University of Nevada, Reno Upgrading Biomass by Hydrothermal and Chemical Conditioning A dissertation submitted in partial fulfillment of the requirements for the Doctor of Philosophy in Chemical Engineering By Mohammad Toufiqur Reza Dr. Charles J. Coronella/ Dissertation Advisor May, 2013 i Upgrading Biomass by Hydrothermal and Chemical Conditioning Abstract There are two widely known thermal pretreatment technologies, known as hydrothermal carbonization and dry torrefaction. In dry torrefaction, also known as torrefaction or mild pyrolysis, dry solid biomass is treated in an inert gas environment in a temperature range of 200-300oC for more than one hour. In hydrothermal carbonization (HTC), also known as wet torrefaction, biomass is treated with hot compressed subcritical water (200-260oC) for 5 min-8 h. The solid product, HTC biochar, contains about 55-90% of the mass and 80-95% of the fuel value of the original feedstock. The HTC process takes any wet waste biomass and converts it to a homogenized, friable, hydrophobic, and, mass and energy densified HTC biochar similar to lignite coal. Subcritical water, the temperature between 180-280 °C has ionic strength much higher than water under ambient condition. Hemicellulose hydrolysis occurs at temperatures as low as 180 °C, while cellulose hydrolysis starts around 220-230 °C. Many monomers, aldehydes, and intermediates are produced as a result of hydrolysis of biomass. Reactive intermediate species promote chemical reactions such as decarboxylation, dehydration, aromatization, and condensation-polymerization in the presence of subcritical water. As a result of these reactions, complete degradation of hemicellulose and partial degradation of cellulose was observed in the solid phase. Some carbon-rich cross-linked hydrophobic polymers are produced from the cellulose ii hydrolyzed intermediates. Van Soest fiber analysis is incapable of distinguishing those new cellulose-derived polymers from naturally present lignin. Slagging and fouling are two major problems that result from biomass combustion or co-firing with coal, especially for the biomass with high inorganic content. HTC provides biochar with the slagging and fouling indices which will predict slagging and fouling, regardless of the biomass type, primarily due to reduced chlorine content. Hot compressed water leaches both loose soil and a major portion of structural minerals in biomass by degrading its constituents during HTC. Up to 90% of calcium, magnesium, sulfur, phosphorus, and potassium were removed at low temperature HTC (200 °C). All heavy metals were reduced by HTC treatment, which opens the door to use HTC biochar as soil amendment. However, HTC still might not be appropriate for some specific thermochemical and biochemical conversion processes as the remaining ash can inhibit these processes. Many biochemical processes require hemicellulose and cellulose, while HTC degrades them, even at its minimum severity. However, an effective chelating agent like sodium citrate can preserve the organic carbohydrate fractions, while effectively dissolving metals. More than 75% structural and 85% whole ash was reduced by treatment with 0.1 of g sodium citrate per gram of raw dry corn stover at mild conditions. FTIR analysis demonstrated that the main components like lignin, cellulose and hemicellulose were unaffected by sodium citrate chelation. HTC biochar exhibits the glass transition at 140 °C and thus can be used as a binder to make durable pellets from raw biomass or even from torrefied biochar. Although torrefied biochar shows similar energy value and hydrophobicity, it is quite iii different than HTC biochar. Torrefied biochar pellets have poor durability compared to pellets of HTC biochar or even raw biomass pellets. Engineered pellets, the pellets of a mixture of torrefied and HTC biochar, are denser, more hydrophobic and durable than torrefied biochar pellets. HTC biochar was found very effective in making solid bridges among the torrefied biochar. The engineered pellets' durability is increased with increasing HTC biochar fraction. Water in subcritical condition is also effective in conversion of digested sludge. A liquid bio-oil type fuel product was discovered from the hydrothermal treatment of sludge (HTS). The HTS biosolid has higher energy value and ash than raw sludge. Moreover, the dewaterability can be increased greatly by treating waste water sludge with subcritical water. iv Acknowledgments First of all, I would like to express my sincere gratitude to my advisor Dr. Charles J. Coronella, for his continued guidance, discussion, motivation, and support during my research works. It would have been impossible for me to complete this work without his mentoring and moral supports. I would like to