Effects Of Halloysite Nanoclay Filler On Mixed Matrix .
Effects of Halloysite Nanoclay Filler onMixed Matrix Membrane (MMM)for CO2 RemovalbyKuan Chuan Hong14802Dissertation submitted in partial fulfilment ofthe requirements for theBachelor of Engineering (Hons)(Chemical Engineering)JANUARY 2015Universiti Teknologi PETRONAS32610 Bandar Seri IskandarPerak Darul Ridzuan
CERTIFICATION OF APPROVALEffects of Halloysite Nanoclay Filler on Mixed Matrix Membrane(MMM) for CO2 Removal.byKuan Chuan Hong14802A project dissertation submitted to theChemical Engineering ProgrammeUniversiti Teknologi PETRONASin partial fulfilment of the requirement for theBACHELOR OF ENGINEERING (Hons)(CHEMICAL ENGINEERING)Approved by,(DR. OH PEI CHING)UNIVERSITI TEKNOLOGI PETRONASBANDAR SERI ISKANDAR, PERAKJANUARY 2015i
CERTIFICATION OF ORIGINALITYThis is to certify that I am responsible for the work submitted in this project, that theoriginal work is my own except as specified in the references and acknowledgements,and that the original work contained herein have not been undertaken or done byunspecified sources or persons.(KUAN CHUAN HONG)ii
ACKNOWLEDGEMENTI would like to express my gratitude to all those who provided me with the possibilityto complete this project. A special appreciation I give to my final year projectsupervisor, Dr. Oh Pei Ching, whose contribution in stimulating suggestions andencouragement, as well involvement in purchasing / renting suitable equipment andmaterials helped me to coordinate my project especially in writing this report.Furthermore I would also like to acknowledge with much appreciation thecrucial role of the staff of UTP’s Chemical Engineering Department, who gave thepermission to use all required equipment and the necessary materials to complete theproject. A special thanks to chemical engineering department’s lab executive, En.Fadhullah Hakimi and lab technicians who provided me access to necessary equipmentrequired to finish the project. Last but not least, many thanks go to my colleaguesinvolved in the project, Mr. Asif and Chua Yin Ching who gave me important advices,as well as teaching the dos and don’ts of the project.I have to appreciate the guidance given by other supervisor as well as theevaluators especially in my project presentation, Dr. Hilmi that has improved mypresentation skills thanks to their comment and advices.iii
ABSTRACTMembrane separation technology plays an important role in natural gas CO2/CH4separation. Mixed matrix membrane (MMM) is one of the many types of membraneused and its advantage over other types of membrane is that it has the mechanicalstrength and cheap production cost of organic membrane, in the same time have thesuperior selectivity – permeability trade off of inorganic membranes. There are variouscombinations when it comes to synthesis of MMM. Generally, an inorganic filler isembedded into a polymeric matrix to form MMM. One of the combinations neverventured by researchers is the polysulfone (PSf) – halloysite MMM. This project aimsto elucidate the casting formulation of pristine PSf membrane (a type of organicmembrane) and to study the effects of halloysite nanoclay filler in PSf membrane. Themembranes synthesized will be characterized using FESEM, TGA, and DSC. The firstpart of the project involves synthesis of membranes using pure polysulfone and amixture of polysulfone – halloysite nanoclay fillers. In the second part of the project,the membranes synthesized are characterized using analytical tools. The effects ofhalloysite nanoclay fillers in polysulfone membrane are investigated and the bestcomposition will be determined. The best MMM chosen is 20wt% PSf – 3wt%halloysite mixed matrix membrane. It has a decomposition temperature of 519.18oC.The total remaining residue after heating the membrane up to 730oC is 27.63wt%. Theglass transition temperature, Tg of the membrane is 184.34oC.iv
TABLE OF CONTENTSCERTIFICATION OF APPROVAL . iCERTIFICATION OF ORIGINALITY. iiACKNOWLEDGEMENT . iiiABSTRACT . ivLIST OF FIGURES . viiLIST OF TABLES . viiiABBREVIATIONS AND NOMENCLATURES . ixCHAPTER 1: INTRODUCTION . 11.1 Background . 11.2 Problem statement . 21.3 Objectives of study . 31.4 Scope of study . 31.5 Project feasibility. 4CHAPTER 2: LITERATURE REVIEW / THEORY . 52.1 The Robeson’s curve . 52.2 Polymer characteristics and comparison . 62.3 Halloysite nanoclay filler . 72.4 Dry/wet phase inversion method . 82.5 Mixed matrix membrane . 92.6 Synthesis of pristine polymer membrane and mixed matrix membrane . 11CHAPTER 3: METHODOLOGY / PROJECT WORK . 133.1 Overall research methodology . 133.2 Gantt Chart . 143.3 Chemicals / glassware / equipment List . 153.4 Synthesis of pristine polysulfone membrane . 163.4.1 Experimental procedure . 16v
