide. During the operation. displayed an increased fuel conversion when compared to oxygen carriers of NiO supported by NiAl2O4. the problem with this is that they used the word ³seemed´ to explain this phenomena connecting it to the Ni/NiO ratio. decreased CH4 conversion. et al.. the primary products of the fuel reactor exhaust gas are CO2 and H2O. air to fuel ratio and temperature are varied. very low residence times and a high power solid inventory ratio. or where a small amount of MgO was added. 2. the conversion of natural gas is relatively low. that is NiO/CH4 molar ratio. again they used an oxygen carrier based on NiO and supported on -Al2O3 was used during more than 50 hours of operation and the effect of different operating variables like temperature. this study showed that there was reasonable conversion of CO and H2 but. et al. which makes it suitable to be an oxygen carrier for a CLR system which was actually used in the aforementioned study (de Diego et al. the pilot rig was fuelled with methane at 140kW fuel power. used 24 different oxygen carriers. 2008). In this study. and a dual circulating fluidized bed (DCFB) system was designed to obtain high solid circulation. they stated that further investigation is surely required (BolhàrNordenkampf. The air reactor exhaust has consists mainly of nitrogen with some excess oxygen. 2009). but the adding of natural olivine resulted to a moderate increase of CH4 conversion (Pröll et al.. because. which transports oxygen and heat from one reactor to another. according to most studies. it was found that the oxygen carrier particles maintained their physical and chemical properties. For both oxygen carriers high CH4 conversion and CO2 yield is achieved. which very much appeared like they didn¶t find anything conclusive to really explain why this happened which is why at their conclusion. This basically showed that natural minerals such as oxygen carriers aren¶t as effective as metals. with NiAl2O4 and/or MgAl2O4 and were produced with spray-drying. 2009) which is quite adverse. These systems consist of two reactors where different gas streams are in contact with circulating solids. and in the second.. Metal oxides allow such a transport. If hydrocarbons are used as fuel in CLC (although in princicple. In the study of Bolhàr-Nordenkampf et al. is when they used natural ilmenite and natural olivine (only as an additive) as an oxygen carrier material.This technology was first introduced by Richter and Knoche (1983) and Ishida et al.2. molar ratio and solid circulation rate on CH4 conversion and gas product distribution was analyzed. presented results using CLR in a 900 ÛC circulating fluidized bed reactor using a methane as fuel. when converting hydrocarbons. two different Ni-based oxygen carriers in a 120kW chemical looping pilot rig was used. de Diego. In the fuel reactor. Higher air to fuel ratio and temperature. a relatively pure CO2 stream is left. CH4 conversion was very high (greater than 98%) and the most important variable affecting the gas product distribution was the solid circulation rate. and found that oxygen carriers supported by MgAl2O4. They found in all conditions.. Another study by Jerndal et al. any kind of major fuel can be utilized in CLC). Another study connected to this. 2009). the metal oxide is reoxidized. After condensation of water.2 Adsorption 10 . The limit of the before combustion cases would not exceed 60-70%. They followed on the theoretical framework of Dubinin¶s theory. therefore separating it from the other gases that would provide the heat required prior to energy conversion (Feron & Hendriks. They also noted special cases which resulted to higher values which indicated that CO2 uptake upperbound around10±11 wt% seemed more realistic for standard activated carbon after combustion. et al. The adsorption isotherms yielded the values of micropore volume and the energy characteristic of the carbons. In their study. 2005). they used almond shells as adsorbents for carbon dioxide. They used physical adsorption to determine maximum capacity of carbon to CO2 before and after combustion processes. It is the process wherein a substance of gas and liquid becomes attached to a solid. The substance adsorbed by the special solid is called an adsorbate. This process also gave greater carbon yield and shorter soaking time than CO2 activation (M. produced narrow microporosity in the char and incorporated stable nitrogen functionalities enhancing CO2 selectivity. They used the process of carbonisation followed by CO2 activation or heat treatment with ammonia (amination). (2007) affirmed successful CO2 capture depending on the development of the special solid used and the adsorption capacity. reducing raw carbon capacity. caused the significant decrease in microporous volume of carbon. The analysis of these results also gave the equilibrium CO2 uptake of the carbons at various temperatures and pressure. Another study by Martín et al. (2010) showed the effectiveness of adsorption to capture carbon through techniques on characterization of carbon. to trap CO2 gases. usually amine based solvents.Adsorption is the process which will be used for this study. 2010). 2010). G. The said procedures resulted to CO2 with high adsorption capacity in pure CO2 and in 15% CO2 in N2. Absorption can be held at the pre-combustion stage or the postcombustion stage. In 11 . As said earlier. As a succeeding result. CO2 physisorption occurred. absorption decarbonisation is favoured at pre-combustion. This can be applied in both combustion and pre-combustion stages but according to Feron and Hendriks (2005). 