An- Najah National University Faculty of Engineering and Information Technology Material Engineering Department “Carbon dioxide Capture and Sequestration: Materials and Technology Potentials” Prepared by: Anagheem Battah Aseel Bouziyah Diana Mustafa Farah Seddah Supervised By: Dr. Hamdallah Bearat This project was submitted in partial fulfillment of the requirements for the degree of Bachelor in Material Engineering Submission Date: July 5 th , 2020 I اإلهداء بسم هللا و الحمد و الشكر هلل رب العالمين الذي بنعمته تتم الصالحات الحمدهلل الذي بتوفيقه و تسهيل منه جل في عاله و بعد خمس سنوات حملت في طياتها الكثير من الصعوبات و المشقة و التعب ها نحن نقف و كلنا .مونا و أثرو بنا بكالماتهم فخر بأنفسنا و بكم لنهدي هذه السنوات لكم و لكل من دع نهدي هذا المشروع من تلذذت بالمعاناة و كانت شمعة تحترق ... الى أمي القلب الحنون من كانت وما زالت بجانبنا بكل المراحل .لتنير دربنا الى من علمنا الصعود و عيناه , الى يدنا اليمنى , الى أبي من علمنا أن نقف وكيف نبدأ األلف ميل بخطوة .راقبنات .الى من هم هدية من الرحمن أخوتي دليلي في الحياة و شمعة تنير دربي .أصدقاؤنا و أحبتنا الذين أعانونا في مسيرتنا العلمية الى من لهم الفضل بارشادنا الى طريق العلم و المعرفة الى دكاترتنا األفاضل الذين حملو أقدس رسالة من .السماء كم نحن فخورون بكم وكليتنا التي نفتخر بها .. اللحظات أجملالتي قضينا فيها " جامعة النجاح الوطنية " عتنا بيتنا الثاني الى جام ال ننسى الساحات .. التي جمعتنا بمن يستحقون كل الشكر والتقدير " كلية الهندسة وتكنولوجيا المعلومات" .والذكريات الجميلة ... باأليام و الساعات و الدقائق التي أمضيناها معا, مرها وبهذا نكون أنهينا أجمل سنين العمر بحلوها و بضحكاتنا المتتابعة... بجلساتنا الجميلة II Abstract The rise in the earth’s surface temperature caused by global warming due to industrial development and human activities that have caused many gases to be emitted into the atmosphere, including carbon dioxide (CO2); is a greenhouse gas. Several technologies have emerged that aim to convert CO2 from its gaseous state into a solid-state. It is an effective way to protect the environment and reduce global warming. Returning it from solid-state to gas can also provide us with a new source of CO2 at a relatively low cost. The technique of capturing CO2 based on the interaction of carbon dioxide and water with sodium carbonate (Na2CO3) is inexpensive and does not cause environmental effects. The aim of this study was to test the efficiency of absorbing CO2 using Na2CO3 and Ca(OH)2. Ca(OH)2 experiments were carried out at room temperature. The results were that with increasing time, CO2 absorption increased by flow method. According to Na2CO3 experiments were carried out at temperatures 65 o C and 85 o C at different times (0.25, 0.5, 1, 2, 3) hours. The carbonation process begins at 60°C, that is, the Na2CO3 begins to convert into sodium bicarbonate (NaHCO3). The results showed that absorption of the substance at a temperature of 65°C was more efficient than 85°C especially at the beginning (at 0.25 hours). Also, absorption was high initially then decreases with increasing time over the same temperature. Moreover, the weight loss was greater at 85°C; increased absorption of CO2 was observed when increasing the amount of water. A problem was encountered in leaking CO2 during the experiments, which led to the idea of developing a reaction system that guarantees higher efficiency and more accurate result in capturing CO2. III Acknowledgment While preparing this report and completing this project, we got help and guidance from some respectable people who deserve our deepest gratitude. Therefore, we would like to express our appreciation to all who provided us with the possibility to complete this project and direct us in writing the report. Special thanks to the project supervisor Dr. Hamdallah Bearat for his suggestions and encouragement to complete the work and helped provide the basic equipment in the project, which always pushed us to make every effort. We also extend our thanks and appreciation to the examiners Dr. Amer Al-Hamuz and Dr. Majd Shhadi who were a symbol of help and giving to the student. We admit the appreciation of the engineering laboratory engineers, (Eng. Maha Fuqha) and (Mr. Yusuf Ratroot), who have permitted us to use the laboratory equipment needed to complete the work. We thank our distinguished university, An-Najah National University, for its support of students and their projects. IV Content I ................................................................................................................................................. اإلهداء Abstract ........................................................................................................................................... II Acknowledgment .......................................................................................................................... III List of Figure................................................................................................................................. VI List of Tables ............................................................................................................................... VII Chapter One: Introduction .............................................................................................................. 