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TITLE:
HYDROTHERMAL CARBONIZATION OF MALAYSIANS BIOMASS FOR
PRODUCTION OF COAL
PREPARED BY:
NORHANISAH BT MOHD ZAMRI
(17668)
SUPERVISOR:
DR TAZLI AZIZAN
Preliminary report submitted in partial fulfillment of the requirements for the Bachelor of
Engineering (Hons)
(Chemical Engineering)
JANUARY 2014
ABSTRACT
Hydrothermal carbonization (HTC), a thermochemical pretreatment process, is a method used to
treat biomass under hot compressed water to produce hydrochar. Oil palm residues, which are
palm trunks, palm fronds and palm shell will be used as feedstock for producing carbonaceous
hydrochar .The main purposes of this study are to investigate the effect of reaction temperature,
residence time and the type of catalyst used on HTC process. In this study, a carbon rich
products, or hydrochar is synthesized by HTC of oil palm residues, at different operating
temperatures of 180 to 340C and different residence time between 30 to 150 minutes with the
presence of citric acid or ascorbic acid as a catalyst. The conversion of raw biomass to its
hydrochar occurred via dehydration and decarboxylation. To gain a detail insight on the raw
biomass and hydrochar produced, the materials will be characterized by CHNS, FTIR and SEM
analysis. Thermal gravimetric analysis (TGA) also will be conducted to study the combustion
behavior of the raw biomass and hydrochar produced.
Table of Contents
CHAPTER 1 ................................................................................................................................................ 2
INTRODUCTION .................................................................................................................................... 2
1.1 Background of Study ...................................................................................................................... 2
1.2 Problem Statement .......................................................................................................................... 3
1.3 Objective ......................................................................................................................................... 3
1.4 Scope of Study ................................................................................................................................ 3
1.5 Relevancy of the Project ................................................................................................................. 4
1.6 Feasibility of project ....................................................................................................................... 4
CHAPTER 2 ................................................................................................................................................ 5
LITERATURE REVIEW ......................................................................................................................... 5
2.1 Biomass ........................................................................................................................................... 5
2.2 Biomass Conversion Technology ................................................................................................... 6
2.3 Hydrothermal Carbonization........................................................................................................... 7
2.4 HTC of Oil Palm Wastes .............................................................................................................. 11
CHAPTER 3 .............................................................................................................................................. 12
METHODOLOGY ................................................................................................................................. 12
3.1 Project Flowchart .......................................................................................................................... 12
3.2 Project Gantt Chart........................................................................................................................ 13
3.3 Materials ....................................................................................................................................... 13
3.4 Experimental Method.................................................................................................................... 14
3.5 Characterization of biomass and hydrochar .................................................................................. 15
CHAPTER 4 .............................................................................................................................................. 17
CONCLUSION ....................................................................................................................................... 17
REFERENCES .......................................................................................................................................... 18
CHAPTER 1
INTRODUCTION
1.1 Background of Study
Nowadays, energy demand is increasing constantly as a result of population growth and evolving
industries. According to Euan (2015), 86% of energy consumed in 2014 represented by fossil
fuels. Due to depletion of fossil fuels and its effect on environment, the search for alternative
energy sources has gained great importance. Biomass is considered as one of the renewable
energy sources with the highest potential and some of the countries in Asia have established
targets to use fuels produced from biomass to replace fossil fuels (Ong, Mahlia, & Masjuki,
2011). Substitution of fossil fuels for energy for energy production with biomass will result in a
net reduction in greenhouse gas emissions and the replacement of a non-renewable energy
source. The biomass which is consisting mainly of agricultural and forestry waste can be
regarded as a renewable energy source with potential to supply the global energy demands.