2. Carbon dioxide activation produced porosity in most of the micropore domain.3 Absorption Absorption is another carbon capture process that involves the use of sorbent liquid solvents.2. Plaza et al. (2010). They also considered the effect of impregnation with the use of commercially activated carbon. The best examples of adsorbates are the pollutants in our environment such as carbon and greenhouse gases (Mithra. the hydrogen gas (H2) must be taken into account since this gas provides significant amount of heat to power steam turbines or fuel cells. Their results showed that the amine coating. First to be discussed are the parameters considered for different combustion stages where absorption is to be employed. they used low cost sorbent. Many successful carbon capture experiments were done using the process of adsorption and CO2 with a special solid. Heat treatment with ammonia at 800 ÛC on the other hand.. Adsorption happens every day in our environment. In the study of Plaza et al. They sought different alkylamines as potential sources of sites for CO2 capture. Plaza. similar to absorption. making the carbon more basic and also increased the amount of nitrogen found in carbon. this process is favoured when decarbonisation was done at pre-combustion. However. What Yang would like to point out. it is easily worn out by other absorbable waste gases such as SO2. Hoff. and thus the design of high volume reactors (Alix et al. In fact. Yang also justified that MEA has a small CO2 loading. & Juliussen. energy regeneration and cyclic capacity are also significant in analyzing the absorption capacity of solvent. Furthermore. & Pennline. Resnik. 2-(2-aminoethyl12 . equations cannot be justified due to the variations of methodology and concentrations. absorption can be preferably done right after gasification of gases before allowing entrance to the equipments. 2(methylamino)ethanol (MMEA). absorption efficiency of solvents would depend on physical properties such as its solubility. To address that problem. like monoethanol for instance. Svendsen. and also including principles in physical chemistry such as reaction kinetics. (2007) operated the screening apparatus illustrated in Figure 2. vapour pressure. mass transfer of incoming gases and equilibrium between absorbed particles and absorbent must also be considered (Blauwhoff. foaming tendencies and its ability to wear equipment. HF and oxygen and it also corrodes equipments(Yeh. Moreover. equipments that will have to control the parameters such like letting CO2 react with MEA to form a carbamate and heating it later for the release of CO2. Next is the selection of the solvent for absorption. (2005). therefore making carbon capture process more effective. 1983). Recent studies proved that there are other solvents that could compete with the absorption capacities of MEA in terms of cost and efficiency. as Blauwhoff pointed. collecting and transporting the CO2 through lower pressure at a higher elevation. molecular mass. was that the repetitive regeneration and reheating of MEA actually constitutes 70% of an energy plant¶s total cost.). In addition to that. Pennline (2008) stressed the fact that precombustion absorption requires gasification of fuel produces more concentration of CO2 against CO. & Mahmud) and specifically designed fabric membranes of which their efficiencies conform to the principles of hydrodynamics (Alix. 2005). The use of MEA however is not economically friendly as it used to be. et al.). 2-(butylamino)ethanol (BEA). Versteeg. Alkanoamines. the volume of the gas should be considered since carbon capture requires the exiting gases to be at low pressure. As for postcombustion absorption process. and then by design. (1983): Ž‘‰  The availability of such data therefore makes monoethanolamine a good specimen to study absorption. & Van Swaaij. But for the other alkanolamines. HCl. NO2. 2007). N-methyldiethanolamine (MDEA). have been one most commonly used since industries sought to address problems on pipe corrosion due to acidification of H2S and CO2. basing upon the study conducted by Idem et al. according to Yang (2008). One such study conducted by Ma¶mun et al. According to by Aronu et al. 2-(ethylamino)ethanol (EMEA). (2009).1 at 80ÛC atmostpheric pressure to observe the absorption/desorption capacities of the nearly pure assays following solvents: monoethanolamine (MEA).order to avoid corrosion of equipment due to the acidic properties of CO2 (Ma'mun. Rygle. Its rate of reaction (being found with utmost accuracy among all other alkanolamines) was given by the following as compiled and formulated by Blauwhoff et al. physical designs are incorporated along with absorption like packed columns (Khan. Krishnamoorthi. and Ma¶mun et al. N¶di. comparison of the efficiency of each sorbent was based off monoethanolamine as a common material used in industrial operations. But since TEPA had the least tendency of desorption. evaluates solvents of almost pure concentrations (ranging from 85-99. like for instance. However. In this study. In so far. et al. Also. 2005) as solvent and liquid sorbent-membrane systems that uses chemical and physical means to sequester CO2 (Teramoto. storing captured CO2 and regeneration of this medium may be a problem. this will be discussed in detail in the following section. Among the solvents TEPA was able to absorb the most CO2 among other sorbents. (2009) Another study conducted by Aronu et al. taking into account the differential increase in temperature as the gas travels through the apparatus.1 was utilized at the same conditions as the previous. Although there may still be considerations in analysis. the fact that AEEA has a lower vapour pressure which indicates that it has lesser volatility. Since the main focus of the research is the ammonium absorption technology. tetraethylenepentamine (TEPA). Besides the use of alkanolamine other amine derivatives. N.. there also proposed the use of ammonia (Resnik.9% by mass) namely monoethanolamine (MEA). Takeuchi. To determine the sorbents¶ the same screening apparatus for analyzing the solvents shown in Figure 2. as obtained from Aronu et al. & Matsuyama. Nevertheless. 13 . Yeh. 2004.1 Rapid screening apparatus incorporated in the methodologies of Aronu et al. AEEA exhibited an almost consistent. there appeared to have a decrease in performance due to viscosity when concentration is increased. TEPA exhibits the capture of more CO2 compared to MEA whose efficiency lowers upon continuous cycles.