1 Chapter Two: Constraints and limitations ...................................................................................... 3 Chapter Three: Literature Review .................................................................................................. 4 3.1 Carbon capture and storage (CCS) technologies .................................................................. 4 3.2 The characteristics of CCS.................................................................................................... 5 3.3 Methods for carbon dioxide capture and sequestration ........................................................ 6 Chapter Four: Methodology ............................................................................................................ 9 4.1 Materials and supplies........................................................................................................... 9 4.1.1 Carbonation and its effect .............................................................................................. 9 4.2 Material and Equipment ...................................................................................................... 10 4.3 Reaction Procedure for static method experiments ............................................................ 14 4.4 Measurements ..................................................................................................................... 15 4.5 Improvement reaction system ............................................................................................. 16 Chapter Five: Results & Discussion ............................................................................................. 19 5.1 Carbon dioxide capture using Ca(OH)2 .............................................................................. 19 5.2 Carbon dioxide capture using Na2CO3 ............................................................................... 21 5.3 Carbon dioxide capture using ammonia and amines .......................................................... 24 V Chapter Six: Conclusion ............................................................................................................... 25 Chapter Seven: Recommendation ................................................................................................. 26 Chapter Eight: References ............................................................................................................ 27 Chapter Nine: Appendices ............................................................................................................ 29 9.1 Appendices A ...................................................................................................................... 29 9.2 Appendices B ...................................................................................................................... 35 VI List of Figure Figure 1: CCS technology aims to capture carbon (Carbon Capture and Storage Schematic diagram of potential CO2 capture, storage and transport systems ................................................. 4 Figure 2 : CO2 capture and storage from power plants . ................................................................. 5 Figure 3 : Reactor.......................................................................................................................... 11 Figure 4: Reaction system installation. ......................................................................................... 14 Figure 5 : Electronic balance. ....................................................................................................... 15 Figure 6 : Graduated cylinder. ...................................................................................................... 15 Figure 7: The dimension of reactor. .............................................................................................. 17 Figure 8 : Closed cylinder. ............................................................................................................ 17 Figure 9 : The piece used to make the top part. ............................................................................ 18 Figure A 1: Calcium hydroxide. ................................................................................................... 29 Figure A 2: Sodium Carbonate. .................................................................................................... 29 Figure A 3: Ammonia. .................................................................................................................. 30 Figure A 4: Amine. ....................................................................................................................... 30 Figure A 5: Thermal Jacket........................................................................................................... 31 Figure A 6: Gas detector. .............................................................................................................. 32 Figure A 7: Tubes and valve. ........................................................................................................ 32 Figure A 8: Reaction installing. .................................................................................................... 