Moreover, the use of biomass contributes to reduce the greenhouse effect. There are several
methods to convert biomass into value added product and one of it is hydrothermal carbonization
(HTC). HTC process is achieved in water at low temperature basically from 150C to 350C and
the pressure is held as high as to maintain water in liquid phase for several hours(Lin et al.,
2015). According to Lin et al., during the HTC treatment of the biomass, there are series of
significant decomposition such as dehydration, decarboxylation, condensation, polymerization
and aromatization before the solid hydrochar are produced. The aim of HTC is to produce a coal
like hydrochar which are more energy dense, easily friable and more hydrophobic than starting
material(Smith, Singh, & Ross, 2016). There are a lot of benefits from HTC process such as
increased the carbon efficiency, reduced pollutant emissions and also increase the heating value
of biomass. The purposes of this project are to investigate the effects of hydrothermal
carbonization temperature, residence time and also the presence of catalyst on the hydrochar
produced from the oil palm residues.
1.3 Objective
The objectives of this project are:
i.
ii.
To determine the effect of process variable such as operating temperature, residence time
and catalyst use on hydrochar products
Operating temperature
ii.
Reaction Time
iii.
Presence of Catalyst
CHAPTER 2
LITERATURE REVIEW
2.1 Biomass
Biomass, which is mainly composed of carbon, hydrogen and oxygen, have solar energy
composed on its molecular bonds which made the biomass has high potential among the
renewable energy sources (Tekin, Karagz, & Bekta, 2014). According to Sue (2013), biomass
has always been a major source of energy for mankind, which contributed 10-15% of worldwide
energy demand. However, by 2050, nearly half of the global energy will be supplanted by
biomass as it is predicted that the world wide supply for oil reserves would be exhausted (Tekin
et al., 2014).
Biomass is commonly used as electrical or thermal energy, as fuel for transportation and as raw
materials for the production of chemicals; the applications for biomass continue to grow and are
increasing rapidly. Interest in biomass continues to grow and variety of studies has been
conducted on the use of biomass as a source for renewable energy and an alternative to fossil
fuels. There are several factors that play important roles in the selection of biomass as energy
source such as the calorific value, volatile matter content, ash content and also moisture content
(Sexena, Adhikari & Goyal, 2009).
Malaysia has tremendous biomass and wood waste resources available for immediate
exploitation. Annually, a minimum of 168 million tonnes of biomass waste is generated in
Malaysia and palm oil waste accounts for 94% of biomass feedstock while the remaining
contributors are agricultural and forestry by-products, such as wood residues (4%), rice (1%),
and sugarcane industry wastes (1%).
In 2000, Malaysia becomes worlds largest producer of palm oil by producing half of the world
palm oil production (10.8 million tonnes). Palm oil has made impressive growth in past four
decade and will be continue projected in period 2016 to 2020. Today, 4.49 million hectares of
land in Malaysia is under oil palm plantation compared to 3.31 million hectares in 1999. Table 1
shows the breakdown shows the breakdown of wastes from palm oil production in
2007(Abdullah & Sulaiman, 2013).
Wastes
Quantity (ktonnes)
Fronds
46,837
18,022
11,059
10,827
Shell
4,506
Table 1: Oil Palm Wastes
Reaction conditions
Process
Pyrolysis:
slow
Pyrolysis:
intermediate
Pyrolysis:
fast
Gasification
HTC
Temp. (C)
Vapor
residence
time
Char
Liquid
Gas
400
hour-week
35
30
35
500
10s-20s
20
50
30
500
1s
12
75
13
800
10-20s
10
85
180-250
(1- 12 h
processing
time)
50-80
5-20
(dissolved in
process
water, TOC)
2-5
Reference
Libra et al.
(2011)
There are several reaction mechanisms that occur to biomass during the HTC process such as
hydrolysis, dehydration, decarboxylation, polymerization and aromatization. Figure below show
the reaction pathways for degradation of biomass.
In HTC process, biomass is converted into a solid product called bio-char, a liquid product called
bio-oil and a gas product(Tekin et al., 2014). Biomass can be converted into a the target products
by manipulating the process variable such as reaction time, reaction temperature and also the
catalyst used, Figure 3 shows the products from the hydrothermal conversion of biomass.
Temperature
Temperature will determine the fate of degradation reactions in HTC process. High
temperature leads to extensive dehydration and an increase in the degree of condensation
of the hydrochar.
ii.
Residence time
Reaction time plays an important role in the extent of reaction and the distribution of
different types of products and their quality. Longer residence time will cause excessive
polymerization and leads to condensed products.
iii.
