Synthesis and application of aerogel composites from agricultural by products in wastewater treatment

VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY VU VAN PHU SYNTHESIS AND APPLICATION OF AEROGEL COMPOSITES FROM AGRICULTURAL BY-PRODUCTS IN WASTEWATER TREATMENT Major: Chemical Engineering Code: 8520301 MASTER THESIS HO CHI MINH CITY, January 2023 ` THIS RESEARCH WAS CONDUCTED AT HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY – VNU-HCM Supervisor: Assoc Prof Dr Le Thi Kim Phung Reviewer 1: Assoc Prof Dr Nguyen Truong Son Reviewer 2: Dr Tran Phuoc Nhat Uyen The master thesis was defended at Ho Chi Minh city University of Technology, VNU-HCM, January 6, 2023 The members of the Assessment Committee including: Assoc Prof Dr Nguyen Thi Phuong Phong - Chairman Assoc Prof Dr Nguyen Truong Son - Reviewer Dr Tran Phuoc Nhat Uyen - Reviewer Assoc Prof Dr Le Thi Kim Phung - Committee Dr Tran Tan Viet - Secretary Confirmation of the Assessment Committee Chairman and the Head of Faculty after the thesis has been corrected (if any) Assessment Committee Chairman Dean of Chemical Engineering Faculty ` Vietnam National University – HCM City SOCIALIST REPUBLIC OF VIETNAM HCMC University of Technology Independence - Freedom – Happiness MASTER THESIS MISSIONS Full Name: VU VAN PHU Date of Birth: 25/10/1998 Student’s ID: 2070481 Place of Birth: Binh Phuoc Major: Chemical Engineering Code: 8520301 I THESIS TITLE: SYNTHESIS AND APPLICATION OF AEROGEL COMPOSITES FROM AGRICULTURAL BY-PRODUCTS IN WASTEWATER TREATMENT TỔNG HỢP VÀ ỨNG DỤNG TỔNG HỢP AIRGEL TỪ PHỤ PHẨM NÔNG NGHIỆP TRONG XỬ LÝ NƯỚC THẢI II MISSIONS AND CONTENTS:  Synthesis and investigation of physical-chemical properties of cellulose aerogel composites from pineapple leaf fibers and cotton waste fibers  Evaluation of adsorption performance for dye and oil of cellulose aerogel composites in wastewater treatment  Synthesis and investigation of physical-chemical properties of silica-based aerogel composites from rice husk ash and shrimp-based chitosan  Evaluation of adsorption performance for the dye of chitosan-silica aerogel composites in wastewater treatment III DATE OF ASSIGNMENT: 01/2022 IV DATE OF COMPLETION: 12/2022 V SUPERVISOR: Assoc Prof Dr Le Thi Kim Phung Ho Chi Minh City, December 28, 2022 SUPERVISOR HEAD OF DEPARTMENT DEAN OF CHEMICAL ENGINEERING FACULTY i ` ACKNOWLEDGEMENTS There are no proper words to convey my deep gratitude and respect for my thesis and research advisor Assoc Prof Le Thi Kim Phung She has inspired me to become an independent researcher and helped me realize the power of critical reasoning She also demonstrated what a brilliant and hard-working scientist can accomplish My sincere thanks must also go to my brilliant friends who are always beside me from joyful moments to hard times, cheering me on, and celebrating each accomplishment I will also never forget the sleepless nights in many coffee shops and the buffet parties I am most grateful to the collaborators for giving me many memories at RPTC There is no way to express how much it meant to me to have been a member of RPTC Last but not the least, I would like to express my gratitude to my family for their unfailing emotional support, unconditional trust, timely encouragement, and endless patience I acknowledge the support of time and facilities from Ho Chi Minh City University of Technology (HCMUT), VNU-HCM for this study Ho Chi Minh City, December 2022 Vu Van Phu ii ` ABSTRACT In a world where demands for freshwater are ever-growing, wastewater remediation becomes a global concern However, the development of innovative processes for wastewater treatment is still a major obstacle Therefore, the utilization of agricultural byproducts as a feedstock for successfully making adsorbents not only meaningful turns waste into high-value materials but also lowers production costs Concerning their fast removal rate and environmental compatibility, cellulose aerogel composites and silica-based aerogel composites are recently considered potential contributors to water remediation In this study, cellulose aerogel composites are fabricated using the sol-gel method from