33 Figure A 9: Describe design of Reactor. ....................................................................................... 33 Figure A 10: Reactor design. ........................................................................................................ 34 Figure A 11: Pipe wrench. ............................................................................................................ 34 VII List of Tables Table 1: Describe the characteristics of the used reactor. ............................................................. 12 Table 2: Theoretically obtained results of Ca(OH)2......................................................................20 Table 3: Describe the result of Ca(OH)2 reaction………………………………………………..20 Table 4: Theoretically obtained results of Na2CO3....................................................................... 21 Table 5: Describe the result of reaction at 65 o C. .......................................................................... 22 Table 6: Describe the result of reaction at 85 o C. .......................................................................... 23 1 Chapter One: Introduction Carbon management is the most affecting issue for the health and well-being of society over the coming years. Where human activities and increased consumption of fossil fuels contributed to the emission of gases in the atmosphere, mainly carbon dioxide (CO2), which led to negative environmental impacts such as global warming and was considered a major environmental issue in the early twenty-first century. Therefore, the development of technologies that can capture carbon dioxide was of the utmost importance. One such technique is carbon dioxide capture and sequestration (CCS), where calcium hydroxide (Ca(OH)2), sodium carbonate (Na2CO3), ammonia (NH3), and Amine (RNH2) could be used as a scavenger to capture CO2. Global warming increasingly thought to be associated with the atmospheric emission of greenhouse gases, principally CO2. Annual CO2 emissions in the year 2000 in the United States were about 5.9 billion metric tons, roughly equally divided between the transportation, commercial and residential, and industrial sectors. Initial efforts to limit CO2 emissions will no doubt focus on large stationary sources, with fossil fuel-fired power plants' obvious prime targets. A number of new power generation concepts that may result in CO2 control are being developed. These include O2 combustion with CO2 recycles, precombustion decarburization, and chemical looping combustion (Spigarelli et al., 2013). This project aims to choose the most efficient material for absorbing carbon dioxide, and study the best conditions to achieve the best results, so after reading several types of research related to capturing and storing carbon dioxide, a set of materials was approved for experiments that include calcium hydroxide and sodium carbonate that was used in the first graduation project using the static and flow method at room temperature and the results showed increasing time increasing absorption, in the second graduation project, experiments were conducted on sodium carbonate using the static method at temperatures 65ºC and 85ºC at different times, and it was supposed to use ammonia and triethylamine in addition to making a membrane in order to capture carbon dioxide emitted from cars and chimneys but not implemented due to the spread of COVID 19 virus. Parallel to this, a more efficient response system has been improved and 2 developed than the one used by SOLIDWORKS 2016 x64 Edition program (SOLIDWORKS, 2005). This report consists of eleven main chapters, Chapter One introduces carbon dioxide Capture and Sequestration: materials and technology potentials and clarifies the problems that will tend to be solved. Chapter Two shows the main constraints and standards in this study. Chapter Three shows the previous researches and studies published on this subject and included a literature review of the topics related to carbon dioxide Capture, general information about it. Chapter Four includes a brief methodology of our work, summarizes what has been done, and includes experimental work. Chapter Five shows the results and discussion. Chapter Six shows recommendations. Chapter Seven is conclusion. Chapter Eight are references. Finally, Chapter Nine are appendices that contain pictures and samples of calculation. 3 Chapter Two: Constraints and limitations There are many challenges encountered during the study and during the experimental work. It includes the following: - Delay in receiving the necessary materials for experiments, especially chemicals. -There was some difficulty in obtaining the research published on scientific sites. -The laboratory manager’s did not always match our free time. -Delayed replacement of the carbon dioxide cylinder. - The laboratory balance was inaccurate, as the sample reading was changing. In addition, the outbreak of COVID 19 in the first days of March was one of the challenges that we have faced, which has halted experimental work in the Laboratories. We could not complete the experiments and achieve the desired goals. However, we were able to improve reaction system to be more efficient than the one being used in experiments by means of a SOLIDWORKS 2016 x64 Edition Program (SOLIDWORKS, 2005) that will reduce the leak problems in experiments and improve the measurement of reaction temperature inside the reactor. 