Use of Catalyst
Catalyst will enhance the reaction rate reduces the energy of activation for the hydrolysis
of biomass.
iv.
Substrate Concentration
Low concentration of reactants will minimize cross reaction of the involved species and a
higher reactant to water ratio will lead polymerization at shorter residence time.
Table 1 shows the example previous study of HTC on different types of biomass by
manipulating their operating parameters.
Biomass
Operating Parameters
Temperature Residence Time
Catalyst
(C)
(Min)
References
Guo, Dong, Wu,
Shi, and Zhu
(2015)
Erdogan et al.
(2015)
Corn stalk
180 - 290
480
N/A
Orange pomace
175-260
30-120
N/A
Brewers spent
grain
200-240
840
Citric acid
Poerschmann et al.
(2014)
Wheat straw,
poplar wood &
olive residues
180-230
480
Citric acid
Wiedner et al.
(2013)
Paper sludge
180-300
30
N/A
Water hyacinth
240
30-1440
N/A
Y. Gao et al.
(2013)
Eucalyptus bark
220-300
120-600
N/A
Rice husk
200-300
120-960
N/A
Kalderis et al.
(2001)
Bamboo
180-260
10
N/A
Fresh forest
residue
175-225
10-60
N/A
Primary sewage
sludge
140-200
30-240
N/A
Rapeseed husk
150-200
5-30
N/A
Cassava and
tapioca
flour
250
480
N/A
Seaweed
200&250
60
N/A
Danso-Boateng et
al. (2013)
Elaigwu &
Greenway(2016)
Biomass
Description
References
EFB
Parshetti, Kent
Hoekman, and
Balasubramanian
(2013)
EFB
Kongpanya (2014)
Palm Shell
Nizamuddin et al.
(2015)
Palm Shell
Nizamuddin et al.
(2016)
Palm leaves
Youssef et al.(2015)
11
CHAPTER 3
METHODOLOGY
3.1 Project Flowchart
Conclusion
-Conclude the experiment and
prepare report for the project.
Data Collection
-Conduct the experiment and collect the
data. Analyze the data and come out with
results and discussion.
Experiment
- Design an experiment to study the
relationship between parameters
-Prepare chemical and equipment needed for
experiment
Literature review
-Preliminary research on existing studies on the topic
from journals and books
-Understnding HTC concept
Key Milestones
12
Detail Work
1 2 3 4
Proposal defence
10 11 12 13 14
10
Process
Milestone
3.3 Materials
The oil palm residues which are the palm fronds, palm trunks and palm shells will be used as raw
materials in this research. The oil palm residues will be collected from local supplier. Then the
biomass will be grinded into small pieces ranging from 1 to 5 mm. The biomass then will be
stored in sealed container until use.
13
Run
Biomass
Palm trunk
Palm frond
Palm shell
Catalyst
Operating
Time (min)
Operating
Temperature
(C)
N/A
220
60
220
60
Citric acid
Ascorbic acid
180
220
260
9
10
11
*Plam trunk/
palm frond/
palm shell
60
300
*Citric acid/
Ascorbic acid
340
30
12
60
13
220
14
90
120
15
*Decided based on highest yield of hydrochar from Run 1-5
150
14
(1)
The elemental contents of biomass and hydrochar were determined by vario Micro cube
elemental analyzer (Elementar, Germany). The samples will be weighed around 1.5mg to 2.0 mg
in aluminium container before entering the analyzer. The equipment will evaluate the
composition of carbon, hydrogen, nitrogen and sulfur in the samples. The composition of the
oxygen will be calculated by difference method. According to Friedl, Padouvas, Rotter, and
Varmuza (2005), the value of HHV can be predicted from the elemental analysis by using the
following equation:
HHV(kJ/kg) = 3.55C2 232C -2230H + 51.2CH + 131N + 20600
(2)
where C, H and N are carbon, hydrogen and nitrogen contents of the samples. The energy yield
will be calculated by equation 3 expressed as follows:
Energy yield = (HHVhydrochar / HHVbiomass) X hydrochar mass yield
(3)
ii)
Heat from 50C to 800C at 20.00C/min with nitrogen flow rate of 20ml/min
15
From TGA profile, the moisture content, volatile matter, fixed carbon and ash of the samples will
be determined.