(2 hydroxyethyl) piperazine (DIHEP). 2001).amino)ethanol (AEEA). piperazine (PZ). linear relationship of loading CO2 and its capacity to absorb CO2 from the water bath at 40ÛC up until it reaches 80ÛC at the end of the cycle. It may still be necessary to conduct experiments that could determine the diverse effects due to the different concentrations on one particular solvent. 2-amino-2-methyl-1-propanol (AMP). (2009). N-2-hydroxyethylpiperzine (HEP) and potassium salt of sarcosine (KSAR). Figure 2. the lean loadings (by mols of CO2 per mol of solvent) given the same reaction rate is sufficient to prove that there are more economic alternatives than the use of MEA. Maki. whereas ammonia could be used at temperatures as ambient as 20ÛC. Having defined other factors to be taken in account for the study of ammonia absorption.3 Incorporation of Ammonia in Decarbonisation Absorption Ammonia decarbonisation technology has not yet been employed in actual industrial settings however Puxty et al. The end concluded that in order for MEA can absorb CO2 around 1. However. 2010).5 to 2 times than ammonia does. For the regeneration of ammonia. Figure 2. & O'Connell. ranging from 5ÛC to 20ÛC at CO2 partial pressure range of 0 to 20 kPa which is different from the usual method of analyzing the loading capacities of alkanolamines which are held at temperatures from 40ÛC to 80ÛC. But in order to make up for the decrease in reactivity with the lowering of temperature. is based upon the mass of CO2 transferred upon passing through an absorbent wetted wall column (Puxty. Results showed relationship of absorption flux as a function of CO2 loading. In the said procedures. low energy requirement for regeneration and its resistance against oxidation. Yeh and his colleagues¶ paper may serve a 14 . temperature and CO2 partial pressure of both solvents and comparison of the values. Mathias et al. Yeh et al. the exhibited release of CO2 as shown in the said author¶s results accounts to 60% to that of the total CO2 originally absorbed. et al. (2005) showed and stressed that the reaction mechanisms involved during the dissociation of ammonium bicarbonates to CO2 and H2O have the lowest enthalpy. temperature is kept low. a larger contact area by enlarging the dimensions of the absorber column.. Example of procedures testing the loading of ammonia as compare to the commercial absorbent. 2009). MEA.2 Schematic diagram of the procedures used by Puxty et al. The overall schematic diagram of the procedures used by the author is as shown in figure 2. (2010) in determining the load capacities of ammonia and MEA In addition to the problems that may yet be encountered in using ammonia to replace alkanolamines would be the energy requirement for the compressor for refrigeration and the fouling of the stripper at temperatures below 50ÛF(Mathias. In addition to that. (2009) pointed that an increase in pressure is one way to physically reduce the energy needed for compression. There also stated a precaution procedure in handling absorbed gases. Reddy.2. (2010) stated that ammonia has been proposed as a medium for carbon capture due to its high loading.2. although it has to be kept at a low temperature due to its volatility. where cold water (at 4ÛC) is mixed with the laden absorbent to avoid the evolution of gases before sealing. MEA will have to be kept at a temperature not lower than 40ÛC. Details about the theoretical perspectives obtained will be discussed in the next chapter.good introduction. 15 . 820° 17.817 at -79ÛC while the specific gravity if 0. 2010) consisting of one nitrogen atom bonded to three atoms of hydrogen. The following vapour pressures of 1 mmHg to 760 mmHg and their corresponding temperatures are summarized in table 3.4ÛC at atmospheric pressure which therefore classifies ammonia as a highly volatile compound.2 Vapor pressure of ammonia (NH3) and corresponding temperature as obtained from Perry¶s Chemical Engineering Handbook Pressure.496° 14. Svendsen.Chapter 3: Theoretical Framework 3. & Chen. Two free electrons on the nitrogen atom allow this compound to attain a trigonal pyramidal structure.1 Physical properties of ammonia (NH3) obtained from Perry¶s Chemical Engineering Handbook formula weight refractive index specific gravity melting point ( C) boiling point ( C) solubility in 100 parts: cold water hot water other solvents 89.) 0. vapour pressures much lower than 1atm must be achieve.90° 7.325 (lq. There. To retain its liquid form. Table 3. The physical properties of ammonia recorded in Perry¶s Chemical Engineering Handbook (Green & Perry.1. Wang. Furthermore. (2010). Table 3. maintaining ammonia in its liquid form will once again depend on the partial pressure the incoming flue gas exerts. 2008) are summarized in table 3. it can be seen that ammonia attains a specific gravity of 0. since ammonia is less likely to saturate given the operating temperature (20ÛC) which is still near ambient. °C 1 109.5971 (A) 77. ammonia will have to be mixed with solvents with lesser volatility while vapour pressure contributes to the compression of molecules into liquid form as did Rivera-Tinoco et al. Boiling point is at -33.5 .4   Since low pressure drops are expected upon the entry of the CO2 gas into the reactor.03 1.1 Chemical Properties of Ammonia Ammonia (NH3) is a weak alkaline inorganic compound (Qin.7 33.5971 at ambient temperature.817 79° 0.1 5 16 97.2 as obtained from the previous source. mmHg Temperature. Hartono. 4 57.2 91. (2009) listed down the equilibrium reactions that were observed in a CO2 ±H2O-NH3 during the absorption process. Darde et al.4 33.6 Reactions Involved in Ammonia Decarbonization Several journals have stated the reaction mechanisms involved in vapour-liquid equilibrium in literature. reactions under the liquid-solid equilibria show that the left side is consisted of binary to ternary reactants of heterogenous gas liquid mixtures. There. The capability of forming these solids is something to be considered when designing since as Yeh(2005) says. ammonia carbonate ((NH4)2CO3·H2O). 