4 Chapter Three: Literature Review 3.1 Carbon capture and storage (CCS) technologies CCS technologies are the mitigation measures aiming to reduce CO2 emissions from energy and other energy-intensive sectors (e.g. cement metallurgy, petrochemical, etc.). CCS applied to a modern conventional power plant could reduce CO2 emissions to the atmosphere by approximately 80–90 % compared to a plant without CCS, as apparently in Figure 1. The first generation of CCS technologies, i.e. scrubbing with amines, is energy-intensive. Second and third-generation CCS technologies such as carbonate looping or chemical looping combustion have been proposed to reduce costs (Haaf et al., 2017). Figure 1: CCS technology aims to capture carbon (Carbon Capture and Storage Schematic diagram of potential CO2 capture, storage and transport systems (Metz et al., 2005) 5 3.2 The characteristics of CCS The capture of CO2 can be applied to large point sources. The CO2 would then be compressed and transported for storage in geological formations, in the ocean, in mineral carbonates, or for use in industrial processes. Available technology captures about 85–95% of the CO2 processed in a capture plant (Metz et al., 2005). A power plant equipped with a CCS system (with access to geological or ocean storage) would need roughly 10–40% more energy than a plant of equivalent output without CCS, of which most is for capture and compression. For secure storage, the net result is that a power plant with CCS could reduce CO2 emissions to the atmosphere by approximately 80–90% compared to a plant without CCS, as shown in Figure 2 (Metz et al., 2005). Figure 2 : CO2 capture and storage from power plants (Metz et al., 2005). 6 3.3 Methods for carbon dioxide capture and sequestration The process of transporting and storing carbon dioxide in long-term pools is called "carbon sequestration" which can be emitted or stored; it may be a natural process or process by humans. This strategy requires sequestrating CO2 from human activities using safe and environmentally acceptable techniques and does not cause leakage risks as much as possible. There are many technological options for CO2 sequestration, including abiotic and biotic. Biotic components are the living organisms present in an ecosystem, such as bacteria, fungi, plants and animals, and elements produced by them. The abiotic depends on physical and chemical reactions and engineering techniques and has received great attention from researchers, such as scrubbing, and mineral carbonation, geological injection and oceanic injection (Lal, R., 2008). Free-flowing Hydrated Sodium Carbonate (Na2CO3) Powders (HSCPs) with 30 wt % of water can achieve a very high CO2 sorption capacity within 60 min and fast CO2 uptake (90% saturation uptake within 16 min). A series of HSCPs with different Na2CO3 contents were prepared by thoroughly mixing an appropriate amount of Na2CO3 and deionized water at room temperature (Cai et al., 2018). Magnesium hydroxide carbonation was established at a high concentration of CO2. Many methods used to analyze carbonation reactions such as x-ray diffraction. MgCO3 precipitate as a thin layer. At 0.76 atm CO2, the reaction rate of carbonation increased up to 375 o C and decrease at high temperature because of the thermal stability which decomposes to MgO + CO2 (Béarat et al, 2004). Carbonation of olivine minerals are a choice for sequestration because of their low cost (4_5 $ / ton). 2Mg2SiO4 + CO2 MgCO3 + 2SiO2 During the reaction, the layer of SiO2 achieved, CO2 decomposition this layer and react with Mg +2 to form MgCO3 studies clarify that aqueous solution carbonate is promising, 30_50% carbonation achieved if > 37 Mm olivine at 135 bar CO2 and 185 C use in an hour with 1500 7 rpm stirring. ( Mg.95 , Fe.o85 ) 2SiO4 determine using X- ray emissions and impurities were below 1% with aqueous 0.64 M NaHCO3 + 1M NaCl (Béarat et al, 2006). Technologies for carbon dioxide capture and sequestration are under development. So, there are various routes (Kolle, J. M. 2020, Stolaroff, 2006):  Organic Carbon Production: Many organisms (flora and forest) naturally capture CO2 through photosynthesis.  Metal Carbonate production: Add materials such as CaCO3, K2CO3, and Na2CO3.  Capture with a regenerated Sorbent: Most likely, this would be coupled with deep geological sequestration of CO2.  Metal hydroxide Sorbents include sodium hydroxide (NaOH) or calcium hydroxide (Ca(OH)2).  Amine, Ammonium, Zeolite, polyethyleneimine and monoethanolamine. Carbonate solutions have distinct properties (Spigarelli et al, 2013):  Nonhazardous, nonvolatile, and non-fouling.  Environmentally benign.  No degradation in the presence of oxygen.  Low equipment corrosion rate.  Possible multi-pollutant control system (SOx capture).  Easy retrofit to current wet flue gas desulfurization units. Monoethanolamine is being used in removing CO2 from exhaust streams and is a subject inculcated for a period of about the last 80 years. The NH3 absorption of CO2 has proven experimentally to be more effective than amine-based absorption that is so far the most acceptable method. This method was shown to more effective than the amine-based process due to its several advantages (Bandyopadhyay, 2010): i. Having higher loading capacity (mol CO2 absorbed/mol of absorbent). 