16
CHAPTER 4
CONCLUSION
As conclusion, this project is important as it deals with biomass which is one of alternative
energy that could be used to reduce the dependence on fossil fuels. Hydrothermal carbonization
(HTC) is believed to be one of effective ways to convert biomass into value added product which
is coal. Compared to other technique, the fact that hydrothermal carbonization takes place in an
aqueous reaction medium means that wet biomass can be used, thus eliminating any energyconsuming pre-drying steps before the HTC process. HTC process is still developing nowadays,
hence, further study and understanding of the hydrochar produced by HTC process is very
necessary.
17
REFERENCES
Abdullah, N., & Sulaim, F. (2013). The Oil Palm Wastes in Malaysia. doi: 10.5772/55302
Comparing gasification with other biomass thermal conversion alternatives (2012). Retrieved from
http://www.bioenergynet.com/articles/technology/innovation/1320-comparing-gasification-with-otherbiomass-thermal-conversion-alternatives
Danso-Boateng, E., Holdich, R. G., Shama, G., Wheatley, A. D., Sohail, M., & Martin, S. J. (2013).
Kinetics of faecal biomass hydrothermal carbonisation for hydrochar production. Applied Energy,
111, 351-357. doi: 10.1016/j.apenergy.2013.04.090
Erdogan, E., Atila, B., Mumme, J., Reza, M. T., Toptas, A., Elibol, M., & Yanik, J. (2015).
Characterization of products from hydrothermal carbonization of orange pomace including
anaerobic digestibility of process liquor. Bioresour Technol, 196, 35-42. doi:
10.1016/j.biortech.2015.06.115
Euan Mearns (2015, June 12). Global Energy Trends BP Statistical Review 2015. Retrieved June 11,
2016 from http://euanmearns.com/global-energy-trends-bp-statistical-review-2015/
Friedl, A., Padouvas, E., Rotter, H., & Varmuza, K. (2005). Prediction of heating values of biomass fuel
from elemental composition. Analytica Chimica Acta, 544(1-2), 191-198. doi:
10.1016/j.aca.2005.01.041
Gao, P., Zhou, Y., Meng, F., Zhang, Y., Liu, Z., Zhang, W., & Xue, G. (2016). Preparation and
characterization of hydrochar from waste eucalyptus bark by hydrothermal carbonization. Energy,
97, 238-245. doi: 10.1016/j.energy.2015.12.123
Gao, Y., Wang, X., Wang, J., Li, X., Cheng, J., Yang, H., & Chen, H. (2013). Effect of residence time on
chemical and structural properties of hydrochar obtained by hydrothermal carbonization of water
hyacinth. Energy, 58, 376-383. doi: 10.1016/j.energy.2013.06.023
Guo, S., Dong, X., Wu, T., Shi, F., & Zhu, C. (2015). Characteristic evolution of hydrochar from
hydrothermal carbonization of corn stalk. Journal of Analytical and Applied Pyrolysis, 116, 1-9.
doi: 10.1016/j.jaap.2015.10.015
Jain, A., Balasubramanian, R., & Srinivasan, M. P. (2016). Hydrothermal conversion of biomass waste to
activated carbon with high porosity: A review. Chemical Engineering Journal, 283, 789-805. doi:
10.1016/j.cej.2015.08.014
Kongpanya. (2014). Influence of Reaction Temperature and Reaction Time on Product from
Hydrothermal Treatment of Biomass Residue. American Journal of Environmental Sciences,
10(4), 324-335. doi: 10.3844/ajessp.2014.324.335
Lin, Y., Ma, X., Peng, X., Hu, S., Yu, Z., & Fang, S. (2015). Effect of hydrothermal carbonization
temperature on combustion behavior of hydrochar fuel from paper sludge. Applied Thermal
Engineering, 91, 574-582. doi: 10.1016/j.applthermaleng.2015.08.064
N. Abdullah and F. Sulaiman (2013). The Oil Palm Wastes in Malaysia, Biomass Now - Sustainable
Growth and Use, Dr. Miodrag Darko Matovic (Ed.), InTech, DOI: 10.5772/55302. Available
from: http://www.intechopen.com/books/biomass-now-sustainable-growth-and-use/the-oil-palmwastes-in-malaysia
Nizamuddin, S., Jayakumar, N. S., Sahu, J. N., Ganesan, P., Bhutto, A. W., & Mubarak, N. M. (2015).