3.5 Synthesis of polysulfone-halloysite mixed matrix membrane . 173.5.1 Experimental procedure . 173.6 Characterization tests . 193.6.1 Field emission scanning electron microscopy (FESEM) test . 193.6.2 Thermogravimetric analysis (TGA) . 193.6.3 Differential scanning calorimetry (DSC). 20CHAPTER 4: RESULTS AND DISCUSSION . 214.1 Membrane synthesis . 214.2 FESEM . 224.2.1 Membrane Morphology (Top Views) . 224.2.2 Cross Sectional Morphology . 234.3 TGA . 264.3.1 Individual TGA Curves . 264.3.2 Combined TGA Curve. 294.4 DSC . 30CHAPTER 5: CONCLUSION AND RECOMMENDATIONS . 31REFERENCEvi
LIST OF FIGURESFigure 1: Upper bound correlation for CO2/CH4 separation (1991)[12] . 5Figure 2: Upper bound correlation for CO2/CH4 separation (2008) (TR: Thermallyrearranged.)[13]. 6Figure 3: Plasticization pressure for different polymers. . 7Figure 4: Schematic representation of mass transfer path of dry/wet phase inversionmethod [25] . 9Figure 5: Schematic diagram of MMM [27]. 10Figure 6: Ideal gas transport properties [27] . 10Figure 7: Non-idealities / flaws in MMM[27] . 11Figure 8: Flat membrane synthesized by phase inversion method[16]. 12Figure 9: General Procedure of MMM synthesis[27] . 12Figure 10: Overall research methodology. 13Figure 11: Process flowsheet / Sequence of Work . 18Figure 12: Defect-free polysulfone membrane (20 wt%) . 21Figure 13: Top views of fabricated membranes (500x magnification). . 23Figure 14: Cross sectional views of fabricated membranes (500x magnification). . 24Figure 15: Cross sectional view of 3 wt% halloysite loading membrane (3000xmagnification) . 25Figure 16: Cross sectional view of 5 wt% halloysite loading membrane (3000xmagnification) . 26Figure 17: Individual TGA curves . 29Figure 18: TGA curves of different compositions of membranes . 30vii
LIST OF TABLESTable 1: Estimated duration per trial . 4Table 2: Summary of CO2/CH4 separation performance for different membranes. . 7Table 3: Chemicals / Glassware / Equipment List . 15Table 4: Membranes synthesized . 22Table 5: Thichness of fabricated membranes . 23Table 6: Decomposition temperature of the fabricated membranes. . 27Table 7: Glass transition temperature of the fabricated pristine PSf membrane andPSf-halloysite MMM . 30viii
ABBREVIATIONS AND NOMENCLATURESPSf: PolysulfoneMMM: Mixed matrix membraneFESEM: Field emission scanning electron microscopyTGA: Thermagravimetic analysisDSC: Differential scanning calorimetryix
CHAPTER 1: INTRODUCTION1.1 BackgroundCarbon dioxide (CO2) is the largest contributor to global warming. In the past fiveyears, 34 billion tons of CO2 emission is recorded globally [1]. Common sources ofCO2 are natural gas streams, flue gas from fossil fuel combustion, and biogas fromanaerobic digestion [2]. The separation of CO2 from methane gas (CH4) is importantin many industrial processes, for example increasing the calorific value of natural gas,natural gas sweetening and landfill gas purification [3]. Therefore, effective andeconomically feasible techniques to remove CO2 from CH4 streams are highly soughtand attract great interests.There are several methods or techniques used to separate gases, either to isolatea single product or to produce multiple products. Compared to other gas separationtechniques such as swing adsorption techniques (i.e. pressure swing adsorption,vacuum swing adsorption, and temperature swing adsorption), cryogenic distillationand amine absorption [2, 4], membrane gas separation technologies are comparativelyless developed and hence less widely used. Generally, membrane gas separation usesthe characteristic of a partially permeable membrane which allows the unwanted gas(i.e. carbon dioxide, CO2) to pass through the membrane and be removed, while thedesirable gas (i.e. methane gas, CH4) remains in the original airstream.Synthetic membranes used in membrane gas separation technologies aredivided into two types – organic membranes (i.e. polymeric membranes) such aspolyethylene, polyamides, cellulose acetate, polysulfone, etc. as well as inorganicmembranes (i.e. ceramic membranes) such as silicon carbide, montmorillonite,halloysite, etc [2, 5-7]. Organic materials-based membranes are characterized by theirlower costs, better processability, and their intrinsic properties of gas transportation [2,7, 8]. Comparatively, inorganic materials-based membranes provides strongercapabilities to differentiate gas species in spite of high temperature, pressureconditions and harsh environments [2, 6, 9].Mixed matrix membranes (MMM), also known as hybrid membranes, are acombination of both inorganic and organic membranes. It contain a separating layer1