17 Liquid-solid equilibria     •             • (13) (9)     • (11)   Ž (10) (12) . Aside from the formation of solid crystals. in which states that application of pressure at the side containing more reactants may shift the reaction into forming a more compressed product (Maron & Lando.9 85. this could build up on walls and eventually clogging pipes at prolonged accumulation.0 45. pressure plays a significant role optimizing the absorption of CO2 with ammonia.3 List of equilibrium reactions involved in ammonia absorption Speciation equilibria  ƒ“         ƒ“    Vapor-liquid equilibria  ‰  ƒ“  ‰  Ž (1) (3) (5) (6) (8)   •  ƒ“  Ž  ‰  Ž     ƒ“   •  (2) (4)   (7) The author noted that among those equilibrium reactions. ammonia carbamate (NH2COONH4).1: Table 3. 1974).10 20 40 60 100 200 400 760 3. five of them include the formation of solids namely ammonia bicarbonate (NH4HCO3). Among the reactions were the following as shown in table 3.3 68. sesqui-carbonate ((NH4)2CO3·2NH4HCO3) and frozen water. Hence. it can be seen that Le Chatelier¶s principle may apply.8 79.2 74. Figure 3. 2005) mentioned that the principle of absorption has been used in obtaining high concentrations of gas solute and the remaining solvent maybe discarded and reused.4.1 Material balance 18 .3.. The blue lines represent tie lines of which systems compositions enable the precipitation of solids indicated while the black line is that solely for the formation of hydrated ammonium carbonate. McCabe (McCabe.4 Absorption Absorption is defined as the introduction of inert gas into solvent wherein which the former will be soluble (McCabe. the focus will be on mass transfer and physiochemical properties. 2005). However. factors such that the composition of three compounds must be considered in order to facilitate the flow of gases while controlling the amount of crystals while in contact. To give a fundamental introduction of the appearance of the three liquid diagram. The author further added that the opposite of such operation is known as stripping or desorption wherein there involved the counter flow of an inert gas upon contact with solute laden absorbent. & Harriot. Smith. et al. 3. figure 3. Since the thesis only covers the absorption capacities of different ammonia concentrations.1 is as presented by Thomsen¶s Extended UNIQUAC model in comparison to Jänecke¶s (1917) findings. this may not be a reliable basis for determining the equilibrium systems at 20ÛC which has yet to be analyzed.1 Ternary diagram of NH3-CO2 ±H2O system at 40ÛC and 1 bar as presented in UNIQUAC model The solid-liquid ternary diagram is a Type II: Binary Compound Formation in terms of Maron and Lando¶s (1974) classification.3 NH3-CO2 ±H2O Equilibrium Diagram Since aqueous NH3 form crystals with CO2. 3. O2.0089.4. CO. 2005) where L and V represent the molal flow rates.2 Limiting Gas-Liquid Ratio When operating the absorption column.. 3.For any reactor used in absorption. (2010).2 Overall volumetric mass transfer coefficient vs. gas-liquid ration to be observed will be at 0. 3. 19 . 2010). 2005) where subscript B represents component B of the system. yB and yA is the mol fraction of component B in vapour phase and liquid phase respectively. the material balance is as follows: (McCabe. gas-liquid ratio (Qiu. N2 and SO2. et al.. However. Therefore in this research. the overall volumetric mass flow reaches its highest (Qiu. et al. there will be components such as CO2. Based on findings by Qiu et al... et al. the overall volumetric mass transfer coefficient with respect to gas-liquid ratio is as follows: Figure 3. 2010) It can be seen clearly that the increase in overall volumetric mass transfer was due to the increase in solvent which is the 10% (v/v) aqueous ammonia. the line seems to deflect horizontally as it goes beyond which indicates that further increase in solvent¶s molal volumetric rate will not result into any significant increase in absorption efficiency. x and y represent the mol ratios of solute in liquid and gas phase respectively.007 for all concentrations. et al. it is important to know the limiting gas-liquid ratio (L/V) to ensure that the process is done efficiently and economically. Although it is not yet certain which of the gases except nitrogen shall be absorbed. a and b represent the input and output positions respectively. the material balance for multicomponent absorption is given by: (McCabe. With the liquid-gas ratio at 0. xB* is the mol fraction of solute in equilibrium with the liquid phase.3 Multicomponent Absorption Since combustion of fuels such as coal are not often complete. H2.4. Subscripts a and b indicate the input and output positions respectively. One of the most recent studies conducted by Qian (2009). 2010). (dimensions for for height and diameter are 0. Hence. Wang.0127m respectively) will be converted to one such like Qian¶s. 2005). Wetted-wall columns simulate packed tower reactors such that both involve the counter flow of two different fluids (Puxty. & Chen. while maintaining film thickness of 1. 2009). 20 .3. However the difference is the liquid inlet that is made to flow through a smaller cylinder which is the column. 