Hydrothermal carbonization of oil palm shell. Korean Journal of Chemical Engineering, 32(9),
1789-1797. doi: 10.1007/s11814-014-0376-9
Nizamuddin, S., Mubarak, N. M., Tiripathi, M., Jayakumar, N. S., Sahu, J. N., & Ganesan, P. (2016).
Chemical, dielectric and structural characterization of optimized hydrochar produced from
hydrothermal carbonization of palm shell. Fuel, 163, 88-97. doi: 10.1016/j.fuel.2015.08.057
Ong, H. C., Mahlia, T. M. I., & Masjuki, H. H. (2011). A review on energy scenario and sustainable
energy in Malaysia. Renewable and Sustainable Energy Reviews, 15(1), 639-647. doi:
10.1016/j.rser.2010.09.043
18
Pari, G., Darmawan, S., & Prihandoko, B. (2014). Porous Carbon Spheres from Hydrothermal
Carbonization and KOH Activation on Cassava and Tapioca Flour Raw Material. Procedia
Environmental Sciences, 20, 342-351. doi: 10.1016/j.proenv.2014.03.043
Parshetti, G. K., Kent Hoekman, S., & Balasubramanian, R. (2013). Chemical, structural and combustion
characteristics of carbonaceous products obtained by hydrothermal carbonization of palm empty
fruit bunches. Bioresour Technol, 135, 683-689. doi: 10.1016/j.biortech.2012.09.042
Poerschmann, J., Weiner, B., Wedwitschka, H., Baskyr, I., Koehler, R., & Kopinke, F. D. (2014).
Characterization of biocoals and dissolved organic matter phases obtained upon hydrothermal
carbonization of brewer's spent grain. Bioresour Technol, 164, 162-169. doi:
10.1016/j.biortech.2014.04.052
Reza, M. T., Andert, J., Wirth, B., Busch, D., Pielert, J., Lynam, J. G., & Mumme, J. (2014).
Hydrothermal Carbonization of Biomass for Energy and Crop Production. Applied Bioenergy,
1(1). doi: 10.2478/apbi-2014-0001
SaxenaRC,AdhikariDK,GoyalHB.Biomass-basedenergyfuelthrough biochemical
routes:areview.RenewSustainEnergyRev2009;13:16778.
Smith, A. M., & Ross, A. B. (2016). Production of bio-coal, bio-methane and fertilizer from seaweed via
hydrothermal carbonisation. Algal Research, 16, 1-11. doi: 10.1016/j.algal.2016.02.026
Smith, A. M., Singh, S., & Ross, A. B. (2016). Fate of inorganic material during hydrothermal
carbonisation of biomass: Influence of feedstock on combustion behaviour of hydrochar. Fuel,
169, 135-145. doi: 10.1016/j.fuel.2015.12.006
Sue R.S (2013, September 2013). IEA Task40: Biomass provides 10 percent of global energy use.
Retrieved June 11, 2016 from http://biomassmagazine.com/articles/9444/iea-task40-biomassprovides-10-percent-of-global-energy-use
Tekin, K., Karagz, S., & Bekta, S. (2014). A review of hydrothermal biomass processing. Renewable
and Sustainable Energy Reviews, 40, 673-687. doi: 10.1016/j.rser.2014.07.216
Titirici, M.-M., Funke, A., & Kruse, A. (2015). Hydrothermal Carbonization of Biomass. 325-352. doi:
10.1016/b978-0-444-63289-0.00012-0
Wiedner, K., Naisse, C., Rumpel, C., Pozzi, A., Wieczorek, P., & Glaser, B. (2013). Chemical
modification of biomass residues during hydrothermal carbonization What makes the
difference, temperature or feedstock? Organic Geochemistry, 54, 91-100. doi:
10.1016/j.orggeochem.2012.10.006
19