made of continuous phase (usually a polymer) embedding a second, dispersed phase,the chemical nature of which is different [2, 6, 10, 11]. The combination of twodifferent materials with different gas diffusivity and solubility into a new membraneallows an optimal combination of high permselectivity (selectivity, permeability) ofthe inorganic component with the characteristic of ease of production of the polymericcomponent.1.2 Problem statementThe current CO2/CH4 separation membrane technologies are led by organicmembranes due to their cheaper production costs, and the nature of them being easilyshaped into both flat sheets and hollow fibers. It is also relatively easy to scale themup to whichever industrial size [2]. However, organic membranes suffer from eitherlow selectivity or permeability. They form an inverse relationship and can be observedin Robeson’s upper bound curve [2, 12, 13].Inorganic membranes, on the other hand, has the capability to maintain asuperior selectivity and permeability at high temperature and pressure [2, 7] However,the use of inorganic membranes are limited due to their expensive nature as well asreproducibility problems in the preparation steps when it comes to industrial scale [2,6, 9].Polysulfone-halloysite mixed matrix membrane has not been reported in paststudies, and hence the casting solution formulation for the MMM has to be investigatedin order to determine the best solvents to be used, and also the weight percentages ofall the components used in the fabrication of the MMM.2
1.3 Objectives of studyThe objectives of this study are as follows:1. To elucidate the casting solution formulation for synthesis of pristinepolysulfone (PSf) membrane.2. To study the effects of halloysite nanoclay filler on mixed matrix membranefabrication.3. To characterize the resultant membranes using various analytical tools(FESEM, TGA, DSC, etc.).1.4 Scope of studyThe variation of compositions of inorganic membrane component (halloysite nanoclayfiller), organic membrane component (polysulfone – PSf), and solvent (N-Methyl-2pyrrolidone – NMP) will result in different level of performance of the mixed matrixmembrane. The characteristics of a decent MMM that will be observed arepermselectivity, ease of production, and its durability.There are several variables that can be altered throughout the study. Firstly, theoptimal weight percentage of polysulfone in the pristine polymeric membrane mixturecan be determined by trial and error method. Secondly, the effects of the compositionof halloysite nanoclay fillers in polysulfone can be observed. The weight percentageof the other components (solvents and non-solvent) will also change the performanceof the membrane.Tests will be done on the membranes casted, with different weight percentageof polysulfone and halloysite in order to determine their qualities. The tests that canbe done are field-emission scanning electron microscope (FESEM) test, thermalgravimetric analysis (TGA) test, and differential scanning calorimetry (DSC) test.3
1.5 Project feasibilityThe expected experimental process flow are summarized in Table 1:Table 1: Estimated duration per trialStep1Drying of raw halloysite filler and polysulfone powderEstimatedDuration24 hours2Sonication of halloysite in solvent mixture30 minutes3Dispersion (stirring) of halloysite in solvent mixture6 hours4Dissolving polymer in solvent mixture24 hours5Sonication of MMM mixture2 hours6Leaving the mixture to ‘stand up’ overnight12 hours7Membrane casting8Water coagulation bath9Posttreatment30 minutes(methanol24 hoursandn-hexanebath)3 hours(optional)10Drying time24 hoursTOTAL96 hours- Total experiments: 20 (can be done in parallel)- Planned schedule: Refer to Gantt chart below.This project is allocated eight months to be completed. It is believed that thereis ample time to complete the project objectives. According to Table 1, the parametersof membrane to be studied have been chosen carefully in order to suit the timelinegiven for this project. Besides, a reasonable and detailed planning has been devisedfor each part of the project, this is so that the project can be completed within theplanned timeframe and will produce a good outcome by the end.4