8 ii. Being free from corrosion problem. iii. Being stable in the environment of the flue gas. iv. Requiring lower liquid to gas flow ratio. v. Having multi-pollutant capture capability—especially SO2 and NOx removal could be integrated with this process for CO2 removal, thus eliminating the pretreatment of the flue gas in respect of these pollutants as is required for amine-based processes. vi. Consuming much less energy for regenerating the solvent, if necessary; else, the process can be routed to yield valuable products like NH4HCO3, (NH4)2SO4, or NH4NO3 that can be put into the soil as fertilizer. vii. Being more economic than MEA as well a host of other amines. viii. Being associated with ease of transportation of the NH4HCO3 produced as a white crystalline solid; similar to other solid products, it can be easily transported without any extra investment as is often required for ‘‘pipeline transportation of compressed CO2. 9 Chapter Four: Methodology 4.1 Materials and supplies 4.1.1 Carbonation CO2 was obtained from high purity cylinder. H2O was fed using syringe pump, the line was heated to ensure vaporization before gases mixing. Fixed-bed reactors have been used to study the capture of CO2 from simulated flue gas using a regenerable Na2CO3 sorbent. CO2 capture was effective in the temperature range of 60-70°C, while regeneration occurred in the range of 120-200°C, depending on the partial pressure of CO2 in the regeneration gas (Liang et al., 2004). 10 4.2 Material and Equipment There are many different materials that have the ability to absorb carbon dioxide, and these characteristics were adopted in selecting the materials used in this project, and the most important of these characteristics were: their availability, the solubility in water, the extent of danger to the environment and humans, and the possibility of volatilization and price. So the selected materials were: calcium hydroxide, sodium carbonate, ammonia and amine. Many material and equipment were used to complete this project: 1. Calcium Hydroxide (Ca(OH)2) Is used the carbonate anions can interact with the cations present in the water to form insoluble carbonates. For instance, if Ca 2+ is present limestone, CaCO3 is formed, according to the following reaction: Ca(OH)2 + CO2 CaCO3 + H2O As shown in Figure A1 in Appendices. 2. Sodium Carbonate (Na2CO3) Is used as source for carbonate ions to capture carbon dioxide (CO2), according to the following reaction: Na2CO3 + H2O + CO2 2NaHCO3 As shown in Figure A2 in Appendices. 3. Ammonia (NH3) is used to absorb carbon dioxide and produces urea from the reaction and is used as a chemical fertilizer for plants, according to the following reaction: 2NH3 + CO2 CO (NH2)2 + H2O As shown in Figure A3 in Appendices. 11 4. Amine (RNH2) is used in capturing carbon dioxide to produce the carbamate used as a cosmetic preservative and also used in medicine, according to the following reaction: RNH2 + CO2 RNHCOO - + H + As shown in Figure A4 in Appendices. 5. Reactor The used reactor consists of three parts: two cups (like the capsule) and the joint that connects the two cups, Teflon was used to wrap over the teeth of the two cups, and rubber lashes are placed at two sides of the joint to prevent leakage, The reactor was mounted to the vise and being surly tightened after putting the sample to prevent leakage using the pipe wrench. Table 1 shows the characteristics of the used reactor. As shown in Figure 3. Figure 3 : Reactor. 12 Table 1: Describe the characteristics of the used reactor. Reactor Alloy 316L SS Length 8 inch (203 mm) Diameter 1.9 inch (48.2 mm) Thickness 0.24 inch (6.1) Weight 3 lb (1.362 kg) Internal Volume 150 ml Pressure Rating 5000(344 bar) 6. Heating Jacket and thermocouple A cover where the reactor will be placed inside, when switching it on, heat start rises and follows up changing in temperature using a thermocouple. As shown in Figures A5, A6 in Appendices. 7. Ultrasonic Gas Leakage Detector A device used to detect any leakage of CO2 from the system. Its conception stands for using ultrasonic sensors to investigate all connection points. As shown in Figure A7 in Appendices. 8. Tubes, Fittings and Valves These supplements are used to complete the loop of the apparatus. The tube used between CO2 cylinder and the reactor is on SS, 1/16”. As shown in Figure A8 in Appendices. 13 This project was implemented in two interconnected stages, first the cleaning stage, second the preparation stage. In the first stage, the tools were cleaned to avoid errors and the reactor and sample holder were cleaned by H2O2 to remove any corrosion layer. Then a plastic mesh was washed and other equipment with deionized water. As for the second stage, the sample was prepared by weighting Na2CO3, water, mesh, and the sample holder, after loading this sample inside the sample holder, it was placed in the reactor, and then the reactor parts were collected and closed tightly. The reactor is placed inside the jacket and the desired temperature is seated by a thermocouple connected inside the jacket contact with the reactor. Then the temperature is calibrated and read. Carbon dioxide was allowed into the reactor through the valve at the bottom; the remaining carbon dioxide inside the reactor did not come out from the other side because it is closed. The sample was completed after a specified time and then placed inside the oven at a temperature ranging between (50-100°C) and left for 18 hours. Then it took out to cool down at room temperature and finally weighed. 