pineapple leaf fibers and cotton waste fibers in the alkali-urea solution followed by freeze-drying Meanwhile gelation of silica extracted from rice husk ash and shrimp-based chitosan catalyzed by hydrochloric acid (HCl), followed by aging, solvent exchange, surface modification, and cost-effective ambient drying results in monolithic chitosan-silica aerogel composites without fragmented The obtained chitosan-silica aerogel composites show higher equilibrium methylene blue (MB) uptake (53.81 mg/g) than those of chitosan-free silica aerogel (47.52 mg/g) at the MB concentration of 125 mg/L Although the aerogel composites showed both lower porosity (84.67 – 90.54%) and surface area (21.40 – 81.49 m2/g) compared with chitosan-free silica aerogel (94.84% and 457 m2/g), the presence of amine groups enhanced the adsorption efficiency of the aerogel composites The synthesized cellulose aerogel composites are directly applied to adsorb cationic methylene blue and exhibit a maximum adsorption uptake of 34.01 g.g-1 The MTMS-coated cellulose aerogel composites also show their ability to deal with oil pollution with a maximum oil adsorption capacity of 15.8 g.g-1 within only 20 sec Overall, our developed natural feedstock-derived aerogel composites demonstrated their great adsorption perfromance based on their ability to eliminate methylene blue, making them a potential material in dye-contaminated water treatment iii ` TÓM TẮT Ngày nhu cầu việc sử dụng nước ngày tăng việc xử lý nước thải trở thành mối quan tâm mang tính tồn cầu Tuy nhiên, việc phát triển quy trình để xử lý nước thải trở ngại lớn Vì thế, việc tận dụng phụ phẩm nông nghiệp làm nguyên liệu để chế tạo thành cơng vật liệu hấp phụ khơng có ý nghĩa biến phế thải thành vật liệu có giá trị sử dụng cao mà cịn giảm chi phí sản xuất Vật liệu cellulose aerogel composite vật liệu aerogel composite có nguồn gốc từ silica gần coi ứng cử viên tiềm cho việc xử lý nước Trong nghiên cứu này, vật liệu cellulose aerogel composite chế tạo phương pháp sol-gel từ sợi dứa sợi cotton thải dung dịch kiềm-urê sau sấy thăng hoa Trong đó, trình gel hóa silica chiết xuất từ tro trấu chitosan từ tôm xúc tác axit clohydric (HCl), sau q trình lão hóa, trao đổi dung môi, biến đổi bề mặt làm khô môi trường xung quanh hiệu chi phí tạo vật liệu tổng hợp aerogel chitosan-silica nguyên khối mà không bị phân mảnh Chitosan-silica aerogel composite thu cho thấy lượng hấp phụ methylene blue (MB) trạng thái cân (53,81 mg/g) cao so với silica aerogel không chứa chitosan (47,52 mg/g) nồng độ MB 125 mg/L Mặc dù chitosan-silica aerogel composite cho thấy độ xốp (84,67 – 90,54%) diện tích bề mặt (21,40 – 81,49 m2/g) thấp so với silica aerogel không chứa chitosan (94,84% 457 m2/g), có mặt nhóm amin tăng cường khả hấp phụ hiệu vật liệu aeogel composite Vật liệu cellulose arogel composite ứng dụng trực tiếp để hấp phụ methylene blue cho thấy đương lượng hấp phụ tối đa 34,01 g.g-1 Vật liệu cellulose arogel composite phủ MTMS cho thấy khả xử lý nước nhiễm dầu với khả hấp phụ dầu tối đa 15,8 g.g-1 vịng 20 giây Nhìn chung, vật liệu aerogel composite có nguồn gốc từ nguyên liệu tự nhiên chứng minh khả hấp phụ tốt dựa khả loại bỏ màu methylene blue, khiến chúng trở thành vật liệu tiềm xử lý nước bị nhiễm thuốc nhuộm iv ` DECLARATION I hereby declare that this thesis is my original work and it has been written by me in its entirety I have duty acknowledged all the sources of information that have been used in the thesis This thesis has also not been submitted for any degree in any university previously Master student Vu Van Phu v ` CONTENT LIST OF ABBREVIATIONS ix LIST OF FIGURES x LIST OF TABLES xii CHAPTER PREFACE 1.1 Study background 1.2 Research aims and Objectives 1.3 Outline of thesis CHAPTER LITERATURE REVIEW 2.1 Aerogel and aerogel composite 2.2 Cellulose aerogel composite 2.2.1 Pineapple leaf fiber 2.2.2 Cotton waste fiber 11 2.2.3 Cellulose aerogel 13 2.3 Silica-based aerogel composite 14 2.3.1 Silica aerogel 14 2.3.2 Chitosan 16 2.3.3 Chitosan-silica aerogel composite 19 2.4 Synthesis method of aerogel 21 2.4.1 Synthesis of cellulose aerogel composite 23 2.4.2 Synthesis of silica-based