2009.. Tong. 2010). L is the length of the column.38 mL/s. (2009) this instrument is first used by Mshewa (1995). the volumetric flow rate should be at 0. bound by an outer metal jacket. that is only to approximate the workable design since that equation is applicable when no CO2 is yet loaded and when operation is done at atmospheric pressure (Qian & Guo. et al..5 Wetted-Wall Column Simple laboratory settings for the determination of CO2 of absorption of different solvents involve the use of wetted-wall columns (WWC) as reactors (Liu.15×10-4. using the modified wettedwall column made of 1mm spaced steel tube annulus column and 23mm spaced annular jacket (where water bath circulates) exhibits the liquid film thickness of N-methyldiethanolamine given by this equation: Where Q is the volumetric flow rate of the solvent. and was since then commonly used by other researches involving the test of absorption. Calculation is shown in the appendix A.0821m and 0.1.. Puxty. et al. However. say the wetted-wall column used by Puxty et al. Liu et al. This equation may prove crucial in determining the limiting factors when operating the column since increase in thickness (as related to the mass) of the solvent may dilute the solute gas which is to be avoided since it makes stripping of CO2 gas difficult (McCabe. et al. Zhao. tc is the contact time and R is the radius of the inner of the column annulus. Figure 4.4M. Aperture for the gas inlet however will be enlarged to 10mm for a greater pressure drop at the end of combustion.3M.27 cm and outer diameter of 1.1 Materials Carbon dioxide source to be used in this thesis will be from the flue gas produced from the combustion of Semirara industrial grade coal.5M and 0. another glass enclosure is provided to protect the mechanism and allow the monitoring of process. Annular Pyrex glass jacket with an internal diameter of 2.1M. The following dimensions are as follows: annular metal column with 1mm space and inner diameter of 1.1 Qian¶s wetted-wall column design Lastly. Also. 4. figure 3.21 cm. the diagram setup is illustrated in figure 4. Reactor model shall be based upon Qian¶s (2009) model where dimensions applied will be the same as that of Puxty¶s (2010) wetted-wall column. 0. Steel flanges that seal the reactor will have indentions where thermometer can be placed for the monitoring of temperature.6M.37 cm for the plastic tube (assuming metal sheets).2 is provided.2 Experimental setup 21 .04 cm including inlet and outlet for the water bath. The height of the column remains stationary at 8. Specific materials used as described below the figure may not necessarily apply in actual fabrication for this procedure. Absorption of flue gas from the combustion of 10g sample of coal shall be tested upon 10 g samples of aqueous ammonia solutions of different concentrations: 0. In order to show the basis of design. 0.2 Experimental Setup For quick reference.Chapter 4: Materials and Methodology 4.2. it will require gas analyzing instruments such as gas spectrometers to analyze the content of gases. 0. 0.2M. Figure 4. before and after the absorption is to be done.54 cm and an outer diameter of 5. After the analysis with gas spectrophotometer. Semirara coal is combusted with theoretical air. Once cooled. the composition of the flue gas from combusted Semirara coal (10 gram sample) must be determined separately from the experimental set up. before the absorption of aqueous ammonia will be tested.83 mL/s through the annular space of the wetted-wall column by the use of pumping force. flue has is stored temporarily in flask submerged in circulating water bath. 4. 4. Meanwhile. Since a large amount of heat is expected to evolve. another 10 gram sample will be combusted in the same manner as did the previous five trials. (2010) experimental setup however there are a few modifications since combusted coal fuel gas is used. H2. Coal will be combusted such that only ashes remain and there added five minutes of heating after the solid fuels are no longer visible. O2. N2.This is derived from Puxty¶s et al. cold water of 20ÛC will be circulated through the annular space of the outer glass jacket.3 order. gas will be introduced to the saturator (1/8´ stainless steel coil) maintaining a CO2 partial pressure of 20 kPa. SO2). computation will be based upon the data provided by the Semirara Mining Corporation with the assumption that fuel undergoes complete combustion. Flue gas will be temporarily stored inside a flask while being gradually cooled in a circulating water bath. CO. Partial pressures of solute gas may be calculated theoretically with gas correlations to determine the control pressure to attain desired gas velocity. As for the theoretical air to be introduced. At the heat source. As for the outer annulus. the average of five records for each gas composition will be computed for and used for theoretical calculation in material balance. five trials will be held to obtain five records of the flue gas composition (CO2. To ensure the accuracy of data.3. 22 Experimental Procedures The following procedures to be done in the experiment are presented in chronological . 10 grams of aqueous ammonia sample will be placed in water bath while being circulated with a volumetric rate of 0. For the actual determination of absorption. H2O.1 Combustion of Semirara Coal As mentioned in the earlier sections. 1M. The gas flow rate will be controlled with the pressure regulator. For the next five molarities. 0.38mL/sec and will be indicated by an orifice meter. Then the unabsorbed flue gas after the equilibrium will be recorded. and 0. 0.3.2 Preparation of Aqueous Ammonia Sample For the variation of solvent absorbents.3M. ammonia shall be diluted in water in the following molarities: 0. then to the column countercurrently with the solvent sample to be tested.2M. These will be loaded into the sample reservoir and pumped within the reactor.5M. 0.4M. Cooled flue gas will be made to pass through the saturator. Figure 4. 4. While flue gases are left to cool. Gas flow rates for each corresponding molarities above will depend on the partial pressure of CO2 of the flue gas to be analyzed.3 Absorption Determination While flow rate of solvent is maintained constant and the molarity increases. No carbon dioxide loading will be done beforehand.3 Flowchart of procedures 23 . conditioner and then be analyzed with the gas spectrometer until liquid and gas finally comes into equilibrium. 10 g of aqueous ammonia sample will be first placed in water bath for five minutes until it comes to thermal equilibrium. Unabsorbed flue gas composition will then pass through the condenser. another 10 g sample of coal will be loaded. 