CHAPTER 2: LITERATURE REVIEW / THEORY2.1 The Robeson’s curveThe CO2/CH4 gas pair is the second most investigated gas pair for membraneseparation [13]. For the case of organic membranes used for CO2/CH4 gas separation,they are commonly cheap and easily synthesized, but often suffer from either lowselectivity or permeability. They form an inverse relationship and can be observed inRobeson’s upper bound curve [2, 12, 13].Figure 1: Upper bound correlation for CO2/CH4 separation (1991)[12]The first upper bound correlation (Robeson’s curve) study on CO2/CH4 gaspairs was done in 1991, as shown in Figure 1. A review of the initial upper bound forthe new upper bound correlation for CO2/CH4 gas separation was done by Robeson in2008, as shown in Figure 2. The results only show a modest shift in the upper bound,which means that the use of polymeric membrane in CO2/CH4 gas separation is stillvery limited due to the low tradeoff between selectivity and permeability.5
Figure 2: Upper bound correlation for CO2/CH4 separation (2008) (TR: Thermally rearranged.)[13]2.2 Polymer characteristics and comparisonPolyimide (PI) and cellulose acetate (CA) based membranes have been mainly usedfor CO2/CH4 separation commercially [2] due to their relatively low cost and theirstatus as a high performance polymer. Their excellent glass transition temperature (Tg)and high tradeoff for selectivity/permeability made them better choices for various gasseparation applications [14]. However, PI is prone to plasticization in high pressureCO2 environment as they plasticize at 8 bar pressure [14-16]. Plasticization pressurerefers to the point of concentration of carbon dioxide passed through the membranewhere the polymer matrix starts to swell and expands, resulting in lower selectivity.On the other hand, polysulfone (PSf) exhibits similar traits to PI and CA. PSfis one of the most investigated glassy polymer membrane material used for CO2/CH4separation. Its properties are being extensi
Effects of Halloysite Nanoclay Filler on Mixed Matrix Membrane (MMM) for CO2 Removal. by Kuan Chuan Hong 14802 A project dissertation submitted to the Chemical Engineering Programme Universiti Teknologi PETRONAS in partial fulfilment of the requirement for the BACHELOR OF ENGINEERING (Hons) (CHEMICAL ENGINEERING) Approved by, _ (DR. OH PEI CHING) UNIVERSITI TEKNOLOGI PETRONAS BANDAR SERI .
methods and to investigate the effects of nanoclay reinforcement on the wear and microhardness of GICs. The incorporation of small amounts of nanoclay as reinforcing fillers in dental materials has shown a remarkable impact on mechanical properties [11]. The nanoclay (montmorillonite) used in this work is a member of the smectite clay family (2:1 layered silicates or phyllosilicates), and has .
EFFECTS OF DIFFERENT NANOCLAY LOADINGS ON THE PHYSICAL AND MECHANICAL PROPERTIES OF MELIA COMPOSITA PARTICLE BOARD This study investigated the effects of adding a filler of nano-sized particles of Cloisite Na (nanoclay) to urea-for-maldehyde resin on the physical and mechanical properties of particle boards made with this resin. Cloisite Na was introduced at rates of 2%, 4% and 6% of the dry .
Effects of Nanoclay on Cellular Morphology and Water Absorption Capacity of Poly(vinyl alcohol) Foam Jahanmardi, Reza* ; Eslami, Behnam; Tamaddon, Hamed Department of Polymer Engineering, Science and Research Branch, Islamic Azad University, Tehran, I.R. IRAN ABSTRACT: The present work was aimed to examine the effects of incorporation of each of two different types of nanoclay, i.e. Cloisite .
The effects of nanoclay and glass fiber on the microstructural, mechanical, thermal, and water absorption properties of the recycled WPCs were investigated. X-ray diffraction showed that the nanoclay intercalates in the WPCs. Additionally, scanning electron micrographs revealed that the glass fiber is adequately dispersed. According to the analysis of mechanical properties, the simultaneous .
The effects of nanoclay on surface morphology, degradation rate, thermal characteris-tics, mechanical properties, in vitro biomineralization, and cellular interactions were evaluated. We hypothesize that the nanoclay-enriched electrospun structure can support the osteogenic differentiation of hMSCs, along with the pro- duction of mineralized matrix. The features would enable the use of .
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