VIETNAM NATIONAL UNIVERSITY, HANOI VIETNAM JAPAN UNIVERSITY KARUNASENA DHANUKA NAYOMAL RESEARCH ON HYDROTHERMAL CARBONIZATION (HTC) OF PAPER MILL SLUDGE, FOOD AND FORESTRY WASTES - EFFECTS OF PROCESS PARAMETERS ON PROPERTIES OF HYDROCHAR MASTER'S THESIS VIETNAM NATIONAL UNIVERSITY, HANOI VIETNAM JAPAN UNIVERSITY KARUNASENA DHANUKA NAYOMAL RESEARCH ON HYDROTHERMAL CARBONIZATION (HTC) OF PAPER MILL SLUDGE, FOOD AND FORESTRY WASTES - EFFECTS OF PROCESS PARAMETERS ON PROPERTIES OF HYDROCHAR MAJOR: ENVIRONMENTAL ENGINEERING CODE: 8520320.01 RESEARCH SUPERVISORS: Associate Prof. CAO THE HA Dr. VU NGOC DUY Hanoi, 2021 ACKNOWLEDGMENTS The work documented in this report was only possible to achieve with the guidance, support and patience of a number of people that I have the privilege to interact and learn from. First of all, I would like to express my sincere gratitude towards Associate Professor Cao The Ha and Doctor Vu Ngoc Duy for the enthusiastic instructions and encouragement throughout this current study.
Secondly, I take this opportunity to express my gratitude to all the professors, lecturers and students at the Environmental Engineering program, VNU Vietnam Japan University for their inspiration during this project. Finally, I would like to thank my parents for their support and encouragement during this long period. Karunasena Dhanuka Nayomal TABLE OF CONTENTS LIST OF TABLES. i LIST OF FIGURES.
ii LIST OF ABBREVIATIONS .1 Hydrothermal Carbonization of Lignocellulosic Biomass. 3 CHAPTER 2 : LITERATURE REVIEW .1 Historical overview of HTC process .2 Biomass And Thermochemical Processes .2 Biomass: definition, properties, and comparison .3 Overview of HTC Process .1 Reaction mechanism of HTC with biomass .2 The role of water in HTC .3 Effect of process parameters .4 Advantages of HTC.5 Potential uses of HTC coal .6 Products of HTC. 27 CHAPTER 3 : MATERIALS AND METHODS .1 HTC applicable industries .1 Food and Beverage industry.3 Description of the HTC reactor .4 Experimental methods and principles .5 Chemical Oxygen Demand (EPA Method 410.6 Sample treatment: Moisture removal .7 Ash content and volatile matter calculation .8 Calculating gross calorific value. 49 CHAPTER 4 : RESULT AND DISCUSSION .1 Restaurant Food waste (RFW/R) hydrochar .2 Paper mill sludge (PMS/P) hydrochar .3 Saw dust (SD/ S) hydrochar .3 Characteristics of hydrochar process water .1 Restaurant food waste (RFW/ R) process water .2 Paper mill sludge (PMS/P) process water .3 Saw dust (SD/ S) process water.
89 LIST OF TABLES Table 2. Characteristics of biomass torrefaction. Characteristics of biomass pyrolysis. Characteristics of biomass gasification.
Characteristics of biomass Hydrothermal carbonization. Chemical analysis and properties of selected types of biomass (Canzana, 2011) 14 Table 2. Saturated steam table (Kruse et al. Summary of process parameters for HTC process.
Comparison of reaction conditions and product distributions (Libra et al. Distribution of the carbon fraction in the HTC product phases (Marchetti, 2012). Examples of solid yields and elementary compositions of HTC-coal from different substrates (Libra et al. Composition of the process water resulting from HTC (Robbiani, 2013).
Moisture content, Amount of dry solid Volatile, ash and Gross caloric values calculated by equation (5) of biomass feeds. Proximate analysis of biomass after the hydrothermal carbonization gross caloric values were calculated by equation (5) n = 3. Comparison of gross calorific value from the research with literature review 64 Table 4. GCVs of the feed and chosen hydrochar samples from ultimate analysis.