0. and 10 g sample of solvent to be placed in the water bath to attain thermal equilibrium in preparation for another analysis.6M.3. combusted and cooled.4. there should be an equivalent decrease in flow rate for the incoming flue gas. Then liquid will be made to run 0. C. Ludovic. G. Frequently Asked Questions: Coal Retrieved 23 November. Meyer. Karl Anders. 8749 Retrieved 16 November.1016/j. Michel. doi: DOI: 10.. Michel. & Rouzineau. A study on the reaction between CO2 and alkanolamines in aqueous solutions.023 Allied Deviation. Republic Act No.2009. M. Hoff. Victor. Chemical Engineering Science..2010. 19-25. 60(3).com/locations/pipeline/MSDS. F. Energy Procedia. (2009). Hermann. Erling H.egypro. 1035-1042. & Stenby. 1411-1429. Juan. doi: DOI: 10.ph/mmairshed/Policies/ra8749-clean%20air%20act.egypro. Adánez.2008. Pascal. doi: DOI: 10. P.004 DOE Portal: Official website of the Philippine Department of Energy. Solvent selection for carbon dioxide absorption. The world price of coal. Abbe. 1(1). Willy J. Johannes. Alberto. van Well. doi: DOI: 10.2009.cej. doi: Doi: 10.ph/faq's/coal. García-Labiano. Raynal.139 Blauwhoff. & Hendriks. Corrected Proof. M. Robert H. David. 2010.. Abad.137 de Diego.1016/j.htm Ellerman. 451-459. 24 . Mass transfer and hydrodynamic characteristics of new carbon carbon packing: Application to CO2 post-combustion capture. François. Philipp. Kolbitsch. 1(1). (2009). 289-298.005 Darde. from http://www.09.egypro. doi: DOI: 10. Performance of a NiO-based oxygen carrier for chemical looping combustion and reforming in a 120 kW unit. Chemical Engineering Research and Design. Energy Policy.. doi: Doi: 10. & Perry. Oil & Gas Science and Technology . M.1016/j. Tobias... & Juliussen. Francisco.2009. Versteeg. Olav. 38(9). Les différents procédés de capture du CO2 et leurs coûts. 144(2). 499-506. Ugochukwu E.Rev. (2008).. A. & Van Swaaij. Perry's Chemical Engineers' Handbook (8th Edition): McGraw-Hill.gov. Don W. Chilled ammonia process for CO2 capture. from http://www. 2010. & Hofbauer.References Alix. H. 23(6).1016/j. from http://www. (2008). Pilar. Svendsen. P.01. Thomsen. M. 1051-1057. P.1016/j.M. Prevost. Denny. (2005). María. In Press.1016/0009-2509(83)80077-3 Bolhàr-Nordenkampf.. (1995)..alliedaviation. (1983).1016/0301-4215(95)91231-z Environmental Management Bureau.01.pdf Feron.pdf Aronu. 1(1). 2010. Hallvard F.06.. IFP. Energy Procedia. Pröll.01. Material Safety Data Sheet: Ammonia Retrieved 27 November.gov.doe. Green. W. Chemical Engineering Journal. & Gayán. Luis F.cherd. (2009). Ortiz. Synthesis gas generation by chemical-looping reforming in a batch fluidized bed reactor using Ni-based oxygen carriers. Kaj.emb. A. Energy Procedia. 2009.19170230306 Jerndal. Chakma. Svendsen.01..1016/j. Thijs. Safety Science.2010.com/dbderived-f/lafarge/derived_files/derived103612. M.04. T. (1987).06.. Modelling Reactive Absorption of CO2 in Packed Columns for Post-Combustion Carbon Capture Applications. & Lyngfelt. Evaluation of a chemical-looping-combustion power-generation system by graphic exergy analysis. Energy Procedia. Changhe. Snijkers. & Mahmud. 45(8).1016/j.064 Kentucky Educational Television. 479-486. T..1016/j. 2010. Hoff.1016/j. Fundamentals of Physical Chemistry. Wilson. 49-55.ket.2007. (2005). Shujuan. Pilot Plant Studies of the CO2 Capture Performance of Aqueous MEA and Mixed MEA/MDEA Solvents at the University of Regina CO2 Capture Technology Development Plant and the Boundary Dam CO2 Capture Demonstration Plant. Inc.klima. & Juliussen. 251-258. Ernst..Idem. Selection of new absorbents for carbon dioxide capture.ph/RA9729.drying as oxygen carriers for chemical-looping combustion.egypro. doi: Doi: 10.html Khan. M. 933-940. Accepted Manuscript.buildsite.020 Kirchsteiger. & Akehata. H. (2002). (2008). 25 .pdf Liu. New York: McMillian Publishing Co.ssci. Huiling. doi: DOI: 10. Anders. Energy Conversion and Management. Sholeh. from http://files. Ivo. 46(7). 1(1).1016/j. Hallvard F. 2010. J.2006. Bo.enconman. Zheng. (1917).01. (1974).1021/ie050569e Ishida. Karl A.124 Ma'mun. C. Electronic Field Trip to a Coal Mine Retrieved 21 November. Materials Safety Data Sheet Retrieved 29 November. Krishnamoorthi.012 Klima Climate Change Center. Tontiwachwuthikul. Absorption of carbon dioxide in aqueous ammonia. doi: 10. Energy Procedia. doi: DOI: 10. S. B. Erik. (2009). Frans. (2007). V. & Chen. doi: 10.. doi: 10. Energy. Aroonwilas. Zhao. (2009). Über die Konstitution der Eisen-Chromlegierungen. from http://www. 9729 Retrieved 16 November. 2010. Paitoon. Zeitschrift für Elektrochemie und angewandte physikalische Chemie. & Lando. 1149-1154. Malcolm.egypro. Olav.. F. Don. Chemical Engineering Research and Design.007 Maron. 48(1). NiO particles with Ca and Mg based additives produced by spray. Industrial & Engineering Chemistry Research. 2414-2420..2009. 12(2).org/Trips/Coal/AGSMM/agsmmtypes. D. doi: DOI: 10. Raphael. 1(1). Republic Act No. Tobias. Tong. 23(3-4). 147-154. Adisorn. doi: DOI: 10.cherd. Amornvadee. & Gelowitz..pdf Lafarge North America. Jinzhao. from http://www.09.1016/0360-5442(87)90119-8 Jänecke. Wang. Mattisson. Veawab.1002/bbpc. Carbon capture and storage-desirability from a risk management point of view. Amit. In Press. from http://www.1016/j. Tobias. & Alvarez. Energy Procedia. & Rubiera. 897-907. Rubiera. C. 1(1). Anders. F.fuproc. Tobias.01. Rubiera. 89(9).Martín. Modeling and Kinetic Study on Absorption of CO2 by Aqueous Solutions of N-methyldiethanolamine in a Modified Wetted Wall Column. from http://www. Paul M. 915-922. M..1016/j. 2204-2212. 2010. (2010).. 71(1). & Ilconich.2009. Separation and Purification Technology. M. Developing almond shell-derived activated carbons as CO2 adsorbents.need.1016/j. C.09.. Morsi. J.. J. (2007). Pevida.htm Mshewa. Martín. 