14 4.3 Reaction Procedure for static method experiments Sodium carbonate (Na2CO3) was weighed and put it inside in a sample holder. The cylinder was closed from one side using plastic mesh to prevent the substance exit from the cylinder, then was placed in the reactor, after that the reactor was assembled and sealed tightly. The reactor was installed in Figure A9 in Appendices. The reactor was placed inside the jacket and the desired temperature was sitting by a placed thermocouple inside the jacket contact with the reactor then the temperature was calibrated and was read, as shown in Figure4. CO2 gas is allowed to enter the reactor through the valve at the bottom; remained CO2 inside the reactor did not come out from the other side because it is closed. The sample was finished after a specific time and then was placed inside the oven at a temperature ranging between (50-100°C) and left for 18 hrs, then it took out and left to cool at room temperature and finally weighed. Figure 4: Reaction system installation. 15 4.4 Measurements Use the caliber by taking measurements of reactor, as shown in Table 1. The weight of sodium carbonate, calcium hydroxide, mesh and sample holder were taken in gram (g) by an electronic balance in the unit laboratory, as obvious in Figure 5. Figure 5 : Electronic balance. The amount of water was determined using a graduated cylinder and dropper in millimeters (ml), as shown in Figure 6. Figure 6 : Graduated cylinder. The temperature was measured using a thermocouple in o C and also a pressure using gauge pressure in psi. 16 4.5 Improvement reaction system We have three reactors designed and manufactured by Dr. Hamdallah Bearat at Arizona State University and using two alloys 316L or 304L stainless steel (316L contains 16% chromium, 10% nickel and 2% molybdenum, 304L stainless steel contains 18% chromium and 8% nickel. the molybdenum is added to help resist corrosion). The used reactor consists of three parts: two cups (like the capsule) and the joint that connects the two cups, Teflon is used to wrap over the teeth of the two cups, and rubber lashes are placed at two sides of the joint to prevent leakage, The reactor is mounted to the vise and being surly tightened after putting the sample to prevent leakage using the pipe wrench, despite all these steps was done to prevent leakage, they were not sufficient for this purpose. After that, the reactor was placed inside the jacket and the desired temperature was sat by a placed thermocouple inside the jacket attached to the reactor. However, it was difficult to install the thermocouple so wires were used in order to fix it but were not sufficient for this purpose. Because of these obstacles, we developed a reactor consist of two parts, one part of the reactor has thermocouple well, well’s radius less than reactor thickness, one cup was manufactured connected to the joint (as one piece) but we used the Teflon and rubber lashes for the second cup in order to help us to easily take control over leakage. This reactor was designed using SOLIDWORKS 2016 x64 Edition program (SOLIDWORKS, 2005). As shown in Figures 7, (A10 and A11 in Appendices). 17 Figure 7: The dimension of reactor. It was assumed that two reactors were obtained by cutting the closed cylinder shown in Figure 8 into two equal parts. Each part represents the lower cup of the reactor. Figure 8 : Closed cylinder. The two parts shown in Figure 9 represent the upper cup for which improvement has occurred. 18 Figure 9 : The piece used to make the top part. 19 Chapter Five: Results & Discussion Note: the readings of temperature and pressure were taken using equipment from the unit lab, Material Science Department, College of Engineering and Information Technology, An- Najah National University. 5.1 Carbon dioxide capture using Ca(OH)2 This experiment is about the reaction between calcium hydroxide with water and CO2 to produce calcium carbonate, in order to know the efficiency of capturing CO2, according to the following chain of reactions: Ca(OH)2 Ca + + 2OH - CO2 (g) CO2 (l) CO2 (l) + H2O (l) H2CO3 H2CO3 H + + HCO3 - HCO3 - H + + CO3 -- Ca + + CO3 - CaCO3 Ca(OH)2 + CO2 CaCO3 + H2O 20 Table1 2: Theoretically obtained results. Molar mass (g/mol) Number of moles Mass (g) Ca(OH)2 74 0.1 7.4 CO2 44 0.1 4.4 CaCO3 100 0.1 10 H2O 18 0.1 1.8 Table1 3: Describe the result of Ca(OH)2 reaction. Time Mass before reaction (g) Mass after reaction (dry) (g) Mass gain (g) Theoretical gain (g) Extent of reaction % 1 18.4 20.7 2.3 4.4 52.2 2 18.4 21.1 2.7 4.4 61.3 3 18.4 21.4 3 4.4 68.1 The results of the first project showed that the absorption of carbon dioxide by calcium hydroxide increases with the increase in time using the flow method at room temperature. Although Ca(OH)2 aqueous solution can be effectively used as an absorbent to capture CO2. The Ca(OH)2 concentration in the solution strongly influenced the capture performance of the absorbent. The simultaneous Ca(OH)2 dissolution and CaCO3 production in the absorbent may have substantially hindered the combination of Ca 2+ with CO3 2– in suspension. Therefore, a 21 higher Ca(OH)2 concentration in suspension further reduced the CO2 absorption capacity and produced substantially agglomerated CaCO3 with low crystallinity (Han et al, 2011) . 