64 i LIST OF FIGURES Figure 1. Garbage dump in Giong Rieng district, Kien Giang province and Binh Tu landfill, Phan Thiet city, Binh Thuan province.( Ministry of Natural Resources and Environment. Differences between primary and secondary cell wall in plants. Degradation products and sub products during hydrolysis of lignocellulosic biomass (Qadariyah et al.
Comparison of different energy and carbon exploitation schemes for carbohydrates (Titrici et al. Percentage of each product in HTC process. Van Krevelen diagram (Marchetti, 2012). Correlation carbon content and calorific value for different substrates (Oliveira et al.
Food waste collecting site, Canada. Paper mill sludge, Peninsular Malaysia. Forestry waste Terrace Community Forest, Northwest British Columbia. Raw dried restaurant food waste, raw dried paper mill sludge and raw dried saw dust.
Hydrothermal carbonization reactor with Teflon inner compartment and stainless steel outer cover. Carbolite gero laboratory furnace. Calibration curve for total nitrogen. Calibration curve for total phosphorus.
Calibration curve for Chemical oxygen demand. Thermal analysis procedure for Biomass fuel (Hydrochar) Fixed solid, Ash, Volatile solid. Raw biomass feed samples and subsequent hydrochar samples. The dependence of yield of RFW hydrochar from dried food waste with temperature and time (n = 3, triplicate).
Percentages of total solid content and moisture content of RWFHC with time and temperature (n = 3, triplicate). Percentages of Volatile solid content and ash of RWFHC with time and temperature (n = 3, triplicate). Gross calorific values of RFWHC with time and temperature (n = 3, triplicate) 56 Figure 4. Percent conversion of PMS hydrochar with time and temperature (n = 3, triplicate).
Total solid content and moisture content of PMSHC with time and temperature (n = 3, triplicate). Percentages of Volatile solid content and ash of PMSHC with time and temperature (n = 3, triplicate). Gross calorific values of PMSHC with time and temperature (n = 3, triplicate) 59 Figure 4. Yield of SD hydrochar with increasing time and temperature at 220oC (n = 3, triplicate).
Total solid content and moisture content of SDHC with time and temperature at 220oC (n = 3, triplicate). Percentages of Volatile solid content and ash of SDHC with time and temperature at 220oC (n = 3, triplicate). Gross calorific values of SDHC with time and temperature at 220oC (n = 3, triplicate). pH of RFW process water with time and temperature (n = 3, triplicate).
COD of RFW process water with temperature and time (n = 3, triplicate). Electrical conductivity of restaurant food waste process water with temperature and time (n = 3, triplicate). Total nitrogen of RFW process water with temperature and time (n = 3, triplicate). Total phosphorus of RFW process water with temperature and time (n = 3, triplicate).
pH of PMS process water with temperature and time (n = 3, triplicate). Electrical conductivity of PMS process water with temperature and time (n = 3, triplicate). COD of PMS process water with temperature and time (n = 3, triplicate). Total nitrogen of PMS process water with temperature and time (n = 3, triplicate).
Total phosphorus of PMS process water with temperature and time (n = 3, triplicate). pH of SD process water with time and temperature at 220oC (n = 3, triplicate). Electrical conductivity of SD process water with time and temperature at 220oC (n = 3, triplicate). COD of SD process water with time and temperature at 220oC (n = 3, triplicate).