2010.02.1016/j. C.com/what-is-adsorption. M.002 Plaza. A. 2010. Energy infobooks Retrieved 20 November. F. David R. J. P. Mayer. & Harriot. J..11. & Attalla. doi: DOI: 10. Natural minerals as oxygen carriers for chemical looping combustion in a dual circulating fluidized bed system. C. What is Adsorption Retrieved 24 November. Moetaz. Coal Carbonization: Current and Future Applications Retrieved 20 November. National Energy Education Development Project. Kolbitsch.. (2008).2008.2009.. C. 1(1). On the limits of CO2 capture capacity of carbons. Fuel. John P.seppur. (2010). Smith. J. Luebke... Pis... from http://www.. Mattisson. 1227-1234. 65(2).1016/j.2007. 225-229. T.. M. Chinese 26 . C. Chemical Engineering Science.2010.ces. Kenneth L. Myers. F. & Guo.seppur.161 McCabe.. Fuel Processing Technology.2009. Menendez. G. & Pis.. (2009).egypro. Comparison of the rate of CO2 absorption into aqueous ammonia and monoethanolamine. Robert.fuel. doi: DOI: 10.. Energy Procedia. A. Pevida. Carbon Dioxide Desorption/absorption With Aqueous Mixtures of Methyldiethanolamine and Diethanolamine at 40 to 120°C. Pis. 86(14).pdf Mithra.. Plaza. & O'Connell. Kai.wisegeek..gov/PCS/acsfuel/preprint%20archive/Files/34_1_DALLAS_0489_0263.042 Qian.. Henry W.pdf Pennline.06.).008 Plaza. Lyngfelt. J. W. Heintz. R. (2009). CO2 capture by adsorption with nitrogen enriched carbons. Quantitative evaluation of the aqueous-ammonia process for CO2 capture using fundamental data and thermodynamic analysis.009 Mathias. 102-106. Pevida. R. (2010). Rowland. New York: McGraw-Hill. Zhi. F.1016/j. (1995). Badie I. doi: 10. L. (2005). Yannick J.egypro. 74(2). Graeme. Jones... (2009). & Centeno.2009. Johannes.01. Unit Operations of Chemical Engineering (7th ed. Bolhàr-Nordenkampf. Satish. Arenillas. (2010). Progress in carbon dioxide capture and separation research for gasification-based power generation point sources. Reddy. doi: 10..anl. S. (Eds. F. doi: DOI: 10. 27-34. Christina R. Fermoso.006 Puxty. Hermann. J. Philipp.. doi: DOI: 10. doi: DOI: 10. & Hofbauer. G.06. Karl.001 Pröll. M..1016/j.). Jeffery B. Separation and Purification Technology.org/needpdf/infobook_activities/SecInfo/CoalS. Rydén. from http://eh.2009. T..1016/s10049541(08)60246-3 Qin. Gas separation by liquid membrane accompanied by permeation of membrane liquid through membrane physical transport. Lyngfelt. P. 71-85): AMERICAN CHEMICAL SOCIETY.semiraramining. doi: DOI: 10. (2010). doi: DOI: 10. Zhang. 89-104. 24(1-2). Clean Coal Technologies. Wen-Wen. 2010. economy in the 1920's Retrieved 23 November. Anders. Fuel. Richter Horst. 431-434. 235.fuel. (2001). (2010).com/CoalProduct. Hartono. & Bouallou. Aqua ammonia process for simultaneous removal of CO2. Chao-Run. . S. Yeh. (2004). doi: DOI: 10.Journal of Chemical Engineering. Separation and Purification Technology.1920s. De Lasalle University.jclepro.02. (1983). 18-20 June 2010).2010.07. F.004 Semirara Mining Corporation. Aida. pp. Ardi. H.. (2008). 2010.2006. K. Studies on Mass Transfer Process of CO2 Absorption in Aqueous Ammonia in Packaged Column. Synthesis gas generation by chemical-looping reforming in a continuously operating laboratory reactor. Wang. 2010 4th International Conference on.. Comparison of absorption rates and absorption capacity of ammonia solvents with MEA and MDEA aqueous blends for CO2 capture. Feng. J.cpa. (2010). Chakib. & Mattisson.1016/j. Tobias.12. Rivera-Tinoco. (2006). Kinetics of CO2 absorption in aqueous ammonia solution.006 Roces. Gong. 729-738.S.gov. Special issue on: Accounting for global warming.. doi: Doi: 10. 2010. Power Point Presentation.010 Qiu. Paper presented at the Bioinformatics and Biomedical Engineering (iCBBE). Shao-Lin. Magnus. Zhong-Zhu. 875-880. . 18(9). .1016/j.pdf Smiley.2007. 4(5). W. International Journal of Greenhouse Gas Control. & Chen.. Reversibility of Combustion Processes Efficiency and Costing (Vol. International Journal of Environmental Technology and Management. doi: Doi: 10. The U. Shujuan. Huan. Critical Perspectives on Accounting. Zheng. 571-579. Changhe.senate. from http://www. doi: DOI: 10. Journal of Cleaner Production. 17(4). Nao. Li. Department of Chemical Engineering. & Matsuyama.final Sy. 85(1213). (2010). Masaaki. Svendsen. Hideto. Hallvard F. (2010. 9367 Retrieved 16 November.ijggc.04. from http://www. Guo. Pennline. 101-112. Resnik.ph/republic_acts/ra%209367. J. Maki. Lei.php Senate of the Philippines. Takeuchi. 1631-1641.1016/s1383-5866(00)00216-1 27 . Peng..1016/j.net/encyclopedia/article/Smiley. Gene. Rodrigo.1016/j. Li.002 Teramoto. Republic Act No. 4(1-2). & Knoche Karl. Taisuke. 19(4). SO2 and NOx. Coal Product Retrieved 25 November. 20(1).worldcoal. Ian. & Wright. 14-27.1016/j.gov/cneaf/coal/quarterly/html/t35p01p1.int/kyoto_protocol/items/2830. 2010. Resnik. 86(14-15). Coal Consumption at Manufacturing Plants by North American Industry Classification System (NAICS) Code Retrieved 21.fuproc. Energy Information Administration.eia. Coal Statistics Retrieved 23 November 2010. Bland. Rajender. Rygle. from http://www. November.U. Henry W. (2010). Xu. Maohong. Gupta. doi: DOI: 10. doi: Doi: 10. Kyoto Protocol Retrieved 7..S. Journal of Environmental Sciences. November. Kathy.1016/s10010742(08)60002-9 Yeh. U. from http://www. Fan.php World Coal Association. 1533-1546. from http://www. Slimane. Semi-batch absorption and regeneration studies for CO2 capture by aqueous ammonia. from http://unfccc. (2005)..org/resources/coal-statistics/ Yang.. Hongqun.org/coal/what-is-coal/ World Coal Institute. Progress in carbon dioxide separation and capture: A review. & Pennline.. 2010.worldcoal.01. Fuel Processing Technology. 