express my sincere thanks to the committee members, Dr. Victor R. Vasquez, Dr. Kent Hoekman, Dr. Hongfei Lin, and Dr. Glenn Miller for their valuable comments and suggestions. Special thanks to Ms. Joan G. Lynam, and M. Helal Uddin, the two most helpful persons in University of Nevada Reno (UNR), for their enormous invaluable supports on my research, discussions, and collaborative studies. They have provided a lot of technical suggestions, personal encouragements, emotional and moral supports. It would have been impossible without their supports. My research group Tapas C. Acharjee, Cody Wagner, Mike Matheus, Jason Hastings, Kevin Schmidt, Cody Niggemeyer, Alexander York, David Graves, and Chris Moore need special appreciation for their assistance and creating a joyful environment in the laboratory. Dr. Alan Fuchs research group has been always supportive and accommodating. Thanks to Joko Sustrino and Irawan Paramudiya for their support in analytical measurements. Dr. Qizhen Li is been very generous to me. I used some of her analytical instruments and her valuable advice has been very helpful. v Dr. Subramanyan Ravi‟s lab has been always resourceful and his group is always helpful. Special thanks to Dr. Bratindra Mukharjee, Swagotom Sarker, and York R. Smith for their invaluable support in analytical instrumentation. My parents deserve credit for all my achievements. They have supported me whole heartedly in all my endeavors. Special thanks to Ms. Eriko Mukaibo to support me and stay besides me in all my hard times. She has been my source of inspiration throughout my research. Thanks to my brothers and entire family member for their love and support. Finally, I want to thank the US Department of Energy for their financial support. I gratefully acknowledge meaningful discussions with Larry Felix, and Dr. Wei Yan from the Gas Technology Institute (GTI), Dr. Garold Gresham, and Rachel Emerson from the Idaho National Laboratory (INL). vi Content Abstract i Acknowledgements iv List of Figures xiii List of Tables xvi Chapter 1: Introduction 1 1.1 Biomass as energy source 1 1.2 Energy crisis and administrative strategies of USA 2 1.3 Biomass versus fossil fuel 5 1.4 Lignocellulosic biomass 8 1.4.1 Cell wall structure 9 1.4.2 Chemical structure 10 1.4.2.1 Cellulose 11 1.4.2.2 Hemicellulose 13 1.4.2.3 Lignin 14 1.4.2.4 Water extractives 16 1.5 Conversion routes for fuel production from biomass 16 1.5.1 Conversion of dry biomass 17 1.5.2 Conversion of wet biomass 18 1.6 Benefits of biomass pretreatment 20 1.6.1 Torrefaction 21 1.6.2 Hydrothermal carbonization (HTC) 22 vii 1.7 Properties of subcritical water 25 1.8 Project Objective 27 1.9 Organization of Dissertation 29 1.10 References 32 Chapter 2: Prior studies on HTC 41 2.1 History of HTC development 42 2.2 HTC of various feedstocks 46 2.2.1 Effects of process variables 46 2.2.1.1 Temperature effects on HTC 48 2.2.1.2 SEM images of HTC biochar 52 2.2.1.3 Ultimate analysis 55 2.3 Reaction kinetics of HTC for short reaction time 57 2.3.1 Novel two-chamber kinetic reactor 58 2.3.2 Kinetic results 61 2.3.3 Kinetic model for HTC 64 2.3.4 Kinetic parameters of HTC 66 2.4 Pelletization of HTC biochar 68 2.4.1 Glass transition behavior of HTC biochar 69 2.4.2 Mass and energy density of HTC biochar pellets 71 2.4.3 Mechanical strength of HTC biochar pellets 73 2.3.4 EMC of HTC biochar pellets 77 2.5 References 80 Chapter 3: Reaction Chemistry of Hydrothermal Carbonization 87 viii 3.1 Introduction 88 3.2 Materials and methods 92 3.2.1 Biomass and chemicals 92 3.2.2 Hydrothermal carbonization 92 3.2.3 Fiber analysis 93 3.2.4 Ultimate analysis 93 3.2.5 ATR-FTIR 94 3.2.6 Higher heating value 94 3.2.7 Aqueous sample analysis 95 3.3 Results and Discussion 96 3.3.1 Fiber and ultimate analysis of HTC 96 3.3.2 Reaction mechanisms 98 3.3.2.1 Hydrolysis 100 3.3.2.2 Dehydration 105 3.3.2.3 Decarboxylation 106 3.3.2.4 Condensation- Polymerization 107 3.3.2.5 Aromatization 108 3.4 Conclusions 109 3.5 References 110 Chapter 4: Inorganic Analysis of HTC Biochar 115 4.1 Introduction 116 4.2 Materials and methods 119 4.2.1 Biomass 119 ix 4.2.2 Hydrothermal carbonization 120 4.2.3 Analyses 121 4.2.3.1 ICP-AES analysis 121 4.2.3.2 Higher heating value 121 4.2.3.3 Ash measurement 122 4.2.3.4 Fiber analysis 122 4.2.3.5 SEM-EDX 122 4.3 Results and Discussion 123 4.3.1 Fiber analysis of HTC biochar 123 4.3.2 Mass yield and energy value of HTC biochar 126 4.3.3 Ash yield of HTC biochar 128 4.3.4 Inorganic analysis of HTC biochar 129 4.3.5 Heavy metal analysis of HTC biochar 133 4.3.6 Ash analysis of HTC biochar 135 4.4 Conclusions 137 4.5 References 139 Chapter 5: Chemical Demineralization of Corn Stover 144 5.1 Introduction 145 5.2 Materials and methods 148 5.2.1 Biomass 148 5.2.2 Experimental procedure