Total nitrogen of SD process water with time and temperature at 220oC (n = 3, triplicate). 79 iv LIST OF ABBREVIATIONS 13C-NMR: Carbon-13 Nuclear Magnetic Resonance ASTM: American Society for Testing and Materials COD: Chemical Oxygen Demand EC: Electrical Conductivity EDS: Energy Dispersive X-ray Spectroscopy FS: Fixed Solid GC-MS: Gas Chromatography–Mass Spectrometry GCV: Gross Calorific Value GHG: Greenhouse Gas HC: Hydrochar HHV: Higher Heating Value HTC: Hydrothermal Carbonization MC: Moisture Content MSW: Municipal Solid Waste NCASI: National Council for Air and Stream Improvement P/PMS: Paper mill Sludge PINI: Initial Sample of Paper mill Sludge PMSHC: Paper mill Sludge Hydrochar R/RFW: Restaurant Food Waste RFWHC: Restaurant food waste hydrochar RINI: Initial Sample of Restaurant Food Waste S/SD: Saw dust SDHC: Saw dust Hydrochar SEM: Scanning Electron Microscopy SINI: Initial Sample of Saw dust TN: Total Nitrogen TOC: Total Organic Carbon TP: Total Phosphorus US EPA: United States Environmental Protection Agency VS: Volatile Solid v CHAPTER 1 : INTRODUCTION After the Doi Moi resolution, Vietnam sees a prosperous future in its economy. The current economic boom has attracted more and more people into the cities. In 2009 according to the General Statistics Office of Vietnam, the population in urban areas was 25.59 million which accounted for 29.74% (Truong, 2018) of the total population.
However, it was forecasted that, in 2025 half of the total population of Vietnam will be living in cities which is an outcome of the improvements in people’s living standards and the impressive achievements of the economy. With this great influx, the environmental management of the cities especially with the solid waste management will turn into a dire state. When the subsequent changes in spending habits of people generate more and more solid waste, the well-being of the cities and their citizens will be endangered. According to the National State of Environment report published by Ministry of Natural Resources and Environment in 2011, the urban solid waste generation in 2003 was 6.4 million tonnes and it was increased to 12.8 million tonnes in 2008.
While the urban solid waste generation increased by more than 200% the industrial solid waste also increased by 181%. In the year 2003, the industrial solid waste generation was 2.6 million metric tonnes and in 2008 it was increased to 4. Moreover, this report predicted that there would be a 42-46 % increase in nationwide urban solid waste generation with 17% contribution from industries (DoNRE, 2011). In Hanoi, it was estimated that the daily domestic waste generation is 6,500 tons (Phan, 2019).
Domestic waste is a result of ordinary day-to-day activities. The main contributors to the generation of domestic waste are households, schools, markets, restaurants, and hotels. According to Vietnamese Department of Natural Resources and Environment in 2011, 500-700 tonnes of industrial waste, 150-200 tonnes of hazardous waste, 1500-2000 tonnes of construction and demolition waste, and 9-12 tonnes of medical waste generated per day in the city. The majority of this domestic waste consists of organic waste which 1 accounts for 40 - 55% and among them, the recyclable potion counts for 8 – 18% (DoNRE, 2011).
The land fillings are the standard practice of solid waste management in Vietnam. Around 76 – 82% of municipal solid waste is treated in landfill sites all over the country everyday (Truong, 2018). From the total number of 98 landfills and open dumping sites in the country 16 of them operate according to the regulations (Truong, 2018). The rest of the sites follow unhygienic methods which are harmful to people and the environment.
Furthermore, with ever-increasing amounts of solid waste, most of the landfill sites in large cities operate in their full capacities, and extension of the available land is difficult to achieve due to scarcity of the land in cities. Garbage dump in Giong Rieng district, Kien Giang province and Binh Tu landfill, Phan Thiet city, Binh Thuan province.( Ministry of Natural Resources and Environment. Apart from landfilling, many cities use open burning and incineration to treat solid wastes. In a few cities, open burning at the landfill site is a common method to reduce the total volume of waste.
Open burning can be seen in rural areas where there aren’t many facilities to treat or manage the waster. Burning solid waste right in their gardens is a common practice in many rural houses. However, the open burning of solid waste creates a huge health risk since it releases pollutants straight into the atmosphere. In some cities, the 2 hospital waste is treated in incinerator facilities.
Due to the lack of availability of these facilities throughout the country, most of the hospital waste ends up in landfills. In the past decade, solid waste management has undergone numerous changes. According to the sustainability approach, most of the mentioned waste management practices are considered to be outdated. Currently, the recycling and recovery of the resources are the main focus of the waste management systems throughout the world.
In that sense, the organic fraction in municipal solid waste is seen as a source of great potential.