2010. Rachid B. James T. (2008).pdf United Nations Framework Convention on Climate Change.015 28 . Kevin P.S. What is Coal? Retrieved 20 November. Alan E. Zhenghe.2005. Appendix A.1 Approximation of flow rate of aqueous ammonia through the equation suggested by Qin (2010)       29 . Calculations A. Sulfur.1ºC 100% Colorless gas/liquid and pungent odor Stable at room temperature Will react exothermicall with acids and water CAS registry number: 7664-417 Formula: NH3 Molecular weight: 17. (STEL) Federal OSHA PEL NIOSH REL / ACGIH TLV IDLH 30 . Hazardous Decompositions Hydrogen and nitrogen gases above 450ºC (842ºF) can form high heat. etc« Explosive combustion result with mixture of air and the following: hydrocarbons. Nitrogen Oxide. Fluorine.03 Hazard Description Not recognize by OSHA as a carcinogen. Acetaldehyde.4 g/100cc @100ºC 23. Iodine. Mercury. Nitrogen Tetroxide. Ammonia may form hazardous reactions with the following: Silver. etc«. Ammonia can corrode galvanized surfaces. Chloric Acid. Conditions to Avoid Mixing ammonia with halogens. Acrolein. etc«. Perchlorate. Reaction with metals may help dissipate heat Exposure limits 50 ppm 25 ppm 35 ppm 300 ppm 8 hour (TWA) 10 hour (TWA) 15 min. etc.596 @ 0°C (32°F) 10 atm @ 25. Gold.1 Materials Safety Data Sheet Ammonia Description Chemical name: Anhydrous Ammonia Synonyms: Ammonia Chemical family: Inorganic Composition: 99~% Ammonia Physical Properties Boiling point Freezing point Flash point Self-ignition temperature Flammable limits in air Specific gravity (water=1) Vapor/air (air=1) Vapor pressure Solubility in water Surface tension Percent volatile Appearance and odor Reactivity -33°C (-28°F) -78ºC (-108°F) none 651 ºC (1204ºF) catalyzed by iron 850 ºC (1562ºF) uncatalyzed LEL 15% UEL 28% 0. bronze. copper. Silver Oxide.B. Not listed in the National Toxicology Program annual report. Tellurium Halides.4 Dynes/cm @ 11. Boron. Tin. Bromine. and silver. brass. Chlorites. Ethanol and Silver Nitrate. aluminum alloys. mercury. strong mineral acids. strong oxidizers.682 @ 4°C (39°F) 0. Chlorine.7ºC 89. gold. Chloric Monoxide. B. Nitric Acid. Reaction with Silver Chloride. Not listed as a carcinogen by the International Agency for Research on Cancer. Halogens. form explosive products.9 g/100cc @ 0ºC 7. SEEK MEDICAL ATTENTION IMMEDIATELY. Remove contaminated clothes and gears and flush inflamed skin with abundant amounts of water for 15 minutes. exposing the eyeball. bronchospasm. 31 .Emergency Treatment Hazard/Symptoms Lacrimation. Carefully remove contaminated attire in case of material frozen to skin that might cause further abrasions. Move to area with fresh air. Irritation. Avoid eating. Cool fire exposed containers with water spray while upwind *There are no chronic effects. drinking or smoking inside the lab Give plenty of water or citrus juice to drink if conscious. edema or respiratory arrest upon inhalation. Peform transfer under the hood where vapors are drawn away. pulmonary edema and other symptoms similarly occuring in inahalation may occur upon ingestion. Lung irritation. Acute irritation of respiratory tract. Wear personal protective equipments (PPE) at all times until after the cleaning and keeping of equipments. Do not induce vomiting. *FOR ALL EXPOSURES. edema or blindness to the eye. Do not apply any salves or ointment. Notes: *To physician. Properly label container. blister formation on skin. Formation of explosive compounds and/or reactions as mentioned in Conditions to Avoind and Hazardous Decompositions Preventive Measures Wear goggles when handling chemical Fire Extinguishing/First Aid Flush eyes with abundant amount of water for 15 minutes with eyelids held away from each other. Wear protective clothing and pressure postive SCBA. Apply oxygen or artificial respiration if unconscious. Therefore supportive treatment and ventilation should be provided to make sure. inflammation or edemas due to extreme exposure may cause death. corrosive burns. Caustic burn may result from tissues freezing upon contact. Keep away from heat and distance it from other chemicals. *Spasms. Wear masks. lung injury and pulmonary edema may not appear immediately. Flammability. Disposal should comply with environmental legislations.Spillage While wearing protective attire and respiratory protection. CAUTION: adding water directly to liquid spills increase volatility of ammonia. 0 . Isolate diluted run-offs from sewers and bodies of water.Personal Protection *Information for materials safety data sheet is obtained from Allied Deviation 32 . well-ventilated area with container sealed tightly. and spray water downwind.Reactivity. Storage and Handling Considering ammonia as a hazardous material.Health. Labeling/NFPA 3 . thus may result to increase in exposure of environment Waste Disposal Ammonia may be used for manufacturing fertilizers but should be kept from entering bodies of water. H. it should be kept in a cool. 1 . Seek medical attention as soon as possible. Synonyms: Ashes(residues). Do not induce vomiting. Avoid eating in the working area. shoes and protective clothing Emergency Treatment Hazard/Symptoms Inhalation Preventive Measures Wear mask.B. 33 . Contact emergency medical support if the person is not breathing. but drink plenty of water. Note: Exposure route: Eye Contact Wear google in handling coals. Wash contaminated skin immediately with water and soap. First Aid Move person to fresh air.2-2. fly ash Physical Properties Boiling point > 1000° C Freezing point Flash point Self-ignition temperature Specific gravity Vapor density Vapor pressure Solubility in water Solid Reactivity none none none 2.8 not measurable Not measurable < 5% Light tan or beige powder Reacts with water Personal Protective Equipment Respiratory Protection: Appropriate mask Eye Protection: Skin protection: Goggles Gloves. Rinse thoroughly with water at an eye station.2 Lignite or Sub-bituminous Coal Fly Ash Description Product/Chemical name: Coal Fly Ash CAS registry number: 68131-74-8 Health hazards Inhalation Skin Contact Eye Contact Ingestion Crystalline Silica is classified by IARC as human carcinogen. Seek medical attention for skin irritation. Do not rub. Skin Contact Ingestion Wear appropriate gloves and proper clothing.coal ash. Store dry and away from water. Disposal should comply with environmental legislations. *Information for materials safety data sheet is obtained from Lafarge North America (2002) 34 .Waste Disposal Ammonia may be used for manufacturing fertilizers but should be kept from entering bodies of water. Storage and Handling Avoid accidental release. Dispose of containers in an approved landfill or incinerator.