5.2 Carbon dioxide capture using Na2CO3 This experiment is about the reaction between sodium carbonate with water and CO2to produce Bicarbonate, in order to know the efficiency of capturing CO2, according to the following chain of reactions: Na2CO3 2Na + + CO3 - CO2 (g) CO2 (l) CO2 (l) + H2O (l) H2CO3 H2CO3 H + + HCO3 - Na + + HCO3 - NaHCO3 Na2CO3(S) +H2O (L) + CO2 (g) 2NaHCO3 (S) ∆HR° = -135 kJ/mol Na2CO3 Table 4: Theoretically obtained results of Na2CO3. Molar mass (g/mol) Number of moles Mass (g) Na2CO3 106 0.1 10.6 H2O 18 0.1 1.8 CO2 44 0.1 4.4 NaHCO3 84 0.2 16.8 Experimentally, several experiments were carried out on temperatures 65ºC and 85ºC at different times, under pressure = 710 psi. And the results were as shown in Tables 5 and 6 bellow. 22 The results shown in Table 5 are obtained below and weight gain was initially observed, after which weight loss started gradually with increasing time. This indicates that most Na2CO3 was consumed within approximately 15 minutes (Cai et al., 2018). Table 5: Describe the result of reaction at 65 o C. Time (hr) Mass before reaction (g) Mass after reaction wet (g) Mass after reaction dry (g) Mass Gain (g) Theoretical gain (g) Extent of reaction % 0.25 10.62 17.30 14.93 4.31 6.2 69.00 0.5 10.61 17.40 13.86 3.36 6.2 54.00 1 10.6 15.04 13.72 3.12 6.2 50.30 2 10.61 17.18 13.86 3.12 6.2 50.30 3 10.6 16.72 13.43 2.83 6.2 45.64 Based on the results obtained in Table 6, the percentage of carbon dioxide absorption at 85°C was generally lower than the ratio at 65°C, but water was added to a sample of 0.5 hours and 2 hours, increasing from 6.3 to 4.70 g. An increase in the resulting mass was observed, which helped absorb carbon dioxide and reduce the effect of heat on the sample. The extra water on the surface helps create a basic alkaline water environment. When CO2 spreads to the surface, it interacts with water and exothermic reaction (Cai et al., 2018). 23 Table 6: Describe the result of reaction at 85 o C. Time (hr) Mass before reaction (g) Mass after reaction wet (g) Mass after reaction dry (g) Mass Gain (g) Theoretical gain (g) Extent of reaction % 0.25 10.62 17.88 13.70 3.08 6.2 49.67 0.5 10.62 16.17 16.87 6.25 6.2 100 1 10.61 17.66 13.75 3.14 6.2 50.6 2 10.60 17.40 16.00 5.40 6.2 87.09 3 10.61 18.03 13.44 2.83 6.2 45.64 Several factors were observed to influence the reaction including the dissolving of Na2CO3 is partially dissolved in water, where the Na 2CO3 particles are suspended and provide an excellent interface between the gas and the liquid to capture CO2, which leads to an enhanced ability to absorb it (Liang et al., 2004). Generally, in these experiments, the amount of water added to Na2CO3 was 3.6g, except for 0.5 hours and 2 hours at a temperature of 85 o C, the amount of water was increased to 4.70g. Also, the concentration of Na2CO3 has a significant influence of capture, means that at low Na2CO3 concentration (aqueous solution or slurry), it's not ideal for capturing because of low gas _ liquid contact surface area. That why some samples did not get good results (Cai et al., 2018). Bicarbonate formation from carbon dioxide and Na 2CO3 reaction with water has effective for capturing CO2; however, the thermodynamics of this reaction is not well understood (Toan et al., 2019). The carbonation process begins at 60 o C, that is, the Na2CO3 begins to convert into NaHCO3. Whereas the researchers concluded that, at a temperature of 70 o C and 80 o C resulting mass decreases due to the formation of the Wegscheider’s salt (Na2CO3‚3NaHCO3) that leads to a decrease in the resulting mass (Liang et al., 2004). 24 5.3 Carbon dioxide capture using ammonia and amines Due to an outbreak of Covid-19 virus, we were unable to use these substances to know how well they would perform in capturing carbon dioxide. 25 Chapter Six: Conclusion Capture and sequestration technology with a static reaction system holds a promising future, whether in the world of industry, the environment, or academic research. As the world suffers from the problem of global warming because of industrial progress, human activity and increased CO2, which engineers and scientists are seeking to find a quick solution to. Several experiments and new materials have been discovered to contribute to the high absorption of CO2from the atmosphere. According to our experiments the calcium hydroxide that was used in the first graduation project using a constant method and a flow at room temperature showed an increase in absorption over time, whereas for Na2CO3 the CO2 absorption at 65°C was the best and most efficient. However, the increase in the amount of water added to some experiments at 85 degrees increased efficiency. During experiments, we encountered a problem with CO2 leakage, which led to the idea of improving and developing a two-part reaction system. What makes this technique (CCS) useful is that it can be carried out using a simple process design like the design of the reaction static system we used, and by owning the proper tools, providing the appropriate conditions, and to specify more closely the parameters to study. 