aerogel composite 25 2.5 Application of aerogel in wastewater treatment 31 CHAPTER MATERIALS AND METHODS 33 3.1 Cellulose aerogel composite 33 3.1.1 Chemicals and materials 33 3.1.2 Synthesis of PF/CF aerogel composites 33 vi ` 3.1.3 Study on oil removal of hydrophobic PF/CF aerogel composites 34 3.1.4 Study on MB removal of PF/CF aerogel composites 35 3.2 Silica-based aerogel composite 37 3.2.1 Chemicals and materials 37 3.2.2 Synthesis of silica aerogels 38 3.2.3 Synthesis of chitosan-silica aerogel composites 39 3.2.4 Study on MB cationic dye removal of silica-based porous material 40 3.3 Characterization 41 3.3.1 Density and porosity 41 3.3.2 Surface morphology analysis 42 3.3.3 Specific surface area and pore analysis 43 3.3.4 Mechanical strength analysis 45 3.3.5 Infrared spectrum analysis 45 3.3.6 Thermogravimetric analysis 46 3.3.7 Thermal conductivity analysis 47 CHAPTER RESULTS AND DISCUSSIONS 48 4.1 Cellulose aerogel composites 48 4.1.1 Characterization of PF/CF aerogel composites 48 4.1.2 Dye removal of PF/CF aerogel composites 53 4.1.3 Oil adsorption of the MTMS-coated PF/CF aerogel composites 57 4.2 Silica-based aerogel composite 58 4.2.1 Effect of acid concentration on gelation of silica aerogels from RHA 58 4.2.2 Characterization of silica aerogels and chitosan/silica aerogel composites 59 4.2.3 Dye adsorption of chitosan-silica aerogel composite 62 vii ` CHAPTER CONCLUSION AND FUTURE WORK 67 5.1 Conclusions 67 5.2 Future work recommendations 68 LIST OF PUBLICATIONS 69 REFERENCES 70 SHORT CURRICULUM VITAE 79 viii reinforces the abovementioned statement that adding chitosan enhances the adsorption capacity of the synthesized composites by 13.24% (b) (a) Figure 4.14 Effect of initial MB concentration on adsorption of (a) CS00, (b) CS100 Two common isothermal equilibrium models, namely Langmuir and Freundlich, are used to model the equilibrium adsorption capacity of silica aerogels and chitosansilica aerogel composites following the change in the initial MB concentration The analyzed parameters of the MB adsorption isotherms onto CS00 and CS100 samples are listed in Table 4.8 According to the results, the adsorption equilibrium data of the two samples can be presented by the Freundlich model in all solutions because of the higher linear regression coefficient, as opposed to the Langmuir model This adsorption behavior suggests that adsorption of MB by silica aerogels and chitosansilica aerogel composites occurs heterogeneously due to the multi-layer MB adsorption on the adsorbent and the π-π bond among the MB molecules [8] Table 4.8 The Langmuir and Freundlich isotherm models Langmuir Freundlich Sample kL (L/mg) R2 n (g/L) kF (mg/g) R2 CS00 0.002 0.415 0.723 1.784 0.949 CS100 0.0004 0.012 1.004 4.185 0.938 c) Effect of pH on adsorption capacity of chitosan-silica aerogel composite The influence of pH on MB uptake of silica-based adsorbents is shown in Figure 4.15 As the pH value increases from to 5, a significant enhancement in MB 65 adsorption of the aerogel composite is witnessed In detail, an increase from 14.90 to 22.26 mg/g for the MB uptake and from 61.7 to 92.3% for the removal efficiency of the chitosan-silica aerogel composite is recorded However, both the MB adsorption capacity and removal efficiency of the sample seem to be remained with increasing pH from to At low pH (3 – 5), the adsorbent surface is positively charged due to the protonation of amino groups on chitosan chains, causing cation exchange between cationic MB molecules and hydrogen ions of protonated groups The competition between dye cations and free positive hydrogen of an acidic solution reduces the adsorption capacity of the aerogel composite [8] As the pH of the MB solution increases, the hydroxyl groups on the surface of the aerogel composite become negatively charged, leading to strong electrostatic interactions between the active sites on the aerogel composite and cationic MB [126] Figure 4.15 Effect of pH on MB uptake of chitosan-silica aerogel composite CS100 66 CHAPTER CONCLUSION AND FUTURE WORK 5.1 Conclusions In this study, aerogel composites based on agricultural by-products are an opportunity to minimize waste production In addition, the study and application of the adsorption capacity of these materials also bring meaning to the problem of solving environmental pollution, specifically here, wastewater treatment The following findings were obtained as a result of the study: PF/CF aerogel composites were successfully synthesized from the sol-gel process with the NaOH/Urea/H2O solvent system with a mass ratio of 7/12/81 The fiber mixing ratio of 4/1 gives the highest porosity (95.2%) and the lowest density (0.053 kg/m3) The insulation of this fiber mix ratio is the best (0.039 W/m.K) The PF/CF fiber mix ratio is 1/1 for the highest specific surface area (19.37 m2/g) with pore sizes ranging from micro to macroporous At the same time, this fiber mixing ratio also gives better muscle strength (203.72 kPa) than the other two yarn mixing ratios, 2/1 (145.28 kPa) and 4/1 (90.97 kPa) The highest measured oil adsorption (15.8 g/g) at the PF/CF fiber blend ratio was 4/1 In addition, MB color adsorption is also the highest at this ratio (34.01 mg/g) Chitosan-silica aerogel composites were fabricated by in situ formations of an inorganic network in the presence of a preformed organic polymer Low-density silica aerogel was synthesized from rice husk ash via the sodium silicate route Both silica aerogel and chitosan/silica aerogel composite were prepared by sol-gel method and dried at ambient pressure after surface modification with Methyltrimethoxy Silane (MTMS) solution In the process of synthesizing silica aerogel, the optimal conditions for good gels are neutral pH of about – and neutralized HCl acid concentration of 1.5 M 67 Both silica aerogel and chitosan/silica aerogel composite samples proved to be effective adsorbents for the removal of MB from an aqueous solution The percentage of adsorption was maximal at a pH value of 5.0 and decreased in less acidic MB solutions The adsorption kinetics was well described by the pseudo-second-order model equation An adsorption isotherm was fitted by the Freundlich model, with the maximum adsorption capacity of MB on composite material calculated at 52.5 mg/g for composite and 47.5 mg/g for silica aerogel The candidate materials exhibited a high maximum removal capacity and therefore, these hybrid materials behave as good candidates for MB removal in water purification 5.2 Future work recommendations Cellulose-based fibers have the ability to insulate heat and sound due to their low thermal conductivity and high sound insulation coefficient Therefore, it is advisable to study other applications of PF-CF aerogel composites In addition, many studies show that chitosan has an antibacterial ability, so there is potential for the application of materials made from chitosan to antibacterial Therefore, it is necessary to study other applications of chitosan-silica aerogel composites 68 LIST OF PUBLICATIONS International journal P V Vu, T M Le, V T Tran, and P K Le, “Effects of Process Parameters on Conversion of Rice Straw-Lignin into Bio-Oil by Hydrothermal Liquefaction,” Chem Eng Trans., vol 94, pp 823–828, 2022 V T Tran, T M Le, P V Vu, H M Nguyen, Y H P Duong, and P K Le, “Depolymerization of Rice Straw Lignin into Value-Added Chemicals in SubSupercritical Ethanol,” Sci World J., vol 2022, 2022 P V Vu, T D Doan, G C Tu, N H N Do, K A Le, and P K Le, “A novel application of cellulose aerogel composites from pineapple leaf fibers and cotton waste: Removal of dyes and oil in wastewater,” J Porous Mater., vol 29(4), pp 1–11, 2022 69 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Education profile a Undergraduate (2016 – 2020) Graduated from: Ho Chi Minh City University of Technology – Vietnam National University Major: Chemical Engineering Mode of study: Full time Degree classification: Very Good b Post-graduate (2021 – Present) Currently studying Master program at Ho Chi Minh City University of Technology – Vietnam National University – Major of Chemical Engineering Working experience 03/2021 – Present: Research Engineer at Refinery & Petrochemicals Technology Research Centre, Ho Chi Minh City University of Technology – Vietnam National University 79