26 Chapter Seven: Recommendation In the project, many challenges faced, therefore some recommendations for the next generations: 1. Providing the facilities, materials and equipment like flow meter to measure the amount of CO2 inter to the reaction, which is necessary to complete the project. 2. Checking the accuracy of reading laboratory devices and providing more accurate devices. 3. As a futuristic step, designing and manufacturing a membrane that can absorb carbon dioxide beside manufacture the reaction system that was developed within this project and improved more if necessary. 4. Providing laboratories at all times so that students can complete their projects without obstacles. 5. Providing advanced devices for performing sample analyzes to know more accurate information such as X-ray diffraction. 27 Chapter Eight: References Bandyopadhyay, A., 2010. Amine versus ammonia absorption of CO2 as a measure of reducing GHG emission: a critical analysis. Clean Technologies and Environmental Policy, 13(2), pp.269-294. Béarat, H., McKelvy, M., Chizmeshya, A., Gormley, D., Nunez, R., Carpenter, R., Squires, K. and Wolf, G., 2006. Carbon Sequestration via Aqueous Olivine Mineral Carbonation: Role of Passivating Layer Formation. Environmental Science & Technology, 40(15), pp.4802-4808 Béarat, H., McKelvy, M., Chizmeshya, A., Sharma, R. and Carpenter, R., 2004. Magnesium Hydroxide Dehydroxylation/Carbonation Reaction Processes: Implications for Carbon Dioxide Mineral Sequestration. Journal of the American Ceramic Society, 85(4), pp.742- 748. Cai, Y., Wang, W., Li, L., Wang, Z., Wang, S., Ding, H., Zhang, Z., Sun, L. and Wang, W., 2018. Effective Capture of Carbon Dioxide Using Hydrated Sodium Carbonate Powders. Materials, 11(2), p.183. Eloy S., S., Christopher R, M., Stephanie A, D. and Christopher W, J., 2016. Direct Capture Of CO2 From Ambient Air. Washington, D.C.: United States. Dept. of Energy. Office of Basic Energy Sciences, pp.11840–11876. Haaf, M., Stroh, A., Hilz, J., Helbig, M., Ströhle, J. and Epple, B., 2017. Process Modelling of the Calcium Looping Process and Validation Against 1 MWth Pilot Testing. Energy Procedia, 114, pp.167-178. Han, S., Yoo, M., Kim, D. and Wee, J., 2011. Carbon Dioxide Capture Using Calcium Hydroxide Aqueous Solution as the Absorbent. Energy & Fuels, 25(8), pp.3825- 3834. Krekel, D., Samsun, R., Peters, R. and Stolten, D., 2018. The separation of CO2 from ambient air – A techno-economic assessment. Applied Energy, 218, pp.361-381. 28 Kolle, J. M. (2020). Mesoporous Organosilicas for CO2 Capture and Utilization: Reaction Insight and Material Development (Doctoral dissertation, Université d'Ottawa/University of Ottawa), pp: 18, 39. Lal, R. (2008). Carbon sequestration. Philosophical Transactions of the Royal Society B: Biological Sciences, 363(1492), 815-830. Liang, Y., Harrison, D., Gupta, R., Green, D. and McMichael, W., 2004. Carbon Dioxide Capture Using Dry Sodium-Based Sorbents. Energy & Fuels, 18(2), pp.569-575. Metz, B., Davidson, O., De Coninck, H., Loos, M. and Meyer, L., 2005. IPCC Special Report On Carbon Dioxide Capture And Storage. 10th ed. New York, NY: Cambridge University Press, p.4.2013 SOLIDWORKS, D. S. (2005). SOLIDWORKS ®. Spigarelli, B., Hagadone, P. and Kawatra, S., 2013. Increased carbon dioxide absorption rates in carbonate solutions through surfactant addition. Mining, Metallurgy & Exploration, 30(2), pp.95-99 Stolaroff, J., 2006. Capturing CO2 From Ambient Air. Pittsburgh, PA: Carnegie Mellon University, pp.2, 5 and 6. Toan, S., O'Dell, W., Russell, C., Zhao, S., Lai, Q., Song, H., Zhao, Y. and Fan, M., 2019. Thermodynamics of NaHCO3 decomposition during Na2CO3-based CO2 capture. Journal of Environmental Sciences, 78, pp.74-80. Wang, Y., Zhao, L., Otto, A., Robinius, M. and Stolten, D., 2017. A Review of Post-combustion CO2 Capture Technologies from Coal-fired Power Plants. Energy Procedia, 114, pp.650- 665. 29 Chapter Nine: Appendices 9.1 Appendices A Figure A 1: Calcium hydroxide. Figure A 2: Sodium Carbonate. 30 Figure A 3: Ammonia. Figure A 4: Amine. 31 Figure A 5: Thermal Jacket. Figure A6: Thermocouple. 32 Figure A 6: Gas detector. Figure A 7: Tubes and valve. 33 Figure A 8: Reaction installing. Figure A 9: Describe design of Reactor. 34 Figure A 10: Reactor design. Figure A 11: Pipe wrench. 35 9.2 Appendices B Sample of calculation for Table 2: Number of moles = 0.1= mass = 7.4 g Sample of calculation for Table 3: For 1 hr: Mass gain = mass after reaction – mass before reaction = 11.8 – 7.4 = 4.4 g Extent of reaction % = = = 52.2% Sample of calculation for Table 4: Number of moles = 0.1= mass = 10.6 g Sample of calculation for Table 5 and 6: For 0.25 hr in Table 5: Mass gain = mass after reaction – mass before reaction = 14.93 – 10.6 = 